Mineev Samokhin Ocr PDF

Introduction to
Unconventional
Superconductivity
V. P. Mineev
and
K. V. Samokhin
Gordon and Breach Science Publishers

Introduction to Unconventional Superconductivity
Introduction to Unconventional Superconductivity
V. P. Mineev
L. D. Landau Institute of Theoretical Physics
Moscow, Russia
and
K. V. Samokhin
Cavendish Laboratory
University of Cambridge, UK
Translated from the Russian by A. V. Malyavkin
GORDON AND BREACH SCIENCE PUBLISHERS

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Originally published in Russian in 1998 as BBEJ[IEHWE B TEOPMIO HEOBbIYHOM

CBEPXTIPOBOJJUMOCTIH by MFTI, Moscow.
© 1998 MFTI.
No part of this book may be reproduced or utilized in any form or by any means,
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storage orretrieval system, without permission in writing from the publisher. Printed in
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ISBN: 90-5699-209-0
Coverillustration by Liouba Mineeva.

Contents
Preface 2. ee eee eee ee eens vii
Cooper Pairing ©... ee ne eee
Spin Structure of Paired States ....... ee cee ee eee
Phases of Superfluid Helium-3 2.2.2.0... ee eee 13
Superconducting States in Crystals... 6... eee 17
Energy of Elementary Excitations in Superconductors .............. 29
Gap in the Spectrum of Elementary Excitations and Critical Temperature . 37
Temperature Dependence of Thermodynamic Quantities forT—-+0O .....
Effects of Electron NumberParity in Superconductors .............. 47
Paramagnetic Susceptibility and Knight Shift .................44. 55
10 Landau Expansion of Superconductor Free Energy. ............0005. 61
11 Superconducting States with Multicomponent Order Parameters........ 67
12 Ginzburg-Landau Equations and Upper Critical Field. .............. 73

vi CONTENTS
13 Boundary Conditions and Surface Superconductivity.............00. 83
14 Meissner and Mixed States in Unconventional Superconductors ....... 93
15 Magnetic Superconductors ....... 0.0... ee es 103
16 Josephson Effect... 0... ee te ene lil
PartIT .............. .. 117
17 Gor’kov Equations. 6... ene 119
18 Ginzburg-Landau Functional..................0.. . 129
19 Upper Critical Field in a p-wave Superconductor ................. 137
20 Boundary Conditions for the Order Parameter ............. oe 147
21 Effect of Impurities on Unconventional Superconductivity ........... 159
22 Electronic Thermal Conductivity of Unconventional Superconductors . . 171
References 6... eee eee teens 185
Index ........ Le 189

Preface
This book is based on a course of lectures devoted to conventional and unconventional

superconductivity read by one ofthe authors (V. P. Mineev) to students at the Moscow
Institute of Physics and Technologyfor several years. Although the term ‘unconventional
superconductivity’ has been in use for a relatively short period,the start of intense studies
of this phenomenon dates back to the 1970s. This research was prompted by the dis-
covery of the superfluidity of liquid helium-3, some of whose properties are very similar
to those of unconventional superconductors. The point is that liquid helium-3, which in
the normal state is an isotropic Fermi-liquid, transforms at temperatures below the
superfluid phase transition to a liquid crystal, i.e. a material with anisotropic mechanical
and magnetic properties. Spontaneous magnetisation also occurs in superfluid phases A
and A, of He. Thus, in addition to the specific phase coherence in a macroscopic
ensemble of fermions, which givesrise to non-dissipative currents in superfluid helium-3,
spatial and magnetic ordering occursafterits transition to the superfluid state. The type of
superconductivity characterised by similar additional symmetry breakings is termed
unconventional superconductivity.
Recentprogress in the theory of unconventional superconductivity has been stimulated
by the experimental discoveries of high-temperature superconductivity and super-
conductivity in heavy-fermion materials. This book presents the fundamentals of the
macroscopic physics and microscopic theory of unconventional superconductivity. It can
be used as an introduction to the modern theory of superconductivity for both studentsin
physics and experienced researchers. It is desirable that the reader should be familiar with
the standard theory of superconductivity with s-wave pairing (see the widely known
books[1, 2, 3]). On the other hand, manyresults of conventional superconductivity theory
are given in the text in juxtaposition with the respective results of the theory of un-
conventional superconductors. For pedagogical reasons, we have decidedto analyse first
the simplest case of an isotropic Fermi-liquid with anisotropic pairing and then consider
the case of non-trivial anisotropic superconductivity in crystals.
vii
viii PREFACE
The bookconsists of two parts. Thefirst is an elementary introduction to the physics of

unconventional superconductivity. The mathematical techniques utilised in this section
extensively use the method of second quantisation and the usual symmetry considera-
tions. This section describes the classification of unconventional superconductingstates,
calculation of the spectrum of elementary excitations, the Landau expansion of free
energy, thermodynamicproperties, and those of spatially non-uniform problemsthat can
be solved using the macroscopic approach (Ginzburg—Landau—Abrikosovtheory).
The second part of the book describes those sections of the unconventional super-
conductivity theory which require more sophisticated mathematical techniques based on
Green’s functions. They include boundary problems, impurity effects, kinetic phenomena
etc. The second part demands from the reader a good command of the quantum field
theory methodsin the context of their applicationsto statistical physics (see, for example,
the monograph by Abrikosovet al. [4]).
Although such a two-tier structure of the book may be far from perfect from the
viewpointofits integrity, it allows a wider range of readers to study the fundamentals of
the physics of unconventional superconductivity.
We are indebted to G. E. Volovik, L. P. Gor’kov, Yu. S. Barash, E. Ya. Sherman, and
V. L. Ginzburg for reading the manuscript, and numerous constructive remarks. We are
particularly grateful to Tolya Svidzinskii, who checked calculations in the last two sec-
tions of the book and put forth someessential corrections. We also thank G. D. Bulanova
and M. G. Vavilov for help in compiling the original manuscript of the book.
Literature
1. J. R. Schrieffer, Theory of Superconductivity, Benjamin W. A. Inc.; New York (1964).

2. P. G. de Gennes, Superconductivity of Metals and Alloys, W. A. Benjamin Inc.; New
York—Amsterdam (1966).
3. A. A. Abrikosov, Fundamentals of the Theory of Metals, Elsevier Science Publisher;
B.V. (1988).
4. A. A. Abrikosovy,L. P. Gor’kov, and I. P. Dzyaloshinskii, Methods of Quantum Field
Theory in Statistical Physics, Prentice-Hall; Englewood Cliffs, NJ (1963).
Part I
1 Cooper Pairing
Superconductivity, i.e. the complete disappearanceof dc electric resistivity of a material,

has been detected in many metals at sufficiently low temperatures. Superconductivity can
be also treated as superfluidity, ie. vanishing viscosity of liquids composed of conducting
electrons. Similar phenomena take place in other quantum liquids, such as superfluid “He
and *He, nuclear matter, and neutronstars.
Thestart of theoretical research in superfluid Fermi-liquids dates back to 1957, when
J. Bardeen, L. Cooper, and J. Schrieffer [1] created the theory of superconductivity
(hereafter labeled as the BCS theory). This theory is based on Cooper’s theorem about
instability of the ground state of an electron gas with an arbitrarily small attraction
between its particles against formation of boundstates, namely, electron pairs. In most
superconductors, the attraction between electrons which is stronger than their direct
Coulomb repulsion is due to interaction between electrons and vibrations of the crystal
lattice (phonons). This interaction generates an excess of positive charge around an
electron. Theattractive interaction is almost isotropic, so that Cooper pairs are formed in
a state’ with zero orbital angular momentum (s-wave pairing). The situation is quite
different in superfluid *He, where Cooper pairing is due to the interaction between
nuclear spins of helium-3 atoms and fluctuations of the liquid magnetisation (para-
magnons). The interaction mediated by paramagnonsis essentially anisotropic and leads
to formation of Cooperpairs with orbital angular momentum L = 1 (p-wave pairing).
Althoughthe nature of attraction between particles may vary considerably, the Cooper
pairing is a common mechanism responsible for formation of superfluid states in various
Fermi-systems. Following Cooper[2], let us consider the quantum-mechanical problem
of two electrons in a normal metal at zero temperature. Suppose that two electrons
interact via the potential V(r; — rz) independentof their spins, and the presenceof other-
electrons, which occupyall the states below the Fermi level, manifests itself only through
Pauli’s exclusion principle (Figure 1.1). In order to determine the energy levels and wave
functions w(r),r2) of the electron pair, we have to solve the Schrodinger equation
4 INTRODUCTION TO UNCONVENTIONAL SUPERCONDUCTIVITY
FIGURE 1.1 Two electrons with oppositely directed momenta above the Fermi sphere.
2 2 j-2
-5(V} + V5)0(r1, 12) + V(r — r2)%(r1,02) = (a +8) wets) (1.1)
where A is the energy of an electron pair measured with respect to the energy of two
decoupled electrons, i.e. twice the Fermi energy, Whkz/m. ,
From the electron coordinates r) and r2 we can go overto the coordinates ofthe center
of inertia, R = (r; + r2)/2, and ofthe relative motion, r =r; — ro. If the center
of mass
is assumedto beatrest, in other words, if the electrons have opposite momenta k and —k,
the coordinate R in the wave function 7) can be omitted, and the Schrédinger equation
transforms to
_PPye) + V(r)d(r) = (4 + “Ht (1.2)

m Or? m
In the momentum representation of the wave function,
a) = f areye), (1.3)
we obtain
i Bk! NAN hk
alk) + / Om V(k —k')g(k’ ) = (a + =) g(k). (1.4)
The interaction potential
V(k—k') = / Br ek Y(p), (1.5)

which is a function of the momentum direction:
V(k—K!) = S°Vi(k,k!) 37 YinYE,(R'),

oo ]
i=0 m=—l
(1.6)
COOPER PAIRING 5
is assumed to be attractive within a thin layer over the Fermi surface of thickness
E. Xp = WK/2m:
Vi(k, k’) — —V;,l fore F < HE

2m > WE
2m cepte
F ! (1.7)
0, outside the interval (€p, €p + €7).
Here Vip, (ik) are the spherical harmonics with the orbital angular momentum / and its
z-projections m, and k = k/kp.
Let us replace, as usual, the integration over the wave vector in equation (1.4) by
integration over the energy € = fi°k2/2m — ep and the angles defining the direction of k
according to the rule:
[eho-male
3k
0
where
m kp
0= Qh? (1.9)
is the density of states at the Fermi level per one electron spin projection. We have
(Fe) het
-»/« [%oy » Yim(k)Y},(k’)g(k') = 0. (1.10)
m=—l
Onecan easily verify that each value of the orbital angular momentum correspondsto a
specific eigenstate {g;(k), A;} determined by equation (1.10). Indeed, by substituting the
expansion
u
g(k) = gi(k) = S Am (k) Yim (is),

mix fi
in equation (1.10) and using the orthonormality property of the spherical functions
dQ! a A
(1.11)
Ie im (K VY pm (kK) = bubmms
we obtain
El
NoV; / dé g)(k) = 0.
{fw —kp)- A} el) —
0
Hence
gi(k) =
NoVi
|
2E-A,
d& gi(k)
(1.12)
Byintegrating the left-hand andright-hand sides of this equation over £, we get
iadé 8 Mov),
= vom [ay Oy2
1- =
n —&
Hence, given that the interaction is sufficiently weak, NoV; < 1, we find
2
A; = —2¢; exp( a) (1.13)
Thus, a boundstate whose energy is a function ofthe orbital angular momentum occurs in
the case of an arbitrarily weak interaction between two electrons.
This assertion, which has been proved for the case of two electrons, also applies to
many-electron systems (see Section 6). In particular, the superconducting states due to
Cooper pairing with different orbital angular momenta have differentcritical temperat-
ures. The ‘superconducting states
i
Bi(K) = S> din(k)¥im(K) (1.14)
m=-l
with a given / but different sets of the coefficients aj, (k) have equalcritical temperatures.
At a given temperature andpressure, the most energetically favourable state among them
is realised.
Cooper pair dimension .
The characteristic interval 6k in which the coefficients ajp (k) are non-zero is related to
the characteristic dimension £) of the wave function in the coordinate space, i.e., the
Cooper pair dimension, through the uncertainty principle: 96k > 1.! The uncertainty in
the wavevector 6k can beestimated using the pair binding energy:
i
Aw ben rok ~~ hupok.
Hence follows
foe.
hup
(1.15)
! The exact expression 9 = fivg/2nT, for the Cooper pair dimension will be derived in Section
18.
COOPER PAIRING 7
The instability of a normal Fermi gas against Cooper pairing should, apparently, manifest
itself at a temperature T, ~ A. The Fermi velocity is derived from the mean separation
between nearest fermions n~'/3, where n is the electron density, using the formula
ug ~ fin'/3 /m. In conventional superconductors, the critical temperature T, is usually
several kelvins and the electron effective mass is roughly equalto the electron mass in the
vacuum, hence £) + 10~5 cm. In He,the critical temperature is lower by three orders of
magnitude, but, on the other hand, the mass of 3He atomsis larger than the electron mass
by a factor of several thousand, so that ) ~ 10~° cm. In heavy-fermion superconductors,
the effective mass of electrons is 10 to 100 times larger than the electron mass in vacuum,
and in high-temperature superconductors, T, is several tens of degrees or even higher than
100 K, therefore & ~ 1077—10~® cm in these materials.
In all cases listed above, £) > n—'/3, i,.e., Cooper pairs cannot be treated as isolated
composite particles, and the problem of formation of the superconducting state is
essentially a many-body problem.
2 Spin Structure of Paired States
In all Fermi superfluids known at the present time, Cooper pairs are composed of par-
ticles with spin 1/2. The spin componentof a pair wave function can be characterised by
its total spin 5 = 0 (singlet) or S = 1 (triplet), it can also be a superposition of these two
states. The latter option is ruled out in superconducting materials with a definite spatial
parity. It is convenient to consider this issue for the superconducting states with definite
orbital angular momenta.
The orbital wave function given by equation (1.14) is even for even values of orbital
angular momentum / and odd for odd values of 1:
gi(—k) = (—1)!g1(k). (2.1)

At the same time, according to Pauli’s exclusion principle, the total wave function of a
pair expressed in the form ofa productlike g(k)x12, where x12 is the spin componentof
the wave function of particles 1 and 2, should changeits sign after their permutation:
. g(—k)x21 = —g(k)x12. (2.2)

It follows from equations (2.1) and (2.2) that the spin componentof a paired state with
even (odd) orbital angular momentum / should be antisymmetric (symmetric) under the
permutation of particles.
Spin wave functions of a pair of particles with spin 1/2 are constructed from the one-
particle spin wave functions
a= (4) =I") and a (9) =!

which are eigenstates of the operators s” and s,:
Afi 0 A h
6=5(4 *): S20) = 5 OAs SB, = ~5 Pd.
The eigenfunction corresponding to the spin-singlet state of a pair, in which S = 0 and

S, = 0 (where S = s; + 82), and is antisymmetric with respectto the particle permutation,
has the form
OB, ~~ BinO2, = a) ~~ | Lf) = (5, 0) = idy,
i.e., it is expressed in terms of the Pauli matrix oy. As a result, the total wave function of
a pair with S = 0 takes the form
Woaic = k)ioy = > im Yim((k)ioy, (2.3)

m=—l
where / takes the values 0,2,4,.... The respective pair states are labeled, as is traditional
in the atomic physics, byletters s,d,g,....
The complex coefficients a), in equation (2.3), same for all Cooper pairs of a given
superconducting state, represent the superconductor order parameter. In non-uniform
states the order parameter depends on the coordinates, i.e., a),, are functions of r. For
example, the order parameter for a s-wave superconductor is expressed by a single
complex function
aoo(r) = W(r) = |dle’*, (2.4)

whereas in a d-wave superconductor (J = 2) the order parameter includes five complex
functions.
In the case of the triplet state of a pair (S = 1), the wave functions correspondingto the
three different spin projections on the quantisation axis, which are symmetric under the
particle permutation can be written as
1, anor =|11)= (4 3)
S,=< 0, anPay + Brraay = It) +111) = (4

0)
-1, Pirbe, = 11) = (4 ty)
i.e. they are symmetric matrices. The total wave function ofa pair is a linear combination
of these states:
gi(k) go(k) ). (2.5)

Woair = gi(k)| tT) + g2(k)(| TL) + |!
T)) + g3(k)| 11) = (2% g3(k)
! Let us recall the definition of the Pauli matrices:
(0 1 _ (0 -i _f1 0
*=\1 0) 2 li of %=lo 1):
SPIN STRUCTURE OF PAIRED STATES il
Here
8a(k) = > Ain Yin (kk (2.6)

m=-—l
are the amplitudes of states with S, = 1, 0, and —1, respectively.

The quantum number/ in equation (2.6) can be equal to 1,3,.... The respective states
are called p,f,...-wave superconducting states. Another form of equation (2.5) is ob-
tained using the basis of the symmetric matrices iooy = (io,oy, iayoy, io,cy). We have
Wrair ~
= i(d(k )oa:
Oy = (d-(k) ox + d,(k)oy + d,(k)a;)ioy
_ (a tidj(k) (Xk) ) (2.7)

d,(k) d,(k) + id,(k)
The components of the vector d(k), which are linearly related to the amplitudes g,.(k)
through the equalities
gi=—d,+idy go=d, 93> d, + idy,
can be expanded in terms of the spherical harmonics:

!
k) = So p,m (I). (2.8)
m=-l
The coefficients b#, play the role of the order parameter in a superconductor with a
particular type of pairing, i.e. with a given value of quantum number/. So, in the simplest
case of p-wave pairing, the order parameter is expressed as a set of nine complex
functions bf, (m = --1,0, 1).
Exercise
Using expression (2.7) for the spin wave function of the triplet state, derive the formulas
for
(a) the expectation value of the spin of a pair:
= ih in [ —
Tard
dQ.
d*(k) x d(k);
atk) (2.9)
2.
(b) the expectation value of the orbital momentum ofa pair:
L- in | a d*(k) (X x x) d(k). (2.10)

3 Phases of Superfluid Helium-3
The spherical harmonics Yin (k) with 1 = 1 can be expressed as linear functions of the
vector k,
Yii(k) ~ k, + iky,
Yi1(k) ~ & — ky, Yio(It) ~ &,
which allows one to write the vector d in a different form:
da(k) © Agikj. (3.1)

The complex 3 x 3 matrix Ag; is the order parameter in superfluid p-wave Fermi liquids.
This is the type of pairing which takes place in superfluid *He [3-6], whose phase
diagram is given in Figure 3.1.
The vector d in equation (3.1) is a function of the vector k in a certain fixed reference
frame. Given that the componentsof the vectors d and k after three-dimensionalrotations
RS and R° in the spin and orbital (coordinate) spaces are expressed as linear functions of
their components before rotation, i.e.,
we can express the order parameter in an arbitrary reference frame.

Below welist the possible phases of a superfluid p-wave liquid distinguished by the
configurations of the spin vector d (or matrix Agi).
B-phase:
d(k) ~ k, (3.2)
13
,aim A 3He-A
P H, kOe Y
6
4
40 3
Melting line
30 vHe-A
3He-B 3
20r Normal ~He
Fermiliquid
10+ Te
1 J J >
1 2 3 T,mK
FIGURE 3.1 Phase diagram of liquid helium-3 plotted in the coordinates: temperature 7 (mK); pressure P
(atm.); magnetic field H (kOe).
ie. Ag; ~ Si (in an arbitrary reference frame Ag; ~ Rai, where R is the matrix of three-
dimensional rotations). The pair wave function (2.7) takes the form
ye. ~ —k.+ik,
. . kZz .
™ ( k, wea)
= (—ky +tky)| 11) + (111) + LLDD) + he + thy) LL). (3.3)
Thus, the B-phase is described by a linear combination of three equiprobable states
|S, = +1,m = —1), |S, = 0,m = 0), and |S, = —1,m= +1).
There are two other phases which incorporate some states of the B-phase.
Planar phase:
d(k) ~ (&,&, 0), (3.4)

whence follows
Whair ~ (kee + thy)| 11)+(he + thy)| LU). (3.5)

The planar phase is a superposition of two states: |S, = +1,m=-—1) and |S,=-—1,
m= +1).
Polar phase:
d(k) ~ (0,0,k.), (3.6)

whence follows
wee ~ (TL) + 1). 3.2%

PHASES OF SUPERFLUID HELIUM-3 15
The polar phase contains pairs with S, = 0 and m = 0.

There are also phases with non-zero orbital and spin angular momenta.
A-phase:
d(k) ~ (k, + ik,,0,0), (3.8)

ie. AA, oc Vo(Ai +iAY), where V = (1,0,0), A’ = (1,0,0), and A” = (0,1,0). In an
arbitrary reference frame, V is a unit vector in the spin space, and A’ and A” are mutually
orthogonal vectors in the coordinate space. The pair wave function has the form
Wha (hott) (GY) ~bibNTT) ~ [L). 3.)

Thus the A-phase is a linear combination of two equiprobable states |S, = +1,m = 1)
and|S, = —1,m = 1). The total spin in this phaseis zero. The orbital angular momentum
of a vessel containing the A-phase in the groundstate should be of the order of Nh, where
N is the number of Cooper pairs.
A,-phase:
d(k) ~ (& + ik, i(k, + ik), 0). (3.10)

Hence AA! ~ (V! + iV")(Ai +iA!), where V’ and V” are mutually orthogonal unit spin
vectors, and A’ and A”are defined as in the A-phase. The pair wave function has the form
vw ocd (Veda G.11)
tm (ket iy) (2°) = & + i&)IT).
Hence the A;-phaseconsists of pairs,with S, = 1 and m = 1. This phase has both spin and
orbital magnetic moments.
B-phase:
d(k) ~ (k, ik, 0). (3.12)

Hence A%, ~ (V. + iV“)A; and
| ~(1 0 a ae
wae mke( 9) = (G+ th) +iB)ITM (3.13)
ie. the @-phase contains pairs with S, = 1,m = +1 and S, = 1, m= —1, andthus has a
non-vanishing total spin.
4 Superconducting States in Crystals
It follows from the discussion in Section 2 that superconducting states with a definite
spatial parity should be either spin-singlet or spin-triplet. In particular, the pair spin wave
function of a state with even parity
Woair ~ g(k)ioy, (4.1)
g(k) = g(—k), (4.2)

corresponds to S = 0, and that of a state with odd parity-to S = 1, ie.
c Wair ~ (d(k)o)ioy, (4.3)
d(k) = —4(-). (4.4)

The symmetry of the system in the superconducting state includes the spatial inversionif
the pair wave function W,,i does not change under the inversion operation I:
: TVpair = Vpair, (4.5)
which correspondsto singlet pairing, or changesits sign:
TWpair = —Vpair (4.6)
in the case of triplet pairing. Mixed superconducting states like
av’ + bY (4.7)
are forbidden in this case.

If the normal state symmetry, however, does not include the spatial inversion (the
crystal lattice has no inversion centre) or the symmetry under inversion is broken as a
result of the superconducting transition (becauseof a specific type of pairing interaction),
states like those with the order parameter defined by equation (4.7) are possible [7].
17
Hereafter we assume presence of the spatial inversion symmetry and consider super-
conducting states given by either equation (4.1) or equation (4.3).
As wasstated in Section 1, the transitions temperatures to superconducting states with
different orbital angular momenta in an isotropic material should be different, i.e.
T, = T.(l). The functions g(k) and d(k) for the singlet andtriplet states are expressed as
linear combinations of the spherical functions with respective 1:
i
e'(k) = > dim Yim (Kk), for |= 0,2,4,..., (4.8)
m=—l
!
@'(k) = S> bin Yin(K), for 1= 1,3,5,... (4.9)
m=—l
As wasnoted in the previous section, the choice of the reference frame is inessential for
the functions Yin (kk) since the functions Y;,, (k’ ) obtained after rotation of the reference
frame in the three-dimensional space are expressed as linear combinationsof the spher-
ical harmonics with the same /:
i
Yin (k’) = S Dnt Y,lin! (k).
ma 1
In the generalcase,onesays that a set of functions w;(r) formsa basis of an irreducible

representation of a certain spatial symmetry group G if any function from this set is
transformed under any symmetry operation of the group to a linear combination of the
functions belonging to this set [8]:
d
Pilger) = Y(t") = » cythj(r).

In an isotropic system, which is invariant underall spatial rotations, i.e. elements of the
group SO3, the irreducible representations are labeled by the value ofthe orbital angular
momentum /, and the set of 2/ + 1 spherical harmonicswith the given orbital momentum
/ formsthe basis of the irreducible representation. The types of Cooper pairing are in one-
to-one correspondence with the irreducible representations of the group of three-
dimensionalrotations.
This classification principle of superconducting states in accordance with the irre-
ducible representations of the symmetry group in the normalstate is also valid in crystals
where the normalstate anisotropy is present [9-14]. Namely, superconducting states with
different critical temperatures are described by the basis functions ofdifferent irreducible
representations I‘ of the point symmetry group G of the solid,! that is 7. = T,<(L).
Expansions (4.8) and (4.9) transform in this case to
dp
a(k) = > meh;*(b), (4.10)
i=]
' The spatial symmetry groupofa solid is a combination of the point symmetry elementsand translations. The
latter can be ignored since the superconductingtransition does not bring about an additional spatial modulation.
SUPERCONDUCTINGSTATESIN CRYSTALS 19
dr
d(k) = So nd;"(k), (4.11)
i=]
a
where vit (k) and 1;"(k) are the basis functions (index g denotes functions even in k and
u labels odd functions) of irreducible representations [' of group G with dimensionality
dy.
In the case of negligible spin-orbit coupling, the states are degenerate with respect to
rotation of spin vectors:
ne > HP = Rianf’.
In the case of strong spin-orbit coupling, which takes place in materials containing
chemical elements with large atomic numbers, it is convenient to present equation (4.11)
in the form of the expansion
dr
d'(k) = So nw"(k) (4.12)
i=]
in terms of the vector basis functions
Wi"(i) = Yi(ke + 47ES + d7OZ, (4.13)

yi(—k) = —w?" (ik)
of the irreducible representation I’. The basis in the spin space is defined by axial unit
vectors %, 9, and 2 uniquely determined by the crystal axes. Although the electron spin
becomes a ‘bad’ quantum number in solids with strong spin-orbit coupling, electron
states are, nonetheless, doubly degenerate (because of the Kramers degeneracy dueto the
time reversal symmetry), which allows us to classify them in terms of the ‘pseudospin.’
Theattributes ‘spin-singlet’ and ‘spin-triplet’ superconducting states should be also in-
terpreted in terms of the pseudospin.
The set of complex coefficients 7; (or N,) in expansions (4.10), (4.11), and (4.12)is the
order parameter in crystal superconductors. Thus, superconducting states with either a
one-component order parameter 7 = |nle'* or multicomponent order parameters are
plausible.
In addition to the point symmetry operations, the symmetry group G of the normalstate
also contains the operation of time reversal R and gauge transformations U(1)?:
G=U(1)xRxG.
Thetransition to a superconducting or superfluid state brings about phase coherence, i.e.
states with different phases ¢ of the order parameter \nle’® become distinguishable, which
is usually described as the spontaneous breaking of gauge symmetry U(1). As a result of
2 In the absence of spin-orbit coupling, the group G should also include three-dimensional free spin rota-
tions, which form the group SO§.
a b
FIGURE 4.1 Fermi surface cross-section (thick line) in the basal planeofa tetragonalcrystal
(symmetry group
Dy4,). The thin lines show: (a) amplitude of the order parameter of a conventional
superconducting state
(representation Aj,); (b) amplitude of the order parameter of an unconventional
superconducting state
(representation B,,) which lowers the crystal point symmetry to Dy.
the transition in a particular superfluid state, other types of symmetry breaking of the
symmetry properties of a system under the operations of group G may also occur (un-
conventional superfluidity or superconductivity). Therefore, only invariance under sym-
metry operations forming the subgroup H (superconducting class) of the group G persists.
Thus, the problem of determining all possible superconducting (or superfluid) phases
is
reducedto the determination of superconducting classes corresponding to different types
of the normal state symmetry breaking [9].
Among superconducting states permissible from the viewpoint of symmetry properties,
we have to single out the states that can be formed directly from the normal phase.?
According to Landau’s general theory of phase transitions, the order parameters in such
states should transform in accordance with the irreducible representations of the point
symmetry group G in the normal phase [9]. The conventional superconducting state has
the full point symmetry of the crystallattice, i.e. it belongs to the identity representation
Aj, and is described bythetrivial superconducting class H = R x G. The point symmetry
properties of the rest of superconducting states, which belong to non-identity
rep-
resentations (or to the odd identity representation Aj,), are broken, and they are
termed
nontrivial or unconventional superconducting states (Figure 4.1).
In the case of a one-component order parameter, there is a one-to-one correspon
dence
betweenthe one-dimensional representations of group G and superconductingclasses.
On
the contrary, multi-dimensional representations generate several superconductingsta
tes
belonging to different superconducting classes with the samecritical temperatu
re but
different free energies (see for details Section 11). This is the case, for example,
for the
p-wave states discussed in Section 3.
3 Superconducting classes outside this category correspond to the states which can
occur as a result of
additional phase transitions in the superconducting phase.
SUPERCONDUCTING STATES IN CRYSTALS 21
Superconducting classes in a hexagonal crystal
Let us consider superconducting states in a crystal with the hexagonal symmetry char-
acterised by the group G = Den = De x I, where I is the inversion operation. This example
is fairly importantin view ofits application to the heavy-fermion superconductor UPt3. In
this case we have six irreducible representations, namely, four one-dimensional A;, A>,
Bj, and B, and two two-dimensional E, and E2. The symmetry of each superconducting
state is characterised by a subgroup of the group G = U(1) x R x Den.
The group Deg = {Cn, U,} consists of six rotations C, about the Z-axis by the angles
mn/3 (n= 0,1,...,5; Co = E is the unity element) androtations U, by an angle a about
six axes
~ Tm , aH
isin + ycos—.
Amongthe subgroups of the group G, there are four subgroups H that correspond to
the superconducting states characterised by the functions of four one-dimensional
representations of Dg. These are the groups Dg x R, D¢(Ce) x R, Do(D3) x R, and
D6(D},) x R. The subgroupsin parentheses incorporate those elements of the group De;
which are not multiplied by a phase factor from U(1), that is
D6(Cs) = {Cy e™ Un}
Dg(D3) = {Cox Ure, eCorsi, e” Uresi},

Dg(D4) = (Cox, Vreri,eCaras, eo” Une};
where k =0,1,2. It is clear that the subgroup Dg corresponds to the identity rep-
resentation A;. Exactly one half of the elements of the subgroup Dg(C¢) (or De(Ds),
D¢(D4)) are elements of the group Dg, the other half are combinations of the point
symmetry elements and the gauge transformation e’, So, the point transformations U,,
changethe sign of the order parameter of the superconducting state with the symmetry
Dg(Cg). Therefore.this state corresponds to the non-trivial representation Az of the group
Dg (similarly De (Ds) corresponds to By, and Dg(D3) to B2).
High-temperature superconductors
Another example of unconventional superconductivity is presented by high-temperature

superconductors, which include metal-oxide materials with T, ranging between 7K and
100K. The materials of this family which have been studied most thoroughly, namely
Laz_,Sr,CuO4, and YBa,Cu307_,, have crystal lattices of tetragonal symmetry, i.e.
G = Da, = Da x I. Crystal lattices of yttrium—barium compounds have small orthor-
hombic deformations (of about one percent), whose effect will be discussed below.
The group D4, which includesrotations C, around the z-axis by the angles 1/2 and
rotations U, by angle 7 about the axes
a ms _ an
x cos—— 9 sin —
4 4°
where n = 0,1,2,3, has five irreducible representations, four of them are one-dimen-
sional A;, Aj, B;, and By, and one two-dimensional E.
The accumulated data concerning the low-temperature behaviour of the thermo-
dynamic properties [15, 16], combined with the angle-resolved photoemission meas-
urements (ARPES) [17] and the phase-sensitive SQUID measurements [18-20] (see
Section 16) have led researchers to the conclusion that the superconducting state in these
compounds is described by a one-component non-trivial order parameter corresponding
to singlet pairing and transforming according to the By), representation,that is,
a(k) ~ k2 — ke. (4.14)

This type of pairing is traditionally called ‘d-wave pairing,although this term is not
absolutely correct, since the superconducting states in crystals are not characterised by
their orbital angular momentum. In the corresponding superconducting class,
D4(Dz) x RB = {Cox, Ure, e™Copy,Ur} XR (k = 0, 1)

the phase factors e'" = —1 compensate for the sign change in the basis functions under
the point symmetry operations.
Orthorhombiccrystals are characterised by the symmetry group G = D>, which has
four one-dimensionalirreducible representations. The simplest of them is the identity
representation A,, corresponding to conventional superconductivity with the order
parameter invariant under rotations about %, }, and z-axes by angle z.In the case of singlet
pairing, such properties are characteristic, in particular, of the function
g(k) ~a+b(ke — 2B),

which is a mixture of s- and d-wave states and can betreated as the order parameter with
so-called ‘s + d-wave pairing.’ It is remarkable that this absolutely conventional super-
conducting state in an orthorhombic material can befairly similar to the unconventional
superconducting state By, in a tetragonal crystal. This happens when a small ortho-
rhombic deformation in a tetragonal crystal admixes the s-wave componentto the initial
d-wave component of the order parameter (4.14). Another mixed “s + id-state,” often
discussed in the literature, will be considered in the next section.
Magnetic superconducting classes
The superconducting classes discussed above contain operations R explicitly, ie. the
respective states are invariant under time reversal. This, in turn, means the absence of
spontaneous magnetisation of Cooperpairs. The action of the point group operations on
the order parameter, however, can be compensatednot only by the phase factor from the
gauge group U(1), but also by the operation R, which reduces to complex conjugation:
g(k) — g*(k) or d(k) — d*(k). Thereby, the time reversal symmetry is broken and the
symmetry of such superconducting states is described in terms of magnetic super-
conducting classes [9].
The complex conjugation of a one-component order parameter (complex number) is

equivalent to its multiplication by a phase factor. The physical quantities, including the
magnetic moment, which hasto change its sign under timereversal, are not changed as a
result of this operation. This is why magnetic superconducting states are described by
multicomponent order parameters.
A detailed discussion of the issue of magnetism in superconducting phaseswill be given
in Section 15, and here we consider only one example of the magnetic superconducting
classes in tetragonal crystals. One can easily verify that the group G = U(1)x R x Da,
has the subgroup
D4(Dz) = {Crg, Ure, RC2e41, RU21} (k= 0,1),

in which the time reversal operation acts only in combination with rotations around
symmetry axes of the tetragonal lattice. This type of symmetry characterises, for
example, the superconducting phase with singlet pairing and the order parameter
g(k) = (A, + iAg(k2 — K))el*, where A, and A, are arbitrary constants. Such state
(which is often called ‘s + id-wave pairing’) can turn up as a result of two consecutive
phasetransitions: one from the normal to the superconducting state with a one-component
order parameter g(k) = A,e'? corresponding to the Aig representation, and another
transition which occurs at a lower temperature andbrings about another superconducting
phase in which the order parameter g2(k) = Ag(k2 — i2)ei@ corresponding to the By,
representation is admixed to g;(k).
Nodesin the spectra of elementary excitations
The presence of non-trivial symmetry elements, including a gauge transformation, leads

to an important consequence, namely the existence of nodesin the order parameter. Let us
discuss this property of the spin-singlet order parameter g(k) with symmetry D6(Ce) x R:
C,g(k) = g(k), (4.15)

"Ung(k) = g(k), (4.16)
g(—k) = a(k). (4.17)
In particular, for values of the order parameter in the (k,, ky) plane perpendicular to the
y-axis, which is the axis of the Up rotation, we derive the following relation from
equation (4.16):
c Uo8(kx, ke) = 8(kes kz). (4.18)

Onthe other hand, Uk, = —k,, Upk, = —k,, and
Uog(kay kz) = 8(—ke, —ke)

Using equation (4.17), we obtain
os(kis ke) = 8(Kes kz). (4.19)

Conditions (4.18) and (4.19) can be satisfied simultaneously only if
(kx, kz) = 0. (4.20)
Thus, the order parameter turns to zero at the (k,,k,) plane and, moreover, changesits
sign across the plane. This is the property of all planes perpendicular to the symmetry
axes U,,.
The gap in the spectrum of elementary excitations is proportional to the absolute value
of the order parameter*:
Ax ~ |g(k)|, atS=0, Ax~ |d(k)|, atS=1

(see below Section 5). Therefore the energy spectrum of quasiparticles in a super-
conducting state with symmetry Dg(Cs) x R is gapless at the crossing lines of the Fermi
surface and planes perpendicular to axes of U,, rotations.
For the spin-triplet order parameter d(k) with symmetry Dg(Cs) x R, we have
C,d(k) = d(k), (4.21)
e"U,d(k) = d(k), (4.22)
d(—k) = —d(k). (4.23)
The invariance of the order parameter under rotations C,, means that for momenta
pointing along the Z-axis only the z-component of vector d(k) is non-zero:
d(k,) = 2e)*(k,). (4.24)

From equation (4.22) follows
Uod(k,) = —d(k,). (4.25)
At the same time, we derive from equations (4.23) and (4.24)
Uod(kz) = Uod*(ke) = —2*(—ke) = 2*(K) = d(k,). (4.26)

By comparing equations (4.25) and (4.26), we come to the conclusion that
d(k,) =0, (4.27)
ie. the order parameter is zero along the Z-axis, therefore the spectrum of elementary
excitations is gapless at the north and south poles of the Fermi surface. ;
Thus, there is a feature commonto the superconducting states whose symmetryele-
ments include combinations of the point and gauge symmetry operations (or the point
symmetry operations and time reversal), namely, the spectrum of elementary excitations
in such superconductorsis gapless. The order parameter vanishes on lines andatisolated
points on the Fermi surface at S = 0, andatisolated points at S = 1. The latter statement
applies only to the case of strong spin-orbit coupling (a counter-example is the order
parameter in the polar p-wave phase).
’ 4 This statement applies to unitary superconducting states in the absence of impurities (see Footnote 6 in
Section 5 and Section 17).
The inevitable presence of nodes in the spectrum of elementary excitations is a direct

consequence of the superconducting state symmetry. For this reason, nodes of this type
are termed symmetry nodes. Among the symmetry nodes, we can define a specific class
of topological nodes including the symmetry nodes that do not vanish after continuous
deformations, which lower the lattice symmetry. Omitting the details, we just point out
(without presenting the proof) that the symmetry nodesat isolated points are, at the same
time, topological nodes, whereas the symmetry line nodes are not topological.
The symmetry approach to superconducting states leaves a lot of options in selecting
the basis functions of irreducible representations. A particular choice ofthe basis functions
of a given representation T could be based only on a specific microscopic model and is
determined by the desired accuracy of description of the order parameter in the super-
conducting state under consideration. The presence and positions of the symmetry nodes
ate determined not by the specific form of the basis functions, but by the symmetry of the
superconducting state. A specific choice of the basis functions, however, can generate
nonphysical (‘accidental’) nodes in the spectrum of elementary excitations.
Examples of the basis functions for the representations of group Dg, are given in
Tables 4.1 and 4.2. In order to illustrate the statements formulated above, the basis
functions of odd representations in Table 4.1 are given in the form of linear combinations
of two functions. Atarbitrary coefficients a and b, the basis functions we"(Ik) have nodes
only at isolated points on the Fermi surface coinciding with the symmetry axes corres-
ponding to combined symmetry elements of the specific superconducting state (symmetry
nodes). On the other hand, if a = 0 or b = 0, additional accidental nodes of the order
parameter. (including line nodes) are generated in addition to the symmetry nodesof the
order parameter.
TABLE 4.1 Basis functions of even (S = 0) and odd (S = 1, strong spin-orbit

coupling) representations of the group De,
d or wi" (K), wi"(h) H

1 Aig ak? + b(K2 + 2) + c(K§ — 15K+ 15K2Ky — ki) Dg XR
1 Atu ak,2 + b(ky% +6S)
1 Aog (k3 — 3k?) (3 — Bkyk?) De(Cs) xR
1 A2y atk, (k3 — 3k,k?)(K} — 3kyk2) + b(Rky — kx)
1 Big K(k} — 3kyhe) D,(D3) xR
1 Bi az(k3 — 3kxkp) + bk[&(k2 — ke) ~ 2kerky]
1 Bog k.(k — 3kyk?) Dg(D5) x R
1 Bou a2 (k} — 3kyk2) + bk, [S(ky — ky) — 2iKcky|
2 Eig. keks, keky

2 Ew ky, thy kek, bed
2 Eog Re — ke, Ukeky
2 Ey kk — ky, I+ KR Bee (KE — Ko), Zekckecky
x
TABLE 4.2 Basis functions of odd (S = 1, weak spin-orbit coupling)

representations of group Dg,
d r wi" (&) H
1 At ki(ky — 3kxk;) (ke — 3kyk2) Dg x R x SOS
1 Aan k, Dg(Ce) x R x SOS
1 Bi k} — 3kyk? D6(D3) x R x SO§
1 Boy RB _ 3kxks D6(D3) xR*xX SOS
2 Ew keys ky
2 Ey ki(ky — ke), Wkgkyke
TABLE 4.3 Basis functions of even (S = 0) and odd (S = 1, strong

spin-orbit coupling) representations of group D4,
qd by*(K), wh(ke) H
1 Aig ak? + b(k2 + 2) DyxR
1 Ay, kz, + b(ky + Sky)
1 Arg ghey (K2 — K2) D4(C4) x R
1 Aou A(iky + Sky) (kz — KB) + b(Sky — Sky)
1 Big ke — ke D4(D2) x R
1 Bry aky — hy) + b2K,(K2 — K2)
1 Bog exh D4(D}) x R
1 Boy aRhy + Shey) + Dokki
2 E, kkes keky
2 E, Rhy, Bky
TABLE 4.4 Basis functions of odd (S = 1, weak spin-orbit coupling)

representations of group D4,
d r 8 (k) H
1 Aww Kekykz(ke — 2) Dg x R x SOS
1 Ary k, Dg(C4) x R x SO$
1 Biy kykyky D4(D>) xRx SOS
1 Boy k,(k? — k) D4(D3) x R x SO$

2 Ey ky, ky
SUPERCONDUCTINGSTATES IN CRYSTALS 27
TABLE 4.5 Basis functions of odd (S = 0) and even (S = 1, strong spin-orbit coupling)
representations of group Op (€ = exp(2mi/3), O(T) = (E,8C3, 3Co, 6e" U2, 6e'"Cy))
d Pr 8 (k), wi" (k) H

1 Aig B++k OxR
1 Atu Sky + Thy + 2k,
1 Ag (k2 — 2) (K2 — KB)— 2) O(T) xR
1 Aaw tk(k2 — IB) + Sky (Ke — KZ) + Beek — ke)
2 E, Ke + eh + ek, Ke + 7k+ ek;
2 E, Sky + EVky + €78kz, thy + €7Hky + ek,
3 Fig Keykig(k2 — KB), eke (2 — KR), Kerley (I — Bey

3 Fy Pky — ky, By — Kkz, Rhy — Phx
3 Fo, Keykez, keke, kerky
3 Foy Pky + ky, ky + Rkq, Thy + Hk
TABLE 4.6 Basis functions of odd (S = 1, weak spin-orbit coupling) rep-

resentations of group O;,
qd 7 by§(k) H
1 Aw kikiykeg(k2 — 1) (KE — RE) (K2 — ke) Ox Rx SO§
1 Aon kykyk, O(T) x R x SO}
2 E, keckyke (2 + eke + €°K2),

kckyk, (kee + €7k2 + ek?)
Pry ky, ky, k,
Poy kx (ke ~~ ke), ky (kz ~ Re), ke (ke _ ke)
Basis functions of the irreducible representations for crystals of the tetragonal (group
Day) and cubic (group O,) symmetries are listed in Tables 4.3-4.6. The corresponding
superconducting classes H for one-dimensional representations are also given. The
classes of superconducting states corresponding to multi-dimensional representations will
be introduced in Section 11, devoted to the Landau theory for superconductors with
anisotropic pairing.
5 Energy of Elementary Excitations in
Superconductors
The problem of calculating the spectrum of elementary excitations in a superconductoris

solved by diagonalising the Hamiltonian of an ensemble of Fermi-particles! including only
the pair attraction between particles with opposite momenta, whichis the kindof inter-
action essential for the superconductivity (the Bardeen—Cooper—Schrieffer Hamiltonian)’:
1
H= S> & ay Oke + 3 > Ver, uk; k’) a!ke aig Ay) dk (5.1)
k k,k’
Hereafter the summation convention concerning repeating spin indices is used every-
where, & = id /2m* — ep is the energy of excitations measured with respect to the
Fermi energy, and m*is the effective mass. Vig,x,(k, k’) is the potential of pair attraction
with the following symmetry properties:
Vop,u(K, k’) = —Vea,,u(—k, k’) = —Vogalk, —k’) = V,,g0(k’, k). (5.2)
In the absence of spin-orbit coupling, the attractive potential can be factorised:
VosAulk, k’) = Vik, KPo8,\u- (5.3)
Weassumethat the function V(k, k’) is non-zero when the ends of vectors k and k’ are in
a narrow layer near the Fermi surface:
I
Vk, k’) = Vi(k,R) S27 Yim(K)¥in(K'), (5.4)

m=—l
' Bor simpitci we consider a Fermi gas with a spherical Fermi surface and ignore the effects of the lattice
symmetry on the spectrum.
2 Hereafter we use the wave functions normalised to the unit volume, therefore }* f oy = No f dé f dQ
where No = wie is the density of states at the Fermi level per one spin projection.
Wo .
29
' —V), if ep —e, < k?/2m*,k!?/2m* < ep te,

i(k, k ) = : : :
0, outside the given interval.
In this expression, the expansion of the function V(k,k’) in terms of the spherical har-
monics Yj, (k) with different / contains only the interaction component V; which is
responsible for the highest critical temperature (see Section 1).
As regards the spin dependenceof the interaction potential, it is expressed in terms of
the matrices which are antisymmetric under permutation of indices af(Aj) for even I:
1
Dap au = 5 8aB8us (5.5)
where gag = (ioy),,, and symmetric for odd /:

1
Dap. = 5 BapBiye (5.6)
where gap = (igoy),,, and gt and gt denote Hermitian-conjugated matrices.
In solids, where the invariance under the point symmetry operations is essential, the
pair interaction is of the form
Vos,u(k, k’) = Vek, kTop,au at(kk) 7" (k’). (5.7)

i=]
This equation contains only the interaction Vp corresponding to the irreducible repres-
entation I with the basis functions Wr(k}, which gives rise to the highest critical
temperature. The functions [',, for even and odd representations are given by
equations (5.5) and (5.6), respectively.
Equation (5.7) applies to the singlet pairing and triplet pairing with weak spin-orbit
coupling. In the case of S = 1 and strong spin-orbit coupling (see Section 4) the pair
interaction is determined by the potential
Vap.an(lsk!) = 5 Vo(k, S(vi8.0) (wiegt). (5.8)

The instability of the electron gas described by the Hamiltonian (5.1) against formation of
Cooperpairs can be taken into account [1] by expressing the wave function in the form of
the product
U= [[@ + Ux ayay) )[vac). (5.9)
Here v, is the amplitude corresponding to the probability that the (k t,—-k |) pair state is
occupied (for simplicity we consider only the singlet pairing), u;, is the amplitude of the
probability that the pair state is vacant, and |vac) is the wave function ofthe vacuumstate.
In addition, the amplitudes u and v satisfy the following condition:
[axl + [use| = 1.
ENERGY OF ELEMENTARY EXCITATIONS IN SUPERCONDUCTORS 31
In a normal metal
Ug = 1, uy =0, for |k| < kp,

(5.10)
Uy, =0, u=1, for [kj > kp,
i.e. all states below the Fermi level are occupied and ail states above are vacant.
In a superconductor the probability of a state with any k to be vacantis finite, and the
ground state wave function (5.9) contains a set of summands with different filling
probabilities of states with 0,2,...,N,N+2,... paired particles. In other words, the
groundstate of a superconductor is a superposition of states with different numbers of
Cooperpairs.? The consequenceof this fundamental fact is non-vanishing values of so-
called anomalous averages [21]:
Fig, = (Ulaxt aay ¥),

Fey) = (Vlat, ay|W).
Such average values can be also defined at an arbitrary temperature*:
Fya6 = (Ake 4s) (5.11)

FLap = (aka dip) -
The function F\,.g, which has the meaning of the pair wave function, is antisymmetric
under permutation of particles:
Fyop 7 F_x,pa = —Frap- (5.12)
In the case when the function F is even in coordinates, equation (5.12) indicates that the
function is antisymmetric under permutation of spin indices:
Feop = Figas
ie. in the case of singlet pairing we have
Fag = Fraps
et 4 (5.13)
Foag = e8ap
where F_, = F,. For functions F odd with respect to coordinates, equation (5.12) holds
only in the case of the symmetry under permutation of spin indices:
u
Fkoe = PKBa?
3 ‘The main contribution to this superposition comesfrom thestates with the number of pairs Npairs Nparticies /2.
4 The averages in Eq. (5.11) are defined as
Cc -
> Ayn Ba /T
(A) = 5 Ei:
4
ie. in the case of triplet pairing
= Fyg ’
hag = ae (5.14)
Frag =FBaa»
where F_, = —F,.
In orderto diagonalise the Hamiltonian in the mean-field approximation[21], we assume
that the deviations of the products of creation and annihilation operators in equation (5.1)
from their average values given by equation (5.11) are small. By using the identities
Oka = Fiap + (atkatte — Fivary) (5.15)

Ay! 8k! = Fy Ny + (ay!AK, Fe nu)
we express the Hamiltonian (5.1) in the approximation linear with respect to these
deviations:
H= DSelatha + 5 Vosau (Kk,k’)(—FivapFx! Ma

k,k’
Koptk' 4k, + FFik! uFkoa)
+Ff (5.16)
Now weintroduce the functions
Ak op = » Vea,du(K, K’) Fe aus
(5.17)
A = > Vos,prt(k’ sk)Fy
k’ af"
From equations (5.2) and (5.12) we derive
Axap = —A_x pa:
It is obvious that, for the interaction potential even in the momentum, the functions
Ax,ag and Fig should also be even, which correspondsto pairing in the singletstate:
Ata = Ag(k)(ioy)a9. (5.18)

Here
I
g(k) = g(k) = S- Aim (k)Yim (Kk),
m=—l
and the function g'(k) is normalised as follows:
[Gileoor=1.
dQ
= (5.19)
5.1
Note also that

dQ ,
ont =0
aq 8 (k)
for all /, except the case of s-wave pairing (J = 0).
In the case of an odd interaction potential, the functions Ayog and Fy,g ate also odd
and describetriplet pairing:
nap = Ad(k)(i00})a9. (5.20)
Here
d(k) = d'(k) = S> Din(k)Yim (kK);

m=-l
and
[rawr =1, (5.21)
The coefficients aj,(k) and bj,(k) are non-vanishing only within a thin layer of thickness
6k = €;/vp near the Fermi surface.
Using equation (5.17), we transform the Hamiltonian (5.16) to the form?
1 1
A= 3 > &x (ai. aka — Aka a*ke) + 2 > &
1 + 7+ + +
+5 > (Aras AoA+ Aap Aka O49 + Atop Fisa) (5.22)
This equation can be written in a more compact form using the vector operators [22]
Ax, = (ai) 4-ka) = (ie Qe)» FW AKL),
Akt
A= aka _ a (5.23)
Nata) | tee |
ary
We have
1 1 1
H= 5S AL eKy AK +5 2 Atos Fitga +5 > Sk (5.24)
k k ka
which contains the 4 x 4 matrix
Exbas Akag
ek ij = :
C ’ Afap —~&k6as
Pp. indices of the function &, independent of spins

5 Summation over spin Pp: meansthat 2 & = 2) . 7.
cag
4
34 "INTRODUCTION TO UNCONV:ENTIONAL SUPERCONDUCTIVITY
Hamiltonian (5.24) can be diagonalised using a unitary Bogoliubov transformation

which does not affect the anticommutation properties and transforms fermion operators
Ako, to fermion operators by:
Axi = UyByj; (5.25)

where
v=( Uk sep
a,
* ’)
Uk,cy
(5.26)
Ukap Wkap
big
By= (." ) (5.27)
—kg
The elements of the transform matrix are, in turn, 2 x 2 matrices in the spin space and
determined by the following equations:
(Ex + &x) bas

Uap = 5 = Uba8;
(Ex + &)° + AZ
(5.58)
Akas
Uk,ap = it Cd
4/ (Ex + &x)° + A?
where
Ex = 1/6 + Ae (5.29)
and the following notation is introduced (see equations (5.18) and (5.20)):
A? = 1 ATA _ Ale),
2 2 _—
for S = 0, (5.30)
2 A?d(k)d*(k), for S=1.
As a result, we have
+ — +PpoPp.
AtekAk = DBEx.iiBre,j
kK kK
where
® All formulasofthis section given below applyto arbitrary types of singlet pairing, and in the case of triplet
pairing only to the so-called unitary phases, which satisfy the condition (AA*) 6 ~ éag. Among the p-wave
states listed in Section 3, all are unitary, except Ay- and #-phases. In the case of non-unitary phases,
the
Hamiltonian diagonalisation is more difficult (see Ref. 13 and Section 17) and is not discussed here.
Let us rewrite the latter expression using the quasiparticle creation and annihilation
operators Dyo'
1 1 1
3 Ss; ByExBx,j = 3 S> Ex Diy Dice — 3 S> Ex, ba Bea
K k k
= Ds Fa Pia he 3
Oe
Thus, the Hamiltonian of the superconductorfinally takes the form
H = Ey +S) Ex diPas (5.31)

k
where
1 4 1
Eo = ae Ax,ap FyBa + 2 Db ~ Ex) (5.32)
is the ground state energy and E, are the energies of elementary excitations in the
superconductor.
In the case of a superconductor with singlet pairing, we have
= (E+ Mle), (5.33)

i.e. the spectrum of elementary excitations has a gap. In the fully isotropic case (s-wave
pairing) g(k) = |Ale’*, and we deal with a fully gapped superconductor. As was shownin
Section 4, s-wave pairing generates a superconductingstate transforming according to the
identity representation ofthe lattice point symmetry ground.In this case g(k) can turn to
zero at some values of k (accidental nodes). In the case of an anisotropic pairing with
1 # 0 such that the superconductingstate is invariant under combined symmetry elements
(for example, rotation and gauge transformation), the gap should necessarily turn to zero
at some k (the symmetry nodes).
In a superconductor with triplet pairing
Ex = \/ @ + A2|d(k)/. (5.34)
In the B-phase, d = k (see equations (3.2) and (5.21)) and
BB = ,/@ +|A/, (5.35)
ie. as in the case of s-wavepairing, there is a gap which is independentof the directions
of k over the entire Fermi surface.
In the A-phase, d = Vie + iky, 0, 0) (see equation (3.8) with due account of the
normalisation factor), and
EA = /¢ +530 3 sin? 6,
A2(2 +) = /¢ + 5A? (5.36)
{
FIGURE 5.1 Gap in the A-phase spectrum. The gap boundary is shown by thin line, the Fermi sphere by the
thick line.
i.e. the gap in the spectrum has nodesat the north and south poles (0 = 0,7) of the Fermi
sphere (Figure 5.1). The presence of nodes in the spectrum of the A-phase is the con-
sequence of the combined invariance ofstate (3.8) under rotations aroundthe z-axis by an
angle a and a simultaneous gauge transformation, namely multiplication by e~!* (see for
details Section 4).
Exercise
Show that the ground state energy of a superconductor (5.32) is determined by the
following expressions:
1
Eos = Eon — 5 No? (5.37)
for isotropic singlet pairing, and
1 dQ
Eos = Eon — qo Sp qq OK Ak (5.38)
for an arbitrary type of pairing, where Eo, is the normal metal ground state energy.
6 Gap in the Spectrum of Elementary Excitations
and Critical Temperature
of
In order to determine the temperature dependence of the gap in the spectrum
elementary excitations, let us use equation (5.17):
Ak,ap = — Ss; Vosa,\u(K, kK!)Fie!y- (6.1)

we
After substituting the anomalous average (5.11) in this equation and using Bogoliubov’s
transform (5.25), we have
Fyn = (Qn) = (ie,dy Peey + U7 De) (U—k,us b_45 + V—K,u5 Dus)
Using the relations
Ukop = USap, Vk,aB = —V-k,Bo

(b_kabip) = (Pika?i) = 0,
(diab) = bap — (bepbia) = febap,

where
1
fc =f(Ex) = exp(x/T) (6.2)
d by
is the Fermi distribution function for excitations with energy 2, determine
equation (5.29), we obtain
A
Figs = thdy(1— 2fk) = Ge" (1 = 2 (6.3)
37
After substitution of this expression in equation (6.1), we finally have the following self-
consistency condition:
1-2fy!
Akos = — > Vee,du(k, k’) 2B,
k’
Ske (6.4)
whichis also called ‘the gap equation.’ Taking equations (5.33) and (5.34) into account,
we have
g(k) = — Vk, Kk’) (1 — 2fer) a(k’)

(
K 24/8, + Alek’)?
for singlet pairing and
d(k) = — Vik, k= 2fe) d(k’) (6.6)

K’ 24/€2, + A2ld(k’)|?
for triplet pairing.
As T — T,, the gap in the spectrum turnsto zero, and equations (6.5) and (6.6) become
linear. This means that all combinations of the spherical harmonics with given J (in the
general case, of the basis functions of a given irreducible representation of the symmetry
group G) expressed as
I
g(k) = > Aim Yim (Ik) (6.7)
m=—l
or
d(k) = S° Din Yin (he) (6.8)

m=—l
are solutions of equations (6.5) or (6.6), respectively. Thus, we have come to the con-
clusion thatall superconducting states corresponding to a given irreducible representation
of the symmetry group of the normal state have the samecritical temperature. It is
determined by the equation
Ej
1=Nov;
_ tanh(|€|/2T.)
fs ee (6.9)
which is obtained by substituting expansion (6.7) (or (6.8)) in the gap equation. By
integrating the right-handside of equation (6.9) and taking the upperlimit of the rapidly
converging integral to infinity, we obtain
oo
E] Inx
1=NoV,| In — dx——
on 27. | * Gosh? x
URE 39
GAP IN THE SPECTRUM OF ELEMENTARY EXCITATIONS AND CRITICAL TEMPERAT
Hence,
2y 1
T.=—
7 ol exp( -——
Nea) }. (6.10)
10
Here 27/7 = 1.14, where

Iny =C #0577
is called Euler’s constant.
Substituting expansions (5.4), (5.7), or (5.8) of the pair attraction potential in
equations (6.5), (6.6) and using the orthogonality of the basis functions of irreducible
representations, we find that the order parameter at all T<T, is expressed by
equations (6.7) or (6.8). The absolute value of the order parameter and the coefficients aj,
bjm as functions of temperature are determined by nonlinear equationslike!
e joem( C+ 2(7)|e(40F /27)
ay(T) = NoV, Ja “ *(&e(k) (6.11)

pos an 2 + A2(T)|g(k)?
for the singlet pairing, and
e| tanh( /é2 + A2(T)|d(k)|?/2T
0 . e+ A?(T)|d(k))?
for the triplet pairing, which should be supplemented with the normalisation conditions
(5.19) and (5.21).
In the general case, one should solve similar nonlinear equations for the expansion
e
coefficients of the order parameter in terms of the basis functions of the irreducibl
symmetry group. Since the choice of these functions is
representation of the crystal
, the
somewhatarbitrary (see Section 4), and the Fermi surface is usually anisotropic
the order parameter as a function of temperatu re and hence
problem of the calculation of
order
the thermodynamic and kinetic properties of a superconductor derived from the
parameter,is ill-defined in most cases.
In somecases, the gap in the spectrum can be calculated analytically at T = 0. For
example, in the case of s-wave pairing we derive from equation (6.11)
Ei
1 , dé 2€0
—— = === e lh. (6.13)
NoVo J fe + 3 Ao
a more general case,

! If the spherical harmonics with different values of the orbital angular momentum (in
of other irreducible representatio ns), correspondin g to different critical temperatures, are
the basis functions
the superconduct ing state at T <T, is also a
present in the expansion of the pair attraction potential, then
the harmonics with different J. Only the harmonics which do not lower the symmetry of the
superposition of
superconducting phases
superconducting state can be admixed, otherwise a transition between two different
occurs.
Hence follows
0= A(T =0) =2e00m(—57),

Ay = A(T = 0) =2 1 —
(6.14)
6.14
and, by comparing it to equation (6.10), we obtain
Ao == Te % 1.75Te. (6.15)
The spectral gap width as a function of temperature in the case of s-wave pairing is
determined by an equation derived from (6.4): %
£0
F(E)dg
a eos
5 [G2 4. AZ”
Hence, using equation (6.13), we obtain

€o
269 1,280 4 _f(E)aé
In
Ao A J Jl + A?’
or
€0
in? = / a . (6.16)
A 4 (exe( V+0?/7) +1) (EF?
Owing to the rapid convergenceof the integral, the upper limit can be taken to infinity.
As T — 0, we have A/T — oo and
In— &
wren tell pe [9 eo Molt
A= ao(1- 22
oyeho (6.17)
As T > T,, we have A/T — 0 and
Ao_, aT 7¢(3) (AY

mA At en Ve) +
oO
Here ¢(3) = >> n~? is Riemann’s zeta-function.

n=1
Since Ao = aT. /7, then
Wa(QF
GAP IN THE SPECTRUM OF ELEMENTARY EXCITATIONS AND CRITICAL TEMPERATURE 41
Hence follows
812 )" T. (" - "" .

(Fe
A(T) ={=——)
r. (6.18)
6.18
Due to the normalisation conditions (5.19) and (5.21), the temperature dependence of
the gap amplitude in anisotropic superconductors as T — Ty is also determined by
equation (6.18).
Exercises
(1) Calculate the momentum distribution of electrons in a superconductor:

Mop = (AKAs): (N?)—(wy’
(2) Calculate the fluctuation in the numberof particles at T = 0: 6N = Wy where
N= S a, aka:
k
7 Temperature Dependence of Thermodynamic
Quantities for T — 0
The presence of gaps in the spectra of superconductors with s-wave pairing leads to
thermally activated behaviour (~ e~4e/T) of all thermodynamic andkinetic quantities at
low temperatures.
For example, the electronic specific heat of a superconductor!
Cy =r 5, (7.1)
which is given in the case of s-wave coupling by

+00
C, _ 2No Tm 2
/ déf/2+A I
ar (— ere) (7.2)
—cO
in the limit 7 — 0 takes the form

+:
2NoA?* —A/T r 2 /2AT Ao ; f —Ao/T

Cy & pz © d&e 7 No 7 2nT Ao é€ : (7.3)
! Recall that Eq. (7.1) can be easily obtained by differentiating the combinatoric formula for the Fermi gas
entropy
os
=T—
c oT’
where
sa at — fic) In. — fe) +f Inf
43
It is natural to expect that the thermodynamic quantities of unconventional super-

conductors should obey a power law at low temperatures. The formula generalising
Eq. (7.2) to the case of anisotropic pairing has the form
-Foo
dQ 0 1
C, = 2No fale oe a (7.4)
where the excitation spectrum E. is determined by Eq. (5.33) or (5.34).

Consider as an example the specific heat of *He in the A phase. The spectrum of
elementary excitations is expressed by Eq. (5.36), ic. the gap has nodes at the north and
south poles of the Fermi sphere (6 = 0, 7), and the main contribution to the specific heat
comes from the regions around these points”:
6<2
Si?
gE v -~A<—,
<A
E
Hencein the limit TJ — 0 we obtain

oS
+co w +00 E/A

N E2 E/T N, d 2
Cc=—3
T
[a f sino dow
(e£/T +1)* 2T?
| atc
cosh’(€/2T)
[
—oo 0 —oo 0
Ao No dé &* T?
+ O| ex (-2)) 2 | temp oe! 7.5
( 7) ara omen ay 7)
where
-+oo
r=8 | dzz* _ Tn*
— cosh?z 15"
Thus, the electronic specific heat of a superconductor whose gap in the spectrum has
nodesat isolated points on the Fermi surface is proportional to T* as T > 0. A similar
calculation in the case of a superconductor with the gap having line nodes on the Fermi
surface yields C, ~ T? as T — 0.
Superconducting states in which the gap width has isolated nodes of higher orders are
also plausible. For example, in the axial phase with d-wave pairing
g(k) ~ (k + iky)? (7.6)
there are two second-order nodes at the poles of the Fermi surface. For this phase,
calculations similar to those described above yield C, ~ T’.
? In this section we use for brevity the spectrum in the A-phase expressed as Ej! = ./€2 + A? sin? 6, which
is different from Eq. (5.36) by the redefinition of the magnitude of A.
TEMPERATURE DEPENDENCE OF THERMODYNAMIC QUANTITIES FOR T - 0 45
The results of this section can be summarised as follows:
(&)"- Ao/T the gap in the spectrum is nonzero

T everywhere,
C Tr the gap hasfirst-order nodes

G ~ T.}? at isolated points, (7.7)
nIT-0
T the gap has line nodes
Tt or second-order nodesat isolated
c
points.
Here C, is the specific heat of the normal phase.

One can easily verify that other thermodynamic quantities also vary according to a
power law as T — 0, for example, the London penetration depth, Knight shift (or
paramagnetic susceptibility), as well as kinetic coefficients, such as the electronic thermal
conductivity or ultrasound attenuation coefficient.
Power-law temperature dependence in the low-temperature range of the quantities
listed above is a direct indication of an unusual nature of the superconducting state.
Moreover,since in the case of strong spin-orbit coupling fortriplet pairing the symmetry
nodes in spectrum can occuronly at isolated points on the Fermi surface (see Section 4),
the difference between the power exponents in the cases of line and point nodes allows
one,in principle, to distinguish between the spin-singlet and spin-triplet superconducting
pairings.
These simple results, however, are difficult to use in practice because the presence of a
negligibly small amount of impurities in a superconductor turns the line nodes into the
strips of a finite width, hence the specific heat is a linear function of temperature at low
temperatures. Isolated point nodes are blurred by impurities and change to spots of a
finite size aroundthese points [23]. These processes notably affect the temperature depend-
ence of thermodynamic quantities and complicate the interpretation of experimental data.
We will reconsider this issue in Section 21 dedicated to the effects of impurities on the
properties of unconventional superconductors.
8 Effects of Electron Number Parity in
Superconductors
According to the BCS theory, the groundstate of a superconductor described by equation

(5.9) is a superposition of states with different numbers of Cooper pairs. The super-
conductor energy at zero temperature is lower than that of the normal state by
6E, ~ NA? /ep (see Exercise in Section 5), where N is the total number of electrons.
Excited, ic. unpaired, electrons have energy levels separated from the ground state by a
gap of width A. Therefore, if the number of electrons changes by one, N — N + 1, the
change in the energy 6E, should be +A. The sign in front of A is plus or minus,
depending on whetherthe initial numberN of electrons is even or odd. Since the energy
A is usually of the order of several kelvins (since A~T,), it may seem that measuring
6E, due to the unit change in the enormous number N is an insurmountable problem.
Nonetheless, such measurements became feasible with the advent of the so-called Cou-
lomb-blockade or single-electron tunneling (SET) transistors (24, 25].
This section describes the operation of this device, which providesa direct proof of the
existence of Cooperpairs. A calculation of the change in the thermodynamic potential of
elementary excitations in a superconductor for various superconducting states due to a
unit change in the total numberofelectrons [26, 27, 28] is also given.
A Coulomb-blockade transistor (electrometer) is a rectangular piece of aluminum film
(an island) included in anelectric circuit between two tunneling junctions with capacit-
ance parameters C; and C2. The film dimensionsin an experiment performed at Harvard
University [24] were the following:thickness 200 A, width 600 A, and length 2 - 104 A.
The island was connected via a capacitor C, to a gate that allowed one to tune the island
potential by applying the gate bias voltage V, (Figure 8.1). If the coupling between the
island and external circuit is sufficiently weak and the tunnel resistance of each junction
satisfies the condition R > h/e?, the quantum states of the island are characterised by
47
+V/2 ~V/2
T Island
I
Cg ——
Ve
FIGURE8.1 Circuit diagram of the Coulomb-blockade (SET) electrometer.
definite numbers of electrons.! If the total capacitanceofall junctions C = C) + Co + Cz

is sufficiently small, the elementary electrostatic energy E, = e”/2C is higher than the
temperature, and thermal fluctuations can be neglected. Under these conditions, the total
electrostatic energy of the island
_@__, (ent CV)

U (8.1)
5696
is a periodic function of the gate voltage (Figure 8.2a), therefore the current across the
island at a fixed voltage applied to the external circuit should also be an e-periodic
function of C,V,.
This is the case when the aluminumislandis in the normalstate. It was observed in the
superconducting state that at temperatures below 0.3K, which equals 0.47,, the current
peaks corresponding to odd numbers of electrons begin dropping with the temperature,
and the period of the function j (C,V,) changes to 2e. A natural explanation ofthis effect
is that the difference between the free energies (to be exact, thermodynamic potentials 2)
of the island in the superconducting state with odd and even numbers of electrons,
Qoda — even, is about the gap width in the spectrum of elementary excitations at T — 0.
Therefore, the parabolic sections of the curve U(C,V,) corresponding to odd n arelifted
by Qoad — even if A > E, and are no longer observable (Figure 8.2b). Consequently, the
current j = j(C,V,) becomes a function with period 2e.
An island is formed by two Josephson junctions connected in series. We are interested
in the current across the island as a function of its energy. The formula has the simplest
form when the applied voltage is zero”:
j RV Msilts2 Ep . (8.2)
1In order to continue the discussion without interruption, we give the proof of this statement in the
Appendix to this section.
2 The derivation of the formula for the current is given at the end ofthis section.
EFFECTS OF ELECTRON NUMBERPARITY IN SUPERCONDUCTORS 49
“Je -e 0 e@ 2CMh% te -- 0 e@ RCH

a b
FIGURE 8.2 Approximate curves of the island energy as a function of the gate-induced charge C,V,: (a) for
e /2C > T, 60; (b) for 69. > €?/2C > T.
where K is the Josephson energy (amplitude of tunneling) of each junction, which are
assumed to be equal for simplicity, nsj and m2 are the densities of superconducting
electrons in the leads on bothsidesof the island; ® is the ‘external’ phase difference, i.e.
the phase difference between junctions connected to the island, Ep is the island energy,
including both the electrostatic contribution (8.1) and the component changing by
6Q = Qoaa — Meven When the change in C,V, switches the parity of the number of
electrons on the island:
60, if nis odd, (8.3)
Eo =U+ {6 if n is even.
In orderto calculate 6M, we should take into accountthat the thermodynamic potential of
the superconductor is composed of the energy of the Cooper pairs condensate and the
thermodynamic potential of the gas of elementary excitations. The condensate contains
an even numberofparticles, therefore the difference between thermodynamic potentials
of the superconductorin the case of odd and even numbers of electrons coincides with the
difference between 9-potentials of ensembles with odd and even numbers of quasi-
particles. The thermodynamic potential of the quasiparticle gas is expressed as a sum of
potentials of all states labeled by the quantum numbers i = (k,@), each of those can
contain n; = 0,1 quasiparticles with energy EF;:
Q= 7X u( Do ome), (8.4)
where 3 = 1/T. This formula can be rewritten as
Q=- Tin] Jd + ePE)
=-TlIn ( +S ce > SoePEPE >, Soo eBBEA )

i iF i jAik#ij
= —T In(Zoaa + Zeven)s
where
Zeus = DePB: 4aD 3aBEBEt (8.5)

i ffikdij
YeRP
Zeven = 145i j#i (8.6)
are grand partition functions for ensembles of particles with odd and even numbers of
quasiparticles. The corresponding thermodynamicpotentials are given by the equations
I]Q + eh) = Ita —ePhi)

Qoaa/even =-TIn Zodd/even =-Tih-
2
= Ogcs _ Tine
5( + Twn) (8.7)
Hence,
6Q. = Qo dd — Q Aéeyen
vi
1—f(T)
= Thar
+ f(T)’ (8 . 8)
where
1) = []tann*. (8.9)
ka
Nowlet us analyse the effects of particle number parity in a normal metal and various
superconductors. In a normal metal
B oO
T)= [Tenn = exp 4NoV fagin tanh 5 =exp(—2m’NoVT). (8.10)

o a
Here Npis the density of states per spin projection and V is the sample volume. Thus, the
parity effects are negligible,
Qodd — Qeven & 2T exp(—21°NoV T), (8.11)

if the temperature is larger than the spacing between electron energylevels in the island,
5E = (NoV)~', or, to be more accurate,
6E
T>T*s ae . (8.12)
8.12
In microscopic islands fabricated for the Harvard experiments SE ~ 2 -10°*K.

In conventional superconductors, the gap in the spectrum of elementary excitationsis
non-zero everywhere and
co
E EdE 1—e/T
= II tann = exp< 4NoV d | c
JE2 — A2 my + e78/T
| (8.13)
ka
A
S Sl
EFFECTS OF ELECTRON NUMBERPARITY IN SUPERCONDUCTOR
The latter expression can be transformed at low temperatures T <Ato

eff
f(T) = (wn) ; (8.14)
where
= 4NoV Jfr Jmol

Nesp =
EdE -(E-AVT 3 94/
a 2V2nAT NoV, (8.15)
which, in turn, allows us to obtain the following estimate for 62:

60, 2 A— Tin Neg. (8.16)
electron is
This formula has a clear physical meaning: the free energy due to an unpaired
m of the effective
the gap in the spectrum minus the temperature times the logarith
contrast to the case
numberof states occupied by the thermally generated excitations. In
es of odd current
of normal metals, the onset of the parity effects (the drop in the amplitud
peaks) takes place at the temperature
SNe
To
A
. (8.17)
8.17
icles:
At this temperature, the island should contain only a few quasipart
Nop © OOO? = Neg eT. (8.18)
In the Harvard experiments T,* ~ 0.3K.

zero at isolated.
Nowlet us considerthe superconductors in which the gap width goesto
as in the polar
points, as in the A-phase of 3He, or onisolated lines on the Fermi surface,
superco nductors
phase. A calculation similar to that of the specific heat of unconventional
(see Section 7) yields
4 T3
fa(T) © exp (-GMv is): (8.19)
T?2
fooi(T) exp (-crv): (8.20)
case of the super-

where C is a numerical constant of the order of unity. Hence, in the
conductors with gap nodes at isolated points, we have
ar exp(—(T/Ti)’), at T > T;, (8.21)

Qoaa - Qeven =
6E, at T << T;.
Here
18 1/3
Ti = (= a*6E ; (8.22)
odd — QevenA
Tt, Tk Te T
FIGURE 8.3 Schematic curves of the difference between thermodynamic potentials of states with odd and
even numbers of electrons in a conventional superconductor (upper curve) and in superconductors where the
spectral gap has nodesat isolated points or on lines.
One can seethat in this case 62. is always smaller than A. As the temperature drops, 62
increasesinitially, then it also drops. At the peak 60(T;') ~ Tj, where T; is the tem-
perature at which the numberof levels in the energy interval E < Ts is of the order of
unity (compare to equation (8.12)). At temperatures T < T; the discrete nature of the
specrtum must not be ignored, and in this temperature range Qogq — Qeven % OE.
For the superconductors with line gap nodes we have:
2
Ona — Qosey = 2 OP (- (7/73) ) for T > Ty, (8.23)
6E, for T < Ty,
where
. AbE\'?
pol = ( C ) : (8.24)
Asin the previouscase,the function 60(T) is non-monotonic.At the peak 60(Tro) © Tor
In conditions of the real experiment [24], Ty = 0.17, pol es 10-?7..
Qualitative behaviour of 62 for various types of superconductors is shown in Figure
8.3. The electron numberparity effect is considerably weaker in the microscopicislands
fabricated from unconventional superconductors. It takes place at considerably lower
temperatures than in the microscopic islands of conventional superconductors.
53
EFFECTS OF ELECTRON NUMBER PARITY IN SUPERCONDUCTORS
le in the
Thereis another factor thatlimits the possibility for the period 2e to be measurab
from a supercon ductor
current across a single-electron tunneling transistor manufactured
in such a transistor will,
with the gap nodes in its spectrum. The superconducting state
&). The density of states in
most probably, be suppressed in a surface layer with thickness
e the differenc e Qodg — Meven
this layer will be close to that in a normal metal. Therefor
may turn out to be exponentially small.
ducting
Thus the period doubling in the current across a Coulomb-blockade supercon
without gap nodes in the
transistor is feasible, as it seems, only in superconductors
spectrum of elementary excitations.
g of this
In conclusion,let us consider the two issues that were put aside at the beginnin
section in order not to break our discussion of the main topic.
Condition of an island’s weak coupling to an external circuit
connectingit
An island can be considered as an isolated entity provided that the junctions
states extended througho ut the
to the external circuit do not contain delocalised electron
not be affected by boundari es, and
junction volume. Electronstates in the junction should
6E >> AE(the localisat ion condition ).
this condition can be expressed by the inequality
AEis the shift of levels due to the
Here 6E is the spacing between energy levels and
1/SLNo,
boundary effect. In plane junctions with thickness L and area S, we have 6E =
elec-
where Np is the density of states and AE ~ h/t = hD/L?, where 7 is the time of
related to the
tronic diffusion to the boundary (L < JS ), D is the diffusion coefficient
junction conductivity via Einstein’s formula
e’DN =o.
the local-
Substituting all these expressions in the initial inequality, we finally obtain
isation condition [29]:
L h
R=— — 2 26KN.
os?
Current through two Josephson junctions connected in series
d using
The Josephson current in the circuit shown by Figure 8.4 can be calculate
[30], which can readily be generalis ed to the case of a Josephso n
Feynman’s approach
ng an
junction considered as a two-level quantum-mechanical system. After introduci
~, by by
v/2 fi 2 -V/2
FIGURE 8.4. Two Josephson junctions connected in series.

intermediate state, namely, an island with the wave function %p into a two-level system
with the wave functions ~, = \/ng /2e"?', 2 = ./ng2/2 e'®”, we write the Schrédinger
equations
O V
0
ine = Ky, + Ky. + Epo,
oO V
Here is the applied voltage, K is the Josephson energy (tunneling amplitude) of each
junction, and Ep is the island energy. When the applied voltage is zero, a direct current
flows across the junctions. Under these conditions, both the island wave function and the
phasedifference ¢. — ¢, do not depend on time. Thetime independence of the state 4p
yields the condition
— K(dr + yr)
YO
0
Taking account of this condition, the equations can be written as
OY RK?
nae
ih —__— a —
(i + ba),
Oy K?
nae ee hi + ¥2) .
hi = ——
Substituting the expressions for ~; and 7in the first equation and separating the ima-
ginary part, we obtain
O/Ns K? .
h at 7 ign Sin(g2 — d1).
Since the currentis proportional to 7), the final expression for the direct current through
two Josephson junctions in series, when the applied voltage is zero, takes the form
_ 2e R?sin(¢. —
j= F Viaig EO),
9 Paramagnetic Susceptibility and Knight Shift
in superconductors
The measurementof the paramagnetic susceptibility of the electron gas
the supercon ducting state. Althoug h a weak mag-
is an alternative technique for probing
persisten t supercon ducting currents, does not penetrate
netic field, which is screened by
the spin (Pauli) paramag netism in supercon ductors (the
into the superconductor bulk,
id Fermi liquid) is ‘an observab le phenome non.In this
more so in 7He, a neutral superflu
paramagn etic susceptib ility of electron gas in various
section, we will calculate the
superconducting states.
te to the spin
In a superconductor with singlet pairing, Cooper pairs do not contribu
and the entire spin magneti c momenti s determi ned by the
paramagnetic susceptibility,
contribution from the elementa ry excitatio ns:
M = Lp So (f(Ex-) — f (Ex,+))s (9.1)

k
where f(E)is the Fermi distribution function (6.2),
Fis = \/ 2 + A?|g(k)? + pa (9.2)

magnetic field H,
are the energies of excitations with spins parallel and antiparallel to the
, the nuclear magneti c moment). From
jig is the Bohr magneton (in the case of helium-3
equation (9.1) we derive
dQ Of (Ex) dQ. nw
— 9,2
anon |a
& [ae EE — 94,2
2inor F- Y(k,T),
t | _— (9.3)
M=
where
1 +co dé
———- —., 9.4

Y k,T =— 04)
(k,7) 4T | cosh? (E,/2T)
55
Sport ttF
T
FIGURE9.1 Sketch of the Yosida function,
and Ey = 1/2 + A?|g(k)|’. Hence we have an expression for the magnetic suscept-
ibility:
OM
X= By = Xn¥(2), (9.5)
where Xn = 2442No is the susceptibility in the normal state,! and the function
dQ ¥(k,7)
V(T) = It — = {01, aT=T,,
ange (9.6)
is called the Yosida function and determines the fraction of normal electrons in a su-
' perconductor (Figure 9.1).
In the temperature range 0 < T < T,, the behaviour of function Y(T) for different
superconducting states is different. In the low-temperature limit 7 — 0, calculations
similar to those of the specific heat in Section 7 lead to
el,
2
glk) £0,
Y(T) ~ @ , g(k) has nodesat isolated points, (9.7)
f,
c
g(k) has line nodes.
The paramagnetic susceptibility of a superconductor with singlet pairing tends to zero

as T — 0, which meansthat its energy in a magnetic field is higher than that of a normal
metal by ynH?/2 = u3NoH?. On the other hand, at T = 0 the superconducting state has
the energy lower by NoAj/2 (see equation (5.37)). The comparison between these two
energies leads to the conclusion that in a magnetic field higher than
H, (9.8)
V2 Lp
' Let us recall that No is the density of states per one spin projection.
PARAMAGNETIC SUSCEPTIBILITY AND KNIGHT SHIFT 57
the superconducting state is undoubtedly not favourable. In the field Hp, called the
paramagnetic limit of superconductivity, the singlet state of Cooper pairs is destroyed. In
conventional superconductors H, ~ 1 T.In reality, superconductivity is destroyed in type
II superconductors by fields higher than the uppercritical field Hp (see Section 12), or in
type I superconductors atthe critical field H,, both of them are considerably lower than
the paramagnetic limit H,. In addition to the paramagnetic limit, there is a diamagnetic
limit of superconductivity? in superconductors with non-zero orbital angular momentum
of Cooper pairs, irrespective of whether the pairing is singlet, S = 0, or triplet, S = 1:
Hy & (m* /m)Hp. Thefield Hg can be either higher or lower than the paramagnetic limit,
depending on the ratio between the effective electron mass in the material and the
electron mass in the vacuum.
The susceptibility against temperature (equation (9.5)) is measured by the following
method. Nuclear spins of atoms in a superconducting material precess in magnetic field
H with the frequency
w= 7H. (9.9)
At this frequency the nuclear magnetic resonance (NMR)is detected, ie. the resonant
absorption of radio-frequency magnetic field H,» with polarization perpendicular to the
constant magnetic field H.? Owingto the finite probability of an electron to be located at
the nucleus site R,, which is proportional to |. (Ra) ?, there is an interaction between the
nuclear magnetic moments and those of the conducting electrons, }, (the so-called
contact interaction):
Him ~ Hyb.O(r — Rn). (9.10)
The average value of p, in external field is given by the expression
1.) =, n
where x is the paramagnetic susceptibility and n is the density of the electron gas. The
shift of the nuclear spin energy levels due to this interaction
SE ~ pin |(Ra)
shifts the NMR frequency (9.9), i.e. the frequency of the transitions between levels in a
magnetic field (Knight shift) changes by
bw ~
MnX
(Ra) |". (9.11)
nh
Whenthe metal passes to the superconducting state, the paramagnetic susceptibility x in
equation (9.11) changes. Therefore measurement of the ratio 6w./dwn = Xs/Xn allows
one, in accordance with equation (9.5), to determine the density of normal electrons. It
2 See I, A. Lukyanchukand V. P. Mineev, Pis’ma Zh. Eksp. Teor. Fiz. 44 (1986) 183 (JETP Letters 44 (1986)
233).
3 In order to detect this effect, the magnetic field in the sample should be homogeneous, which is the case
when the sample dimension is smaller than the London penetration depth.
follows from equation (9.6) that the Knight shift in a superconductor with singlet pairing
should vanish as the temperature decreases.
Now let us consider a similar effect in superconductors with triplet pairing. The spin
states of all Cooper pairs in a superconductor are determined by the vector d, which
depends on the position of the momentum vector on the Fermi surface. The probability to
find a pair in the state with zero spin projection on the quantisation axis Z is proportional
to |d,(k)/? (see equations (2.5) and (2.7)). It is obvious that, if the external field H (which
defines the quantisation axis) is directed along d(k), the Cooperpair spin is perpendicular
to H and does not contribute to the susceptibility. Therefore it is determined by the
contribution from the excitations alone:
xi (k) = xXn¥ (k, T), (9.12)
where Y(k, 7) is given by equation (9.4) and Ex = \/€2 + A2|d(k)|’.

If the field (i.e. the Z-axis) is in the plane perpendicular to vector d(k), only the x- and
y-components of the vector d(k), from which the amplitudes +d,(k) + id,(k) of the
states with spin projections +1 on the quantisation axis are composed, are non-zero. It is
obvious that in this case both the Cooper pairs and the excitations contribute to the
susceptibility, and it coincides with that of a Fermi-liquid in the normal state:
X|| = Xn- (9.13)

In the case of an arbitrary field direction, the magnetic momentof a superfluid liquid is
determined by the susceptibility tensor:
M, = Xopllg,
which is obtained by combining equations (9.12) and (9.13):
da(K)
(kk) di, (k)da(k)
x00 | Fe [xapace) 1200 (0 Fase
B= k)( 64g -— >.
om)
14
As an example, we give expressions for susceptibility tensors in the A- and B-phases of

helium-3, which are derived from equation (9.14) after substituting the corresponding
order parameters* d4(k) and d®(k) (see Section 3):
x45 = Xn (Sap + VaVa(¥a() — 1), (9.15)

B 2 1
Xap = Xndap {3 +3 Ya(T) J. (9.16)
One can see that in the B-phase the susceptibility is isotropic, and at T — 0 the Knight
shift in a superconductor with the B-phase structure does not vanish completely.
‘In calculating the susceptibilities of the A- and B-phases of helium-3, one should take into account the
changesin the applied field due to the magnetisation of the liquid (Fermi-liquid corrections) [3, 6]. Although the
magnitudeof this effect is quite considerable, it does not lead to changes in qualitative behaviour, andsoit is not
discussed here.
PARAMAGNETIC SUSCEPTIBILITY AND KNIGHT SHIFT 59
In the A-phase, the susceptibility is a uniaxial tensor. In reality, the susceptibility of the
A-phase is always x» at a sufficient distance from the vessel walls since the vector Vv
always turns in a direction perpendicular to the magnetic field so as to minimize the
energy of magnetic interaction. Nearthe walls the vector V is perpendicular to the surface
which meansthat the susceptibility in the A-phase is anisotropic.
A similar effect should occur in superconductors with triplet pairing and strong spin—
orbit coupling fixing the direction of the vector d. Paramagnetic effects (in particular, the
Knight shift) must strongly dependin this case on the direction of external magnetic field
[31-33]. The angular dependenceofthe susceptibility of any triplet phase ofthoselisted
in Tables 4.14.6 is determined after substituting the corresponding expressions for the
order parameters d(k) = 57, nay(k) in equation (9.14). One should keep in mind, how-
ever, that the result depends on the specific form of the basis functions of the irreducible
representation. The temperature dependenceof different components of the susceptibility
tensor should be determined with due account of the function 7;(T) derived from
equations like (6.12). The paramagnetic susceptibility of anisotropic superconductors
with triplet pairing and weak spin-orbit coupling is identical to the Pauli susceptibility in
the normal state.
Exercises
(1) Derive equations (9.5) and (9.14) by calculating the spin magnetic moment directly.
Hint: Find the Bogoliubov transformation that diagonalises the Hamiltonian
H = Hycs — ip So at, (CopH) ang,

k
where Hpcs is Hamiltonian (5.1). Using this transformation, calculate the contribu-
tion to the expectation value of the spin magnetic moment operator which is pro-
portional to magnetic field
M = pp S "(aia Oop Akg)

k
(2) Calculate the Yosida functions Y,(T) and Yg(T) for the A- and B-phases at T — 0
and T — Ty.
10 Landau Expansion of Superconductor Free
Energy
The superconducting state is formed from the normal one through a second-order phase
transition. According to the Landau theory, the change in the free energy density due to
such a transition can be expanded in powers of the order parameter. In the case of one-
component superconductivity, when the order parameter is a complex scalar function
n = |nle® = Ae'® (see Section 4), this expansion has the form
Feona = Fs — Fy = an)’ +E inl = al? + Fat, (10.1)
where a(T) = ao(T — T,)/T. changesits sign at T = T,, a and 6 are positive constants.
The minimisation of F, yields the order parameter as a function of temperature,
A(T) = -F T -T,
a (10.2)
Cc
and the free energy

2 2
_ T-T,
Frond — 2B ( T. ) (10.3)
near the transition temperature. Equation (10.3) allows us to calculate the specific heat
jump at the transition point to the superconducting state:
2
0’ Freond
(Cs _ Ci)lpor.= —-T, (10.4)
OT? T=T, TB
Equation (10.1) and its generalisation to the spatially non-uniform case play an import-
ant role in the theory of superconductivity. It can be derived from the microscopic
61
Bardeen—Cooper—Schrieffer theory. This section is dedicated to deriving such an equation

for an arbitrary type of pairing.
The superconductor free energy has the form
F, = (Hpcs) — TS. (10.5)

where Hgcs is the BCS Hamiltonian (5.31):
_ + 1 + 1
Hgcs = DF Dyce, Piece + 3 » Axop Fag + 5 DG — Ex), (10.6)
and S is the electron gas entropy given by the formula
S=— J (ficlnfic + (1 — fic) In(1 — fic); (10.7)

ka
and J is the Fermi distribution function (6.2).

Let us consider for definiteness the case of unitary phases with triplet paring, when the
order parameter and the energies of elementary excitations are determined by the formulas
Ex = \/& + A?(T)d(k)d*(k),
Axap = A(T)d(k) gq;
Fieap = Fie Bap

(see Section 5). Calculating the statistical expectation values, we have
(oes) = 3 [Bich + 5(A(T)AKF, + 6 — Fe).

ka
At the sametime,
—TS = TS" In(1 — fic) + 1) fcln; A

: 7 —Jk
“ . (10.8)
= TY in — fic) — 0 Bicfie-
ka ka
Substituting these expressions in equation (10.5), we obtain:
F, = 5 [A(2)d(k)Fy + & + 27 In(1 — fic) — Ex]. (10.9)

k
The first summand onthe left of this equation is transformed, using equation (5.17), to
Ad*(k) = ~ S°Vi(k,k)Fy..
k’
LANDAU EXPANSION OF SUPERCONDUCTOR FREE ENERGY 63
By multiplying the left- and right-hand sides of this equation by Ad(k) andintegrating
over the angles with the help of the normalisation condition and the expansion (5.4) of
potential V;(k, k’), we obtain
= Ad(k’)Fy..
A?
—= aatk)'
By taking account of the expression for the free energy (6.10), we obtain, in turn, that
2YE]
NoA*
oO In——
in rT. = » Ad(k’)Ej..
(KF,
Finally,
2YE
F = Nod? Ine + Dee + 27 Im(h — fe) — Exd.- (10.10)
Since weare only interested in the condensation energy,i.e. the difference between the
energies of the normal metal and the superconductor, we take into account the equality
O
BA 2 inl — fc) — Be] = —2d(k)F;,
and rewrite equation (10.10) in the form
A
2
Frond = Not’ In vw _ 2 > faa d(k)F¥. (10.11)
The k
0
Integration over the wave vectors is performed using the rule (1.8), and it is more
convenient to perform the integration over energyfirst:
Ej E]
1-2
No / Fidé = NoAd*(k) / dei
2Ex
El El
At A -+ 0 this equation reduces to the following expression (compare with the derivation
of equation (6.18)):
. 2€9 mT 7¢(3) env (Ay

NoAd*(k) laze nx me d(k)d* (k) (=) |
= NoAd*(k) a2 — ToC) a(k)a"(k) (F) | ; (10.12)
Substituting equation (10.12) into (10.11) and integrating with respect to A, we have
_ vate 63)
Poona = NoA In T, + 1672 No
|< “qe
An (d(k)d (k)) T2"
Giventhat the difference between T and T, is small, we finally have
T-T. 7¢(3) [e AA
Foon ‘ond = N07 7
T, =A? +5
1672 No0 —
aa | (d(k)d*(k))°=.
( ) ( )) T2 ( 10.13 )
Similarly one can obtain the Landau expansion for the case of singlet pairing:
Foond ont = NMon <A? + FEIN No| —(s(k)g*(k))*—.

T-—T, 7¢(3)
F(a" (W)*Ge-
dQ AN
(10.14
10.14
In particular, in the case of a conventional s-wave secon (g(k) = e'*),

T -T, 7¢(3
Feona = No——<A? + os) Nora (10.15)
Thus, we have obtained the Landau expansion for superconductors with triplet! and
singlet pairing deriving from the BCStheory. Thecritical temperature in equations (10.13)
and (10.14) is the same for all superconducting states with given / (i.e. the states be-
longing to the given irreducible representation of the normal state symmetry group). At
the same time, the energies of superconducting states with given / and different sets of
_coefficients in the expansions (4.8) or (4.9) of the order parameter in terms of the
spherical harmonics(in the general case, in terms of the basis functions ofthe irreducible
representation, see (4.10) or (4.11)) are different. Indeed, the equilibrium condensation
energy (10.3)
Fo =~ (7B)([ Brannan?) (10.16)

dependsessentially on the type of the superconducting pairing. For example, after sub-
stituting order parameters from Section 3 into equation (10.16), we find that, among the
p-wavestates, the B-phase (d(k) = k) has the lowest energy. In particular, its energy is
lower than that of the A-phase d(k) = \/3/2 (k, + ik,0,0) by a factor of 6/5 [22].
Actually, at low pressures the liquid helium-3 transforms to the superfluid B-phase
from the normalstate. But in the region of higher pressures (Figure 3.1), the liquid first
transforms to the A-phase, from which first-order transition to the B-phase takes place.
This meansthatat high pressures and about 7, the A-phase energy is lower. The conflict
between this fact and our conclusion is resolved by taking into account that
equation (10.13), from which we concludedthat the B-phase hasthe lowest energy, is not
universal. In deriving this equation, we relied on the seemingly natural assumption that
the pairing interaction does not change in the superconducting state. In particular, we
assumed it to be the same in all superconducting phases with given I (the weak coupling
or BCS approximation). In reality, this is not the case, and V(k,k’) depends on the
specific form of the order parameter (the strong coupling). Although this fact does not
1 Let us emphasize that expansion (10.13) is valid only for unitary phases (see Section 5). The Landau
expansion for arbitrary superconducting states with triplet pairing will be derived from the BCS theory in
Section 18.
LANDAU EXPANSION OF SUPERCONDUCTOR FREE ENERGY 65
change theassertion that all phases with given / have the samecritical temperature, the
form of the fourth-order term in A in equation (10.13) is altered, and the conclusion that
the B-phase hasthe lowest energy at all temperatures and pressures fails. The effect of the
pairing type on V(k,k’) can be investigated only on the basis of a specific microscopic
model (see Refs. 3 and 6), and we will not do this, especially as there is no practical
possibility of verifying one strong-coupling model or another.
11 Superconducting States with Multicomponent
Order Parameters
It follows from the discussion in Sections 4 and 10 that all possible superconducting
or superfluid phases whose order parameters transform according to some (multi-
dimensional) irreducible representation of the point symmetry group G have the same
critical temperature, but different free energies. Calculations based on one or another
microscopic model yield the coefficients in the Landau expansion and allow one to
answer the question about whatis the final state after the transition, as it was done in the
previous section on the basis of BCS theory. One can come, however, to the conclusion
that different states can have the lowest energy in their respective regions of the phase
diagram (for example, not only the B-phase, but other p-wave phasesat different pressures
and temperatures) using phenomenological methods, without a reference to a specific
microscopic model. The starting point for the solution to this problem is the Landau
expansion which can be obtained onthe basis of general symmetry considerations [34].
Landau expansion for free energy in p-wave states
The order parameter in a superconducting Fermi liquid with p-wave pairing is a complex
3 x 3 matrix A,; (see Section 3), which transforms under spin rotations as a vector with
respect to the index a and under coordinate rotations as a vector with respect to the index
i. Being a scalar parameter, the free energy is independentof the reference frame in which
these vectors are defined. In other words, the expansion should be invariant under arbit-
rary and independent(in the absence of spin-orbit coupling) three-dimensionalrotations
of the spin and orbital spaces. The free energy is also a real quantity, i.e. it should be
invariant under complex conjugation of the order parameter (time-reversal symmetry) and
under multiplication of the order parameter by an arbitrary phase factor e® (gauge
invariance).
67
One can formally write all the mentioned transformations as
~ 5S pO
Agi 3 Agi = Rog Ry e'? RAg;,
where R*, and RG are the matrices of three-dimensionalrotations in spin and coordinate
(orbital) spaces, respectively, and RA,; = Aj, is the time reversal operator. The most
general expression for the free energy density satisfying these invariance conditions
contains only five fourth-order terms:
Feond = Agi Ag; + BilAai Aail” + Bo(A%; Aci)” + 634%; Api AX, Agy
+ By Ac Api Ay Aaj + Bs A%j Aoi Ab Ag. (11.1)
In this equation, the matrices A and A* occurin pairs, and in all terms the spin indices are
contracted with spin indices and the orbital indices with orbital.
The free energy density (11.1) has several extrema determined by the equations
6Fcond /bAci = 0. Which of these extrema are minina and which of these minima are
absolute depends on the relations between the coefficients 8, which, in turn, depend on
the temperature and pressure.'! The A- and B-phasesare associated with minima in Fcond:
The order parameters for these phases are expressed by the matrices (see Section 3)
Aa, = *A(T)Va(Al + iA"), (11.2)

AB, = A(T)Raj e’®, (11.3)
where V,A’,A” are unit vectors (A’A" = 0), Rg; is the matrix of three-dimensional
rotations, and A(T)is the absolute value of the order parameter. The A-phasestates are
degenerate in directions of the vector V and the vector pairs A’ and A”, and the B-phase
states are degenerate in the phase ¢ and with respect to three-dimensional rotations
determined by the order parameter matrix R,;.
Unlike equation (10.13), the expansion (11.1) allows formation of the A-phase. Ac-
tually, by substituting equations (11.2) and (11.3) into equation (11.1), we get
Fond = 30d? + 9A* (Ba + 23 + Ba),
FBcond 3aA? + 9A4 («1 + Bo Orth

3
)
Henceis follows that the A-phase is more energetically favourable than the B-phaseif 3;
(or 8s) is sufficiently large.
' The problem of determination of all extrema of functional (11.1) in a general form was solved by
Berezinskii [35]. Similar results were obtained independently in Ref. 36.
SUPERCONDUCTING STATES WITH MULTICOMPONENT ORDER PARAMETERS 69
Multicomponent superconducting states in crystals
Suppose that the superconducting state corresponds to one of the multi-dimensional

representations of the crystal point symmetry group. In the case of strong spin-orbit
coupling the order parameter in such a state has the form (see Section 4)
e(k) = moi (k) + myS(b) +--+ at S=0,

(11.4)
d(k) = mwi'(k) + mwi(k) +--+ at S= 1.
For both singlet and triplet superconducting states, the specific free energy near the
transition point is expressed in the form of an expansion in powers of the complex
coefficients 7;, which should be invariant under transformations of the normal state
symmetry group G = U(1) x R x G. Incalculating such an expansion, one must take into
consideration that the transformation properties of the basis functions 4 (Ik) and 4)(Kk)
under the symmetry operations can be represented as the transformation properties of the
coefficients 7.
For example, the basis functions of the representations E), and E}, of the group De, are
proportional to the components of a vector in the basal plane (Table 4.1), Le.
(WE (kK), BE (kK) ~ (kekxs keky); (11.5)

(wy (k), Wo (k)) ~ (Zk, Zy).
Therefore, one can assumethat the coefficients 7 and 72 are transformed by operations
of the group Dg, as the components of such a vector”. The scalar products nn*, nn, nn"
are invariant underall rotations of the group Ds. They can be used in compiling tworeal
fourth-order invariants. There are no other invariants in the case of hexagonal symmetry.
Hence the Landau expansion has the form
F=onn' +5 (nn) + 2 inn’ (11.6)

The minimum of the free-energy (11.6) at* < Ois scoched at the order parameter of the
form
N = no(cos A, sin de®, (11.7)
2
"I Bi + Ba’
where ¢ and . are arbitrary phases. The degeneracy in islifted only when a sixth-order
invariant is added to the expansion (11.6):
yRe(m + in)’ (nj + ing)”: (11.8)

If y <0, the free energy minimum is attained at A= A, = m/3, n=0,1,...,5, if
+ > 0, at A, = 1/3 + 77/6. All superconducting states described by the order parameter
2 The action of operations of the gauge group reduces to multiplication of the order parameter components
by a commonphasefactor: (m,7™) — e'(m, 7), and the time reversal is equivalent to complex conjugation:
(m2) — (ni, 7)
(11.7) with A given above formally belongto the same superconducting class D2(C2) x R,
butthe directions of symmetry axes for different A, are different. For example, for y < 0
and A = 0 the superconducting class is described by
Do(C2) x R = {E, Cry, e™Cay,Co} x R.

For £2 > 0 the energy (11.6) has a minimum at?
V= no(1, tie", (11.9)
"o
226;
This solution corresponds to the superconducting class
inn inn
D¢6(E) = { exp () C,,, exp (3), \
where n = 0,1,...,5. Like the A-phaseof helium-3, the state (11.9) is not invariant under
the time reversal operation, which implies the existence ofa spontaneous magnetisation
of Cooper pairs. This issue will be discussed again in Section 15.
For superconducting states corresponding to the two-dimensional representations E47,
and E>, of the group D¢n, the free energyis still described by equation (11.6). Its minima
are determined by equations (11.7) and (11.9) and formally belong to the same super-
conducting classes, including however other symmetry elements, in accordance with the
properties of the basis functionsof the representation E> underthe symmetry operations.
In a tetragonal crystal (G = Dy,), the basis functions of the only two-dimensional
representation E also have the form (11.5), i.e. they transform as the components of a
vector in the basal plane. But in this case the symmetry allows the existence of three
fourth-order invariants, and the Landau free energy has the form
Fann + Som’+ 2inn? +2 nl + inf. (1.40)

Depending on the relation between the coefficients 3, and 83 (see Figure 11.1), the
energy is minimal for the solutions of three types:
nN ~ (1,0)(or(0,1)), (1,41), (1, +i). (11.11)

The real phases correspondto the classeslike D){C2) x R, and, as in hexagonalcrystals,
the directions of symmetry axes for different phases are different. The complex states
belong to a magnetic class
imn inn
Dg (E) = {exp (=) Cy, exp () Re, \
where n = 0,1,2,3.
3 Using the results of the previous section, one can easily verify that in the BCS theory
(weak-coupling
approximation) 8; = 2) > 0.
SUPERCONDUCTING STATES WITH MULTICOMPONENT ORDER PARAMETERS 71
B3/Byf
a,b
B,/P;
(1, 1) (1, 0)
B3=— 28,
FIGURE 11.1 Domainsofthe existence of two-componentstates (1,0), (1,/), and (1,1) in a tetragonal crystal
in the (5, 83) plane.
In crystals with cubic symmetry and in superconducting states whose order parameters
1 = (m,™, 73) transform according to one of two three-dimensional representations of
group O; (Tables 4.5 and 4.6), the specific free energy is expressed in the form similar to
equation (11.10):
B= ann’ + emmy? +2 inn? +S(im! + bl! + Il). (11.12)

In the case of a two-component order parameter, corresponding to the two-dimensional
representation, the free energy has the form
Pann’ +2 Bi(qn+2 hal? + vning? tain), (11.13)

where we have added a sixth-order invariantto lift the degeneracy of the real states.
Here we do notlist all possible minima of the functionals (11.12) and (11.13) and
corresponding superconducting classes. This can be done [9] similarly to the simple case
of a tetragonal crystal discussed above.
Exercise
Derive the Landau expansion of the free energy of an isotropic d-wave superconductor.
12 Ginzburg—Landau Equations and Upper
Critical Field
This and several following sections of the book are dedicated to the Ginzburg—Landau
theory for anisotropic superconducting states. We assume that the reader is familiar with
the Ginzburg—Landau theory for conventional superconductors (see, for example, Ref. 37)
and focus our attention on specific issues related to unconventional superconductivity. We
start with constructing the Ginzburg—Landau functionals and calculating the upper cri-
tical fields in type II unconventional superconductors.
One-component superconducting states
The Ginzburg-Landau functional, i.e. the difference between the Gibbs energy! of a
superconductor with a one-component order parameter n(r) = |n(r)|e*" in an in-
homogeneousstate near T, and that of a normal metal is expressed as
G= |ere- [er (r-=), (12.1)
wherethe free energy density F is different from that in equation (10.1) since the gradient
energy and the magnetic field energy are added:
F = ao(—5)+
T-T,
Shalt + Rylan) . (Opn) +5
B?
(12.2)
' In a fixed external magnetic field H, it is more convenient to use the Gibbs energy G(T’, H) instead of the
free energy F(T, B).
73
Here
; 20 ,
D; = -iV; +3 Ai (i =X; 2); (12.3)
0
®o = nhc/e is the magnetic flux quantum,” and B = curlA is the magnetic induction
vector.
The tensor Kj, which is called the effective mass tensor, describes the crystal aniso-
tropy. So, in uniaxial crystals with hexagonal (or tetragonal) symmetry
Ky = (54 — 28)Ki + 2:2)Ka. (12.4)

In cubic crystals K, = Ky, ie. Kj; = K6,;. The coefficients of the gradient expansion of
the free energy will be calculated using the microscopic theory in Section 18.
The distributions of the order parameter 7 and the vector potential A in the coordinate
space should minimise the functional G:
6G
—=0,
5G
—=0. 12.5
én* ” 6A ( )
By varying equation (12.1) with respect to 7* and neglecting the intégral over the su-
perconductor surface (surface effects will be discussed in the next section), we obtain the
Ginzburg—Landau equation:
T-T.
ao 7 *)n + Blnl’n + Ky D;Djn = 0. (12.6)
Comparing thefirst and the last terms in equation (12.6), one can see that the theory has a
characteristic scale in coordinate space, namely the correlation length €(T), which is
different along different crystal axesi:
K, \'?
a(n)
(T) xh ~n( 54) (12.7)
12.7
The formula estimating (7) for an arbitrary direction is of the form
an~a(Ba*) (12.8)
T.—T —1/2
where £9 = fiug/2nT, is the Cooper pair dimension (see Section 1).

Tn general, the superconductor energy should also include the terms of higher orders in
gradients than K;;(Dj;7)"(Djn). The fact that they are neglected in this approach means
that the Ginzburg—Landau theory provides an adequate description of slow changes in the
order parameter on the scale larger than £.
? Hereafter e denotes the absolute value of the electron charge.

GINZBURG-LANDAU EQUATIONS AND UPPER CRITICAL FIELD 75
Uppercritical field
The uppercritical field H.9(T), at which a second-ordertransition to the superconducting

state occurs, corresponds to the lowest eigenvalue of the differential operator in the
linearised Ginzburg—Landau equation. Before discussing the anisotropy of the upper
critical field, which is a specific feature of some crystalline superconductors with a
multicomponent order parameter, let us analyse the case of one-component super-
conductivity in uniaxial crystals. In this case the linearised Ginzburg—Landau equation
has the form
T—T.
oa 7 )n+ KD? + Din + K4D?n = 0. (12.9)
In the case of a magnetic field in the basal plane,
H = H(cos y, sin y, 0),

(12.10)
A= Hsing, —cosy¢, 0),
we derive from equation (12.9)
dn nH T -T,
—K.Gn (Ze) 2n-bao( T, )n =0. .
(12.11)
Using the fact that this equation is formally identical to the Schrédinger equation for a
charged particle in a magnetic field, whose eigenfunctions and eigenvalues are well-
known, we obtain
(12.12)
Doao T. -—T
HoT)
On J/RiRy Ts”
i.e. the upper critical field in the basal plane of a hexagonal (tetragonal) crystal is
independentof its direction.
The uppercritical field depends on the magnetic field direction only whenthefield is
off the basal plane. For example,if the field is in the (y, z) plane,
H = A(0, sin§, cos @),

(12.13)
A = Hx(0, cos 6, — sin @),
the solution of equation (12.9) yields
® TY —-T
Ho(T) = oe (12.14)
274/K,(K; cos? 6 + Ky sin’ 6) T.
In cubic crystals, K, = K, and the uppercritical field is independent of the magnetic field
direction with respect to the crystal axes.
Multicomponent superconducting states in crystals
Let us proceed to the case of the two-component superconductivity with a vector order
parameter 1 = (1x, 7), which belongsto either the E, representation of the group Dg, or
the E representation of the group D4 (see Section 4). The Ginzburg—Landau functionals
are expressed in the form of the expansions in powers of two complex functions 7, and 7
and their gradients, which should be real and invariant underall symmetry operations of
the De, (Dan) group. The latter condition means that all terms in these expansions look
the samein all reference frames whichare transformed from one to another by symmetry
operations of the group De, (or D4). By retaining only the terms quadratic in the order
parameter, which are essential for calculating the upper critical field, we write the
Ginzburg—Landau functional for the vector representation in a hexagonal crystal,
Fi = 29 T-T\_,
an + K, (Dini)*(Dinj) + Ka(Din)*(Dyn)
* * B’
+ K3(Djnj)" (Djni) + Ka(Dem)" (Dem) + re (12.15)
and in a tetragonal crystal,
Free = Fhex + Ks [(Dene)* (Derr) + (Dd. My)” (Dyny)| , (12.16)

where i = x, y.
The free energy density Fhex contains only the scalar products of two vectors in the basal
plane, n and D(nn*, D1 etc.). Therefore it is invariant underall rotations in the basal
plane. Terms specific to the hexagonal anisotropy of a crystal are of higher orders in the
gradients. Given the full invariance of the free energy underrotations by an arbitrary angle
in the basal plane,the uppercritical field is isotropic. This property can be proveddirectly
by solving the equations obtained by varying the free energy (12.15) with respect to 7:
T
K\D?nj + K2DDin + K3D;Djnj + K4D?nj + a ( 7) =0 (12.17)
c
in the gauge defined by equation (12.10). By choosing the reference frame such that the
x-axis be parallel to the magnetic field, we derive a system of two independentdifferential
equations from equation (12.17):
dn Ky (22)"zZony + 00 (“2ne = 0,
Kyat
(12.18)
-K,o+ (Ki + Ka + Ks) (at)2ny + 00 (7
FE)= 0
whose eigenvalues determine two possible values of the field H.2(T):
Poa Te —T
; 12.19
Hey (I)= nVKi
Ky TT ( )
® T, —T
Hg(T) = Qn oe ‘ (12.20)
(Ky + K> + K3)Kg Te
Hh
Fo
Nx
Het My
T, T
FIGURE 12.1 Linesof the phasetransitions for two-component superconducting states in a hexagonal crystal
under magneticfield.
the larger of those corresponds to the uppercritical field, at which the superconducting
phase transition occurs. Thus, the upper critical field is isotropic in the basal plane of a
hexagonal crystal in the case of two-component superconductivity. This property is
proved for the state corresponding to the Ey representation in Ref. 38.
Note another important corollary to equation (12.18). It is clear that in a magnetic field
the phase transition from the normal to the superconducting state brings about one of the
two superconducting phases:
Nx ~ (1; 0)fo(z) (12.21)
ny ~ (0, 1) folz), (12.22)

where fo(z) is the Landau ground state wave function for a charged particle in magnetic
field. On the other hand,if the transition in zero magnetic field for a vector representation
leads to a complex phase (see equation (11.9)),
n~ (1, +4), (12.23)

then the transformation of a superconducting state with the order parameter (12.21) to the
state (12.23) as the magnetic field decreases at T < T, should be accompanied by a
transition generating a phase with the order parameter (12.22) (Figure 12.1). A similar
process should take place if the transition in the absence of magnetic field gives rise to a
state with a real order parameter:
N ~ (cos Ay, sin An), (12.24)
where the parameters A,, are determined by the lattice anisotropy (Section 11).
The isotropy of H.2(T) in the basal plane of a hexagonal crystal, naturally, disappears
when any perturbation breaking the hexagonal symmetry is applied. For example, a weak
yh
ay
FIGURE 12.2 Basal plane anisotropy of the uppercritical field for a two-component superconductingstate in a
tetragonal crystal.
orthorhombic perturbation characterised by vector M in the basal planegenerates a term

in the Ginzburg—Landau functional with orthorhombic symmetry of the form
7(Mn)"(Mn). (12.25)
This perturbation both splits the transition temperature (the components of 1 parallel and
perpendicular to M occur at different temperatures) and leads to a notable anisotropy in
the uppercritical field [39]. The latter property follows from the fact that the equations
for the order parameter components are no longer decoupled (except for the specific field
directions H||M and H lL. M).
Now let us consider a crystal of the tetragonal symmetry. Its specific feature is an
additional term in the gradient energy (12.16), which has a four-fold symmetry axis x. In
this case, the linearised Ginzburg-Landau equations have the form
K,Dinj + K2DjDinj + K3D;Djnj + KyD?n;
T-T,
+ K5(6.;D¢n. + 5yD3ny) + oo ( 7 :) nj = 0. (12.26)
Cc
Let us assumefor simplicity that K. = K3 = 0, then the equations for the order parameter
components are decoupled and, in the case of the field defined by equation (12.10) in
the basal plane, we obtain the following values of H,. for the components 7, and »,,
respectively:
(12.27)
Boao Te —T
HQ(1) = pO
2ny/K4(Ki +Kssin’y) ~°
b T.-T
HO(1) ~ 20 oe ¢ Te (12.28)
Ks(Ky + Ks cos? y)
For each field orientation H(y) one must select the larger of these two values. Thus, we
have obtained the anisotropy of the upper critical field, which is typical of the two-
component superconductivity [40] (Figure 12.2).
Anisotropy of the upper critical field of the same nature takes place also in cubic
crystals in the case of two- or three-component superconducting states [38].
In the general case, i.e. when the applied field has an arbitrary direction with respect to
the crystal axes, the uppercritical field for a multicomponent order parameterin the range
of parameters where the Ginzburg—Landau theory is valid, can only be calculated nu-
merically. The only exception is the problem of calculating H..(T) for a two-component
order parameter in a hexagonal(or tetragonal) crystal under a magnetic field H directed
along the six-fold (or four-fold) axis, which can be solved analytically [41].
In this case, the last term in equation (12.16) does not radically change the equations,
and we will solve the problem at Ks = 0. Since the magnetic field is directed along the
six-fold axis Z (the Landau gauge A = (0, Hx,0) is used), the order parameter can be
considered to be independent of z, and we derive from equation (12.17) the following
equations:
(Kiz3D? + K,D?)ny + (KpDyDy + KxDyDx)ny + 00 (757 my =0, «.29)

12.29
(KinsD% + KiD?)ny + (KsDDy + KDyDz)ne + 00 (7) ny = 0,
where Ky.3 = K; + K7 + K3. Let us introduce the new functions ni = 7, + iny and
operators Dy = D, + iDy, and take into account that [D,,D,] = —27iH/®po. Then the
equations transform to
(co ("2") + Ko(D? + D3) — K_ =) n, + K,Din_ = 0,

20H
(12.30)
K,D?n, + (0 (4*) + Ko(D? + D*) + K_ ag =0,
where Ky = (K123 + K1)/2, Ky = (Ko + K3)/2.
Let us seek the order parameter in the form
ns = exp(—ipy)f(x). (12.31)
Then the Ginzburg—Landau equations have solutions of two types:
Ga ~ (7m) (12.32)
f-(@) 0 7
or
(ros) ~ (Cn) 99)

where g is a constant and the function F,,(x) is related to the Hermite polynomials H,,(x)
by the following formula:
_ nH ®) \ QnH By
F,,(x) = 19|- 2 (, - rh) |a| (ean): (12.34)
That the set (12.33) is indeed a solution to equation (12.30) can be easily checked using
the identities [42]:
2nH
DF, = —An(n _ DF»,
Bo
2nH
DF, = Bo Fraa,
2nH
(Dy + DS)F, = (2n +1) “by
By substituting equation (12.34) into (12.31), we obtain an expression for the transition
temperatures corresponding to this set of solutions:
T-T 27H
a rt [Con +3)Ko+ /2Ko — K_y +4(n+ (n+ 2)| B (12.35)
The maximum uppercritical field corresponds to either the solution
Ga oc (%), (12.36)
f(x) 0
which yields
(1) Poa T —T
H.c2 ( (TT) ) = >.
2n(Ko —K_) Te , ( 12.37 )
(2) (i) vm
or the solution
which leads to
Hg)(T) = - (12.39)
2 BDpao T, —T
2n(3Ko — (2Ko — K_)” + 8K)

The form of the state resulting from the phase transition in a magnetic field depends on
the relations between the coefficients K;. In particular, in the BCS theory K, = Ky = K3
(see Section 18), and the highest uppercritical field corresponds to the state (12.38).
If the applied field is lower than H,.2(T), the nuclei of the superconducting phase
corresponding to different values of the degeneracy parameter p form a periodiclattice of
Abrikosov flux lines, whose shape can be essentially different from the usual triangular
lattice (see for details Ref. 43).
Spatial parity breaking and helicoidal phases
All the multicomponent superconducting states discussed above originate from normal
phases whose symmetry groups contain the spatial inversion operation. If otherwise, then,
firstly, the classification of superconducting states as even or odd does not make any
sense since they can be mixed (see Section 4), secondly, it becomes possible to construct
invariant terms in the free energy linear in spatial gradients (Lifshits invariants).
For example, if the order parameter 7 = (7x, Ny) corresponds to the two-dimensional
F, representation of the group Dg, then, in addition to the terms of expansion (12.15),
there is an invariant like
UmDem+ ¢.c.). (12.40)

Inclusion of such terms leads to notable changes in the thermodynamic and magnetic
properties of the system,in particular, to the existence of non-uniform (helicoidal) phases
in zero magnetic field [7].
Exercises
(1) Prove that the Ginzburg-Landau functional for a two-component order parameter
corresponding to the representation FEof the group Dg (the basis functions are given
in Tables 1 and 2) can also be written in the form (12.15). (Hint: Using the com-
ponents of the vectors D and n, compose the expressions invariant under the
operations of the group De, and find a transformation n; — x; such that the gradient
energy could be transformed to the form (12.15) as a functional of x; 2).
(2) Determine the critical temperature and the states emerging after the phase transition
in a hexagonal superconductor without an inversion center taking into account the
terms like (12.40) in the free energy.
13 Boundary Conditions and Surface
Superconductivity
Nuclei of superconducting phase near surfaces of type II superconductors emerge in

magneticfields higher than the uppercritical field. In order to calculate the surface critical
field, one should solve the linearised Ginzburg—Landau equations taking account of the
boundary conditions for the order parameter. In this section we will derive the boundary
conditions and discuss the issue of surface superconductivity in crystals. Surface prop-
erties of unconventional superconductors essentially depend on the surface orientation
with respect to the crystal axes. Experimental tests of this dependence can be used for
identification of the symmetry of superconducting phases.
Boundary conditions. One-component superconductivity
The Ginzburg—Landau equations were derived in the previous section from the condition
that the free energy variation in the bulk should be zero. However, there is also the surface
contribution to the free energy:
OF\s, eraa = —F ¢ dS nKij(Din)6n", (13.1)

where n is the normal to the surface, which vanishes provided that
niKyDjn|= 0. (13.2)
It meansthat the componentof the current density normal to the surface is zero: nj|,= 0.
Assuming that the order parameter near the surface in zero magnetic field can only vary
in the direction of the normal to the surface, we obtain
(nV)n\s= 0. (13.3)
83
Henceit follows that, in the absence of magnetic field, the order parameterat the surface
is the sameas that in the bulk of the superconductor.
However, even in the case of conventional superconductors, this conclusion derived
from the Ginzburg-Landau theory needs verification from the microscopic theory. The
point is that, as was shown in the previous section, the Ginzburg-Landau theory applies
only to the order parameter varying on scales larger than the coherence length &.
Therefore it does nottake into accountthe changesin the conditions for superconductivity
to emerge close to the surface compared to those in the bulk. The microscopic analysis
(see below in Section 20) indicates that the wave functions of electrons near the surface
within a distance of the order of the lattice constant are notably different from the wave
functions in the bulk. This, in turn, leads to the emergence of additional contributions to
the free energy whichare localised on the distance of about & from the surface. This fact
can be taken into account phenomenologically by introducing a surface energy
Fs= $ dSa(n)|n/?, (13.4)

which depends on the crystal surface orientation with respect to the crystal axes. Here
a(n) ~ No&of(n), f(n) is a dimensionless scalar function ofthe orientation of the normal,
which is invariant under all symmetry operations from the crystal point group.
Boundary conditions for the order parameter can be obtained by varying with respect
to 7° the total free energy of the superconductor,
F=Fy+t+Fs, (13.5)
which includes the conventional bulk component (12.2) and the surface energy given by
equation (13.4), The condition that the variation vanishes at the surface takes the form
inj KyDjn| = a(n). (13.6)

Thus, we have introduced a new characteristic dimension to the problem, namely the
healing length, which is a function ofthe direction of the normal:
Ki
The effective boundary condition for the order parameter near the transition temperature
can be derived by comparing b(n) with the correlation length €(n) in equation (12.8).
Let the normal orientation be such that the surface invariant f(n), and hence the
function a(n), is zero. Then we get the boundary condition (13.3) from equation (13.6).
The healing length in this case turns out to be infinite.
But if f(n) # 0 for a given normalorientation, the healing length b(n) is finite and
independentof the temperature. Therefore, at T — T., the inequality b(n) < E(n) holds,
which leads, in turn, to a boundary condition for the order parameter of the form
nls= 0. (13.8)
The result that for f(m) #0 the boundary condition (13.3) should be replaced by
(13.8) can be obtained using elementary energetic considerations. The increase in the
BOUNDARY CONDITIONS AND SURFACE SUPERCONDUCTIVITY 85
superconductor energy near the surface is the sum of the gradient (13.1) and the surface
(13.4) contributions. Their relative value at T — T, can be estimated, given that the
characteristic length over which the order parameter changes is the correlation length
€(T) ~ (1 — T/T), and its bulk value is || ~ (1 — T/T.)\””. Therefore, we
obtain from equation (13.1)
3/2
T
Fs, grad ~ (1 _— r) ‘ (13.9)
If f(n) 40 and the order parameter at the surface is non-zero, we derive from
equation (13.4)
T
Fs~ (1 -7). (13.10)
The comparison of equations (13.9) and (13.10) indicates that Fs is larger than Fs praa
near the critical temperature. This meansthat the essential increase in the surface energy
vanishes only if superconductivity is fully suppressed at the surface, which leads to the
boundary condition (13.8). Iff(m) = 0, then the surface energy (13.4) does not lead to an
increase in the total energy, and the boundary condition (13.3) holds.
It is obvious that the reflection and transmission conditions for quasiparticles at an
interface between a superconductor and a normal metal lead to changes in their wave
functions in the boundary layer, i.e. f(n} 40 for all directions of n. Therefore, the
boundary conditions (13.8) are always valid in this case as T — T,. As far as an interface
between a superconductor and a dielectric or vacuum is concerned, one should distin-
guish between the cases of specular and diffuse reflection of quasiparticles at the
interface. Let us first consider the case of specular reflection.
In this case f(n) 4 0 forall orientations of the normal with respect to the crystal axes,
except those for which the electron spectrum ¢(k) andthe functions g(k) (or d(k)), which
describe superconducting states and transform according to a one-dimensionalirreducible
representation of the crystal symmetry group, do not change as a result of a specular
reflection in the boundary plane:
e(k — 2n(Kn)) = e(k),

(13.11)
g(k — 2n(kn)) = g(k), (k — 2n(kn)) = d(k).
Actually, if these conditions hold, the trajectories of quasiparticles reflected from the
interface are mirror reflections with respectto the interface of the trajectories of incident
quasiparticles continued into the half-space occupied by the dielectric (see for details
Section 20). Therefore the problem is equivalent to the calculation of the order parameter
in a superconductor unbounded in space, and superconductivity is not suppressed on the
interface, i.e. the boundary condition (13.3) apply.
Thus, the nodesof the function f(n) for a given superconducting state should corres-
pond to such orientations of the interface which coincide with the symmetry planes
common to both the Fermi surface and the superconducting order parameter. In the case
of a spherical Fermi surface and isotropic superconducting state (s-wave pairing), f(m) is
TABLE 13.1 Angular dependences of the order parameter and the

surface energy for the case of a one-component order parameter in a
tetragonal crystal (S = 0, G = Day)
r a(k) f(a)
Aig ki + ky an? (nz +n) + br2nd (ne — 2)?
Arg Keke(K2 — K2) n+ re
Big ke — ky na (ny + ny) + bain,
Bog kek andl + 2) + b(n? — my
an
identically zero for all orientations of n. Therefore, it is generally accepted that the
boundary conditions (13.3) are satisfied at the superconductor—dielectric interfaces.
In the case of conventional superconductivity, corresponding to the identity rep-
resentation Aj, in an anisotropic crystal, the order parameter symmetry coincides with
that of the Fermi surface and incorporates all symmetry operations of the crystal point
group. Thefunctions f(n), which go to zero along all mirror-reflected symmetry axes, are
expressed in the case of cubic, tetragonal, and hexagonal symmetry respectively, as
San (in
n) = alnin
n,(nz—n3)* +nen2 (n2—n?)? +nin2 (np —n2)"], (13.12)
fae(A) = ane (nt, + 0)” + bnzny (ne = 2)’, (13.13)
FREa) = ann? + 2) + Bled —3nar@)*8 — 32). (13.4)

Here a and b are the numbersthat characterise the anisotropy, i.e. the deviations of the
shapes of the Fermi surface and the gap in the spectrum from sphere or cylinder.
The boundary conditions (13.3) apply to a narrow region ofdirections of the normalof
width ~ ./&/€(T),' where the function f(m) is zero. For all other orientations of the
superconductor—dielectric interface the boundary conditions have the form (13.8).
If we deal with an unconventional superconducting state, whose order parameter
transforms according to a non-trivial representation, the number of interface orientations
for which the condition f(n) = 0 is satisfied can only be less than in the case of a
conventional superconductingstate. Table 13.1 lists the corresponding functions for one-
component superconducting states with singlet pairing in tetragonal crystals, which are
popular at present in connection with the studies of high-T, superconductivity.
Table 13.1 clearly showsthat for the A), representation the surface energy turns to zero
for eight directions of n in the basal plane and n||2. Only four nodesin the basal plane and
one nodeat n||Z remain for the representations B,, and Bog. The vertical mirror-reflecting
planesfor the representations A), (Fermi surface) and Ade (superconducting state) do not
! This estimate is obtained by comparing the gradient energy (13.1) to the surface energy (13.4) nearthe axis
along which f(n)is zero.
coincide. Therefore, if the order parameter transforms according to A2,, the function
fa, (m) has only one nodeat nijz, i.e. on the line perpendicular to the commonhorizontal
symmetry plane of the functions e(k) and gy,, (k).
There are no symmetry reasons why the function f(n) should go to zero in the case of
one-component superconducting states in a tetragonal crystal which are odd in spatial
coordinates (S = 1 and strong spin-orbit coupling, see Table 4.3). Therefore the surface
energy in this case is an arbitrary combination ofall scalar invariants of the tetragonal
group.
Here we do not calculate the functions f(m) for non-trivial superconducting states in
hexagonal and cubic crystals and leave this task to the reader (see Exercise at the end of
this section).
Surface superconductivity
Boundary conditions (13.3) and (13.8) for the order parameter obtained in this section
allow us to calculate the critical field for surface superconductivity in the region where
the Ginzburg-Landau theory applies.
Consider a tetragonal superconductorfilling the right-hand half-space x > 0 so that the
tetragonal axis is in the interface plane and the normalto the interface is in the crystal
basal plane. Let the magnetic field be directed along the tetragonal axis:
H = H(0,0,1),
A = (0, Hx, 0).
By substituting the order parameter in the form (x,y) = f(x) exp(—ipy) in the Ginz-
burg—Landau equation (12.9), we obtain
df InH\* &) \7 T—Te

“Ki ga th (Fe) («-ps2) £+ 00( T, \r=o. (13.15)
The solution of this equation and the surfacecritical field are determined by the boundary
conditions.
If the surface orientation is such that the condition (13.8) is satisfied, i.e.
n(x = 0) = 0, (13.16)
then a superconducting phase nucleusis generated far from the surface (pé(T) >> 1). The
corresponding solution of equation (13.15) has the form
TH Bo 2
f(x) ~ exp -# («-r52h) | ,
and the magnetic field in which the superconducting phase nucleus first appears equals
the uppercritical field in the bulk:
_ Poao T. —T
3 (T) = HoT) . (13.17)
— OnK, T
But if the surface orientation is such that the boundary condition (13.3) is satisfied, i.e.
on =0, (13.18)
Ox x=0
then equation (13.15) has a solution localised near the surface:
f(x) « F,(x) (13.19)
_ TH Bo 2 2nH Bo
rls) =o] BE (x=) ||yEE(o—v Bt ,
where H,(x) is the Hermite function (or the parabolic cylinder function) with index
v(A) = 545. (13.20)

Here we have introduced a dimensionless parameter
_ Boag Te —T
2kiH T,
The substitution of the expression (13.19) into the boundary condition (13.18) yields a
transcendental equation
2vH,_\(—r) = —rH,(—r), (13.21)

where
r=p4/ ®o
PN RH
which allowsus to calculate (r). The magnetic field value at which a nucleus of the
superconducting phase emerges near the surface corresponds to the minimum of the
function A(r). Numerical solution of equation (13.21) yields [78] Amin = 0.59, r = 0.77,
hence
H.3(T) = 1.69 Ho(T). (13.22)

In the conventional superconducting state (representation A;,), the boundary condition
(13.18) applies, strictly speaking, only to the surfaces whose orientations are
n = (cos(7k/4), sin(xk/4), 0), where k = 0,1,...,7, or n = (0, 0, 1). If the normal to
the surface deviates from the directions given above by an angle larger than ./f/€(T),
the boundary condition (13.18) is replaced with (13.16), and no surface superconductivity
occurs. '
In real materials, the anisotropy of the conventional superconducting state is not very
strong. The point is that both the impurity scattering and the averaging effect of the
diffuse scattering at the surface lead to a reduction in the function f,,, (m) without sup-
pressing superconductivity, and for this reason the surface superconductivity is always
detected, irrespective of the surface orientation.
The situation is different if the superconducting state transforms according to non-

identity representations. So, in tetragonal crystals, in a state belonging to the Bj, repres-
entation, which is believed to be realised in high-temperature superconductors, surface
superconductivity takes place in the case of a specularly reflecting interface for the
following orientations of the normal:
k sin,
n= (cos, k 0), k=0,1,2,3, n= (0, 0, 1).
If the normal deviates from these directions by an angle larger than ,//E(T), surface
superconductivity does not occur. In contrast to the case of the Aj, state, diffuse boundary
scattering does not create conditions for surface superconductivity near surfaces with
arbitrary orientations, but, on the contrary, leads to the averaging of the order parameter
over momentum directions, thereby suppressing the surface superconductivity.
The ultimate conclusion is the following: the absence of surface superconductivity at
diffusely reflecting surfaces can be an indication of unconventional superconducting
states. Surface superconductivity detected in narrow vicinities of certain orientations of
the normal vector n can help to determine the symmetry of the superconducting state.
Boundary conditions for multicomponent order parameters
In this case, the expression for the surface energy can be obtained in exactly the same way
as the expression for the gradient energy in Section 12. For example, for a super-
conducting state transforming according to the two-dimensional representation E in a
tetragonal crystal, one should compile all possible combinations quadratic in the order
parameter components (7, 7) and the normal vector n which are invariant under all
operations of the normal state symmetry group U(1) x R x Day:
Fs = f as|ax(n)nn’ + ax(a))nns + ry?

+ as(n)(Inst? + Inymy)?)). (13.23)
Here a;(n) ~ No£of;(n) (@ = 1,2, 3) are functions invariant under all operations from D4,.
With the exception of interface orientations coinciding with the crystal axes, both
components of the order parameter transforming as (k,k,,k,ky) have no definite parity
underreflection in the interface (cf. equation (13.11)). Hence follows, as in the case of a
one-component order parameter, that both components of the order parameter go to zero
at the surface, and no surface superconductivity occurs. The surface orientations defined
by the crystal axes deserve a special investigation. We are going to investigate the simpler
case of a two-component superconducting state in a hexagonal crystal, when the formula
for the surface energy is almost the same as (13.23), but without the last summand on the
tight, which meansthat the energy is invariant under arbitrary rotations aboutthe six-fold
axis.
Surface critical field for a vector order parameter in a hexagonalcrystal
Like the upper critical field in the bulk, the surface critical field for multicomponent
superconductors can be calculated analytically only in specific cases. In particular, this
can be done for the order parameter belonging to the Z; representation in a hexagonal
crystal if the field is directed along the six-fold axis and the normalto the interface is in
the basal plane [44].
The surface energy has the six-fold symmetry under rotations around the hexagonal
axis. Therefore, when the surface normal coincides with one of the crystal axes, one can
define the reference frame such that the <-axis coincides with the normal. Then the mixed
terms like 7/7are eliminated, and the surface energy is expressed as
Fs= fas (6, ln ? + beim’). (13.24)
Since the pair (7,7) transforms as (k,k,, k,ky), the component 77; changesits sign after
reflection in the yz-plane, and the component7) retainsits sign. For this reason, the vector
order parameter should satisfy the following boundary conditions at a specularly re-
flecting interface:
Om
Mlr-0=9 Z| =. (13.25)
x=0
In order to calculate the surface critical field of a superconductor occupying the half-
space x > 0 in a magnetic field pointing along the six-fold axis, one should solve the
Ginzburg-Landau equation (12.30)
(a0 (72) + Ko(D? + D2) — K24) n, + K,Din. = 0,

(13.26)
KD?ny + (a0 (5%) + Ko(D? +2) + K4) n_ = 0,
with the boundary conditions (13.25).
Whenthe uppercritical field was calculated for an unbounded superconductor, we had
to imposethe condition that the order parameter should vanish as x —> —oo. As a result, the
solution could be expressedin terms of the Hermite polynomials. In solving the problem of
surface superconductivity, however, we do not impose a condition on the solution at —
hence we have abandonedthe condition that the index of the Hermite polynomial should
be integer and non-negative. Thus we have to deal with the Hermite functions H,(x).
Weare seeking a solution of equation (13.26) in the form
(a) Ory)
where F,,(x) are given by equation (13.19), and index v is derived from the equation
ao Ft
To = (-027+3)Ko+ Vek KP 4+ NW +2) (3.27
2nH
The parameter g is given by the equation
—(2Ko — K.) + /(2Ko ~ K-P +4+ 1)(v + 2)K3

qv) = Atv + 1)(v + 2)Ky
Unlike the case of a one-component order parameter (equation (13.20)), equation
(13.27) does not yield a single-valued expression for v as a function of the dimensionless
parameter
_ PDoao Ty —T
OnkKiH T,
Since the equation is quadratic in v, it can have two roots at fixed A:
3) AKoKi VD
™,2(A) = ~5t 2(Ke — K?) ) (13.28)
where
D = 4Kj + Ki} —5KjKi. — K_(K§ — K{)(4Ky — K_) + VK}Kj.

The values of q;2 in this case are
gi,2(A) = K,(Kg — Ki) (13.29)

(2Ky — K_)(Kj — K3.) + AKi Ki, £ VD Ky
In what follows wewill assumethatthe discriminantis positive and 1,9 and q; 2 are real.”
The eigenvalue of the equation system (13.26) is doubly degenerate. Therefore its
solution is expressed as
(a) Cay) eCei) «30

where s is a free parameter, which can be assumedto be real without loss of generality.
Substitution of this solution into the boundary conditions (13.25) yields a system of two
transcendental equations for A(r,s) (cf. equation (13.21)). By excluding s from these
equations, we obtain the equation for A(r):
Aj (A, r) _ A2(A, r)
(13.31)
BiQ,r) ~ B(A, r) ,
where
Ai(A,r) = rH,(—r) + 24f,-1(—r) ~ rqify42(—r) — 2qi(+ 2)Ay41(-7),

Bi(A, 7) = Hy,(—r) + gifly,42(-7)
? Relaxing this restriction would not lead to principal difficulties since the Hermite functions can be
analytically continued to complex values of index v. Notethat, if K} = K2 = K3 (weak-coupling approximation,
see Section 18), then D > 0.
Here2, gi,2 are functions of ) (see equations (13.28) and (13.29)). Minimisation of the
solution with respect to r solves the problem in principle,i.e. it allowsus to calculate the
critical field H,3 for surface superconductivity.
An important property of equation (13.31) is that it does not explicitly depend on H.
Hencethe solution H.3(T), corresponding to Amin, is a linear function of T, but it seems
impossible to calculate the corresponding coefficient analytically. Numerical calculation
of K, = Kz = K;yields the following result: Appin © 0.89, r+ 0.55, and
Ho3(T) © 1.24 He9(T). (13.32)

Here we have used equation (12.39) for the bulk uppercritical field.
Note that, if the Fermi surface is assumed to have cylindrical symmetry, the surface
critical field is the same for all surface orientations, provided that the hexagonal axisis
parallel to the surface. This result also applies to p-wave superconducting states. In the
general case, as in the case of one-component superconducting states, surface super-
conductivity vanishes if the normal to the surface deviates from a crystal axis by a very
small angle.
Exercise
List the surface invariants f(m) for all one-component states in hexagonal and cubic
crystals.
14 Meissner and Mixed States in Unconventional
Superconductors
Most anisotropic superconductors (high-temperature and organic superconductors, and

heavy-fermion superconducting compounds) are typical representatives of type II super-
conductors. Electrodynamic properties of such materials are described by the London
equation, i.e. there is a local relationship between the current density and the vector
potential at all temperatures down to T = 0. In this section, we will discuss some
properties of unconventional superconductors that can be described in terms of the
Londonelectrodynamics. In addition to the usual effects of anisotropy, these properties
demonstrate, like the thermodynamic quantities, some specific effects due to the presence
of the gap nodes in the spectrum of elementary excitations.
Meissner effect
The combination of the equation
6G
— = 0
6A
(see Section 12) with the Maxwell equation
Ani
curl B = —-4
c
(14.1)
yields an expression for the current density j. For example in a one-component super-
conducting state, when the free energy density is expressed by equation (12.2), the
current density is determined by
ji = —2eKy|n* (Dyn) + n(Djn)’}. (14.2)
93
For a two-component superconducting state in a hexagonalcrystal (the representation E))

we have from equation (12.15)
: 2e %
= = {KinjDinj + Kon;* Din; + Kan;2% Dini + c.c.}, .
i=x,y, (14.3)
. 2e .
i= ~ Kali Dyn; + ¢.c.). (14.4)
Substituting the order parameter in the form »(r) = |n(r)|e? = A(r)e™ into
ji = —en;w; , (14.5)
where we have introduced the velocity of the Cooper pairs condensate (the superfluid
velocity),
h 2e
= owe A 14.6
ve Om (ve + hic ) (14.6)
(mis the electron mass), and the tensorof the density of superconducting electrons (the
superfluid density):
ni6S
= Rp Argip 14.7
(14.7)
For the case of two-component superconductivity with a ‘real’ order parameter of the
form (11.7)
1 ~ (cosa, sin dele),
characterised by a common phase ¢ for both components, the current density can be also
expressed in the form of equation (14.5) with the superfluid density tensor nj, expressed
in terms of the coefficients K,,K2,K3, and K4. The situation is more complicated in
superconductors with a complex order parameter (11.9), and it wiil be discussed in the
following section.
Thus, in non-magnetic superconductors with an arbitrary number of the order para-
meter components, the relation between the current density on the one hand, and the
phase gradient and the vector potential on the other hand in a weak magnetic field has the
form of equation (14.5). It is noteworthy that a linear relation like equation (14.5) holds in
type IT non-magnetic superconductorsat all temperatures. The temperature dependence of
the tensor nj;(7’) will be calculated below.
Like the free energy density, the current density is invariant under gauge transforma-
tions:
A-A+Vx,
2e (14.8)
@ > PFs
C
MEISSNER AND MIXED STATES IN UNCONVENTIONAL SUPERCONDUCTORS 95
which allows us to transform equation (14.5) to
, e ,
i= — ni Al (14.9)
Substituting equation (14.9) into (14.1) we obtain an equation for the vector B (the
London equation):
mc 2
is cut (ios\ ) —1 cutlB 4+B=0. (14.10)
The tensor nj; is uniaxially anisotropic for all superconducting states in uniaxial crystals
(hexagonal and tetragonal) and for multicomponent superconducting states in cubic
crystals, and it can be expressed as
nj, = Nody + n' viv; , (14.11)

where v is the anisotropy axis. Substituting the expression (14.11) into equation (14.10),
we obtain
6 [curl curl B + A curl(v(v curl B))] + B = 0, (14.12)

where
mc 1/2
69 = ;
° (3) , (14.13)
and \ = —n'/(ng +n’).

Let the anisotropy axis v = 2 andthe applied field H = (0, H,, H,) be parallel to the
surface of a superconductor occupying the half-space x > 0. One can easily check that the
solution of equation (14.12) has the form
x
By = A, exp (- is) ; (14.14)
B, = H,exp (-2) (14.15)

0
that is, the magnetic field decays inside the sample (the Meissner effect), and its direction
rotates around the X-axis owing to the crystal anisotropy [45]. The length 6(7), whichis
different fordifferent directions, is called the London penetration depth and is determined
by the tensor of density of superconducting electrons, nj(T). Its typical values at T = 0
are in the range of 10~°-10-> cm.
Density of superconducting electrons
The temperature dependence of the tensor nj, can be determined using the following
reasoning. One can easily prove that equation (5.29) for the energy of elementary
excitations, with due account of the difference between k and —k, takes the form
By = TE (a5) +A2,
2
(14.16)
In a magnetic field which is a slow function of the coordinates,! the momenta of all
elementary excitations acquire an addition mw due to a non-zero velocity of the superfluid
component. From equation (14.16) we derive
Ex —_ Ectmw ra Ex + mvp(k)w, (14.17)
where vp(k) = 0€,/dk. The momentum flux density of excitations is

P= 5 vp(k)f(Ex + mve(k)w) , (14.18)
where f(£) is the Fermi distribution function. Let us introduce the tensor of the quasi-
particle density as the parameter characterising the response ofP to a changein velocity w:
6P; = ny éwy. (14.19)
From equation (14.18) we derive

Of (Ex + mvp(k)w
ny, = —m vp, (Ike,(4) revel) : (14.20)
ka
The difference between the tensors nj, in the normal (ic. at A =0) and super-
conducting states yields the tensor of density of superconducting electrons:
nj, = ny(A = 0) — nj. (14.21)
Neglecting the magnetic field dependence of nj;(the effects related to this dependence
will be discussed below), we obtain
n(T) =2 /Ganenig PM,

s —2m dSp Vp, (kK) pj (Ik) _ A
(14.22)
where Y(k, T) is Yosida’s function (9.4), and the integration is performed over the Fermi
surface. Equation (14.22) yields the tensor nj, for the Fermi surface of an arbitrary shape
and an arbitrary type of pairing. In the range of parameters where the Ginzburg—Landau
theory is valid, a similar expression for conventional anisotropic superconductivity was
obtained first by Gor’kov and Melik-Barkhudarov [46]. For T = 0
ni(0) = ds,F Ve, i(k)

i(k) vp,i(k)
j(k
(14.23)
(20h)? |vr(k)|
If the gap in the spectrum of elementary excitations has nodes, the components of
the tensor of density of superconducting electrons (or the London penetration depth)
are power-law functions of temperature as T — 0, similarly to the specific heat, para-
! To be exact, in the Londonlimit, when the penetration depth is larger than the coherence length, which is
always the case in type IT superconductors.
magnetic susceptibility etc. So, in the A-phase, where AZ = A? sin’ 6, calculations sim-
ilar to those of Section 7 yield [47]
(n3,(0) — n3,(T)) |, 9 ~ (F) ; (14.24)
(00) ~ WO ao (Es (14.25)

where is the total density of particles. Similarly, for the polar phase (Aj = A? cos? @)
we have
(n’,(0) — 03,(T)) ps0 n(z) (14.26)

(13,(0) = nD)rio m5 Cc
(14.27)
The low-temperature behaviour of ni(T) for phases with other configurations of the gap
nodes can be easily established.
Near the critical temperature
This expression corresponds to the case of singlet pairing, and in the case of triplet
pairing one should, obviously, make the substitution |g(k)|’ > |d(k)|’. The function
A(T)is given by equation (6.18). For a fully isotropic superconducting state, we derive
from equations (14.23) and (14.28) the well-known relation
n'(T — Ts) = 2n'(0) (1 - rz): (14.29)

Note that the matrix of coefficients Kj; which determine the lengths on which the order
parameter (equation (12.6)) and magnetic field (equation (14.10)) change is independent
of the electron mass, according to equation (14.7), but is a function (through vp(k)) of the
effective electron mass in the crystal.
Note also that we have not taken into account the mass renormalisation due to the
Fermi-liquid interaction between an electron and the molecular field generated by the
current of the rest of the electrons. This can be done by including the molecular field in
the velocity w:
wi > Ww; — MP, Pj
and resolving equations (14,18) and (14.19) with respect to 6P. Here F),;; is the tensor
of the Fermi-liquid interaction density in the crystal, which is a generalisation of the
parameter F,/(Nok2), which was defined for an isotropic Fermi-liquid. Generally
speaking, the inclusion of the Fermi-liquid effects changes the temperature dependence of
ni even in the isotropic case [49, 50]. In what follows, we will not take into account the
Fermi-liquid effects, assuming that the main contribution to the electron mass renor-
malisation is due to its interaction with the crystal lattice.
Nonlinear Meissner effect [51]
In addition to the power-law decrease in the Londonpenetration depth 6(T) as T — 0, the

presence of the gap nodesin the excitation spectrum leads to an increase in 5(0) with
magnetic field. In order to analyse this effect, let us turn to equation (14.20). At T = 0,
the derivative of the Fermi distribution function in this equation goes to zero forall values
of its argument except zero:
=m\° Ug, (kK) Up,(K)O(Ey + mvp(k)w).

= (14.30)
ka
Henceit followsthat in superconductors with a finite gap width, the tensor of the normal
component density at 7 = 0 is zero for all w which are smaller than the Landaucritical
velocity w. = A/mup.
If the gap width is zero on a set of points at the Fermi surface, the density of excitations
remains finite even at T= 0. For a superconductor with a spherical Fermi surface
equation (14.30) can be rewritten as
> IE Qs » I
naan fh ; _
qEE s(E-+ kw) = 3n f Tk, _, (14.31)
4/E? — Ag (kw)? — Ae
where nis the total electron density, and the angular integration is performed within the
limits determined by the condition (kw) > A2.
Suppose that the gap width is zero on the Fermi surface equator, which is the case in
the polar phase (Aj = A cos’ 6), and the superfluid velocity w = (e/mc)A is directed
along the y-axis (the superconductor occupies the upper half-space z > 0, the external
field is directed along the x-axis, and the condensate phase is constant in the chosen
gauge). Then it follows from equation (14.31) that at T= there is a non-vanishing
density of the normal component’:
h nantly) dp. 4ekp

ny © sal fg
=~ sin’ p|siny| =n omc |Ay|. (14.32)
Hence follows
4ekp
Hy =n (1 A 4). (14.33)
2 The emergence of the normal component density which is a non-analytic functionofthe field in superfluid
phases with the gap nodes in the excitation spectrum at 7’ = 0 wasfirst indicated by Volovik and Mineev [58].
The Maxwell equation (14.1), taking account of equations for the current (14.9) and the
superfluid component density (14.33), can be written as
OPA, 1
az = 524» (14.34)
where
1 me? 4ekp
sa=> tle |A,| }. 14.35
62 ial mmc | I) ( )
Thus, because of the presence of the line node on the Fermi sphere equator, the
expression for the London penetration depth contains a non-analytic term proportional to
the absolute value of the applied magnetic field.? It can be written in a convenient form
by expressing A in terms of the thermodynamiccritical field H¢:
HN,
waa’, (14.36)
in which the work done to expel the magnetic field from the superconductor equals the
gain in energy (5.37) (or (5.38)) due to the superconducting transition. Using the estimate
for the vector potential in equation (14.35), |Ay| ~ Ho, where 69 is given by
6(H) =
=a (14 +54). (14.37)
Mixed state
As in conventional type II superconductors, the Meissner (ideally diamagnetic) state

transforms in unconventional superconductors to the mixed state in which Abrikosov flux
lines (vortices) penetrate into the sample in magnetic fields higher than
& A(T) (14.38)

Mall) ~ ge52(T) *E(P)'
In contrast to the isotropic case, in anisotropic superconductors the direction and loca-
tion of vortices depend on the magnitude andorientation of the applied magnetic field
with respect to the crystal axes. The lowercritical field H.; is also a function of the
external field direction, and the shape of the flux line lattice can be different from a
regular triangular pattern. The theory of the mixed state in unconventional super-
conductorsis largely identical to that in conventional anisotropic superconductors, which
addresses manyspecific issues (the field distributions, the angular dependencesof various
3 In conventional superconductors the correction to the penetration depth is quadratic in the magnetic field.
quantities, etc.). In this book we do not dwell on the common parts of these
two theories
(see Refs. 45, 52-54).
Amongtheeffects specific to the mixed states in unconventional superconductors,
let
us mention, first of all, the phase transitions due to changes in the symmetr
y of multi-
component superconducting states [43]. An example ofsuch transitions was discusse
d in
Section 12. Another feature of multicomponent superconductivity is the possibili
ty of
superconducting states with spontaneous magnetisation [9]. Properties of such
super-
conductors will be studied in the next section. Finally, there is yet another effect
specific
to superconductors with non-trivial pairing: that is the unusual magnetic field dependen
ce
of the specific heat in the mixed state [55]. First let us consider the situation
in con-
ventional superconductors.
It is known thatthe order parameterin a superconductor goes to zero at a vortex
axis
and recovers its equilibrium constant value at a distance p~ &(T) from the vortex. The
presence of such a ‘well’ in the potential A(p) leads to the formation of quasipart
icle
boundstates localised inside the vortex core. The lowest energy of boundstates
can be
estimated using the uncertainty principle:
iit A?
10% TED) ep
eS —____. &
(14:39)
14.3
Since this energy is a factor of A/ép smaller than the lowest energy of excitation
s far
from the vortex core, the spectrum of excitations localised at the core can be deemed
gapless and almost identical to the excitation Spectrum in normal metal. Thus,
the
fraction of the type II superconductor volume in the mixed state occupied by the vortex
cores has the same density of states, as in the normal metal. Hence,
there exists an
additional contribution to the density of states, which is proportional to the fraction
of
area occupied by vortex cores in the plane perpendicular to the flux lines:
S
Moc & No > = Noné*ny. (14.40)
Here No is the density of states in the normal metal, ny = B/®pois the numberofvortices
per unit area, B is the magnetic induction (the average value of the microscopic magnetic
field in the sample).
In strong type II superconductors, where the condition 6(T)/E(T) > 1 is fulfilled, the
induction B is almost equal to the external field H throughout the magnetic field range
Ay, < H < Hog with the exception of the region close to H.,. Given this circumstance
and recalling the fact that the transition to the normalstate occurs in the field
Go
Ho © FEUD (14.41)
4 The density of states is given by the formula
N(E) = 50 8(E — Ex).

ka
in which the separation between vortex cores is comparable to €, we obtain

A
Noe
lo & Ni° Hey (14.42)
As a result, at low temperatures (T < T,) the specific heat of a superconductor in the
mixedstate is largely determined by the contribution of the excitations localised in vortex
cores:
Cy, & Hoo (14.43)
where C,, is the normal metal specific heat, which is a linear function of temperature.
Equation (14.43) applies also to superconductors with non-trivial pairing. If the gap in
the excitation spectrum, however, has nodes on the Fermi surface, additional contribu-
tions to the specific heat due to a non-zero density of states around these nodes are
possible. In the space outside vortex cores, the persistent superconducting currents
j = —en.w flow, which results in a shift in the energy of elementary excitations (14.17).
In the range of fields Hy <H<H., the separation between the flux lines
awn? ~ (®o/H)'”? satisfies the inequalities € < a < 6, and the distribution of the
superfluid velocity
w=-2-=
ens ~ Gren:
curl B
is determined by the contribution of the nearest vortex:
. yo 6
Bei7ol,
h®p
w =f.
om 14.
(14.44)
Here p is the distance from the flux line axis, and @ is the unit vector in the azimuthal
direction. If we again limit our analysis for simplicity to the case of a spherical Fermi
surface, the resulting contribution to the density of states due to the regions around the
gap nodes in the spectrum of elementary excitations is
Noéeloc = My fox 6(Ex + kw). (14.45)

ka
Here integration is performed overthe area of an elementary cell of the Abrikosovlattice.

We have (compareto the derivation of equation (14.31))
5(Ex + kw))=2m | F —__tkwl (14.46)

2 * " 4m Hew)? Az
where the range of integration is determined by the condition (kw)’ > A?. Further
calculations should be performed for a specific superconducting state.
Let us consider as an example the polar p-wave phase, where A? = A? cos? 6. The
main contribution to the density of states comes from the region near the Fermi surface
equator. After integration over the angles in equation (14.46), we obtain
2a
kplw| 4, Akelw|
No TA [ elcosgl = No A
0
After substituting this expression into equation (14.45), we obtain (taking account of
equation (14.44))
Ahy H
Nacloc NyNo re ~ Nowa (14.47)
This result indicates that in the mixed state at H < H.. the main contribution to the
density of electron states in a superconductor with nodes of the order parameter on lines
at the Fermi surface comes not from the vortex cores, but from the volume outside them,
where the superconducting currents flow:
Noeloc Heo
~~ 4/— > 1. 14.48
Nooc H . ( )
The specific heat of such a superconductor in the mixedstate at sufficiently low tem-
peratures should have the form?
e = ba
H
(14.49)
where b is a numerical factor. Such a dependence of the specific heat on magnetic field
was detected in experiments with high-T, (YBazCu307_; [16,56]) and heavy-fermion
(UPt; [57]) superconductors.
Exercise
Show that in a superconductorwith the gap nodesatisolated points at the Fermi surface,
the specific heat at low temperatures as a function of magnetic field is described by the
formula
HA Ho
In, (14.50)
C, Ho H
* See also N. B. Kopnin and G. E. Volovik, Pis’ma Zh. Eksp. Teor. Fiz. 64 (1996) 641 [JETP Letters 64
(1996) 690].
15 Magnetic Superconductors
Superconducting states with multicomponent order parameters can have a spontaneous

magnetic moment. The orbital angular momentum of a Cooperpair in a state corres-
ponding to the representation E, of the group Dg with the order parameters
g(k) ~ klk tik), S=0, (15.1)

d(k) ~ 2% + ik), S=1 (15.2)
equals fi. There are also states in which a pair has a nonzero spin, for example,
d(k) ~&(&+i9), S=1. (15.3)

A
From the viewpoint of symmetry, all such states correspond to magnetic superconducting
classes (Sections 4 and 11).
The magnetic moment MM of a superconducting magnetic material is composed of
magnetic moments of all Cooper pairs, and in a sample with volume V most of which is
occupied bypairs with magnetic moments directed along a unit vector [l, it is given by the
expression
M=MV, M~ fing
= ii. (15.4)
Here n, is the density of superconducting electrons and -y = e/2mcis the gyromagnetic

ratio. One can easily verify that the magnetic moment of a magnetic superconductor
equals that of a conventional superconductor of the same volume containing one Abri-
kosov flux line, multiplied by a dimensionless factor.
The magnetic momentof a superconductor given by equation (15.4) is generated by the
persistent currents flowing near its surface, whereas the magnetisation in the bulk is neg-
ligible. The pointis that the spin angular momentum ofpairs is compensated by the angular
103
momentum of unpaired particles. On the other hand, the wave functions of Cooper pairs
overlap strongly because the pair dimension £ is large compared to the interatomic
distances. For this reason, local currents generating the orbital angular momenta com-
pensate each other almost entirely in the bulk of the superconductor, but there is no such
compensation at the surface, and the surface currents generate a magnetic moment
[58, 59].
Local magnetism
Let us consider the situation at the quantitative level, taking as an example a two-
component order parameter in a hexagonal crystal. In order to calculate the density of
the internal spontaneous moment near the critical temperature, one should explicitly
single out the contributions proportional to the magnetic field in the Ginzburg—Landau
free energy functional (12.15). To this end, let us rewrite the gradient terms in
equation (12.15):
Fgrad = / d’r {K; (Djnj)" (Din;) + Ks(Dzmi)" (Dam)
+2 EE (in)(Dyn) + Om)Brn)
* aos (Dini) (Dini) — (Ding)" (Bimi)] \ (15.5)
Integration by parts of the last term on the right and the identity
2ni
iD;, Dj} = DD; — DD; = By Cue(out A);
lead to the following expression for the free energy componentlinear in the magnetic
field:
Fun = ~ 5, (Ke — K3)(n* x n) curl A. (15.6)
Hence follows an expression for the internal spontaneous magnetisation:
WL
M;i = Bo (Ko — K3)(n* x 0). (15.7)
As was shown in Section 11, the minimum ofthe free energy (11.6) at 82 > 0 corres-
ponds to the complex superconducting state with the order parameter n = mo(1, +i)e.
According to equation (15.7), this phase has a non-vanishing magnetic moment in the
uniform state. This moment is determined by the difference K, — K3 and turns out to be
negligible. It follows from the microscopic theory (Section 18) that in the BCS model for
MAGNETIC SUPERCONDUCTORS 105
the vector order parameter K, = K> = K3, and there is no spontaneous magnetisation.
However, if we take into account the energy dependence of the density of states near the
Fermi surface (electron-hole asymmetry), the difference K, — K3, hence the internal
magnetic moment, becomes non-zero:
T, 2 Ey
i) — K3 ~moi(2) In
c
One can prove that the internal magnetisation of a superconductor is very small even
at zero temperature. The simplest case is the state described by equation (15.3). In this
state, only electrons with spin up are paired (see equation (2.7)). Using the Bogoliubov
transform (Section 5), one can easily prove that the energy distribution of such electrons
has the form
mi(é) = (aang) =5 ft - 50-2718), (15.8)

where f(E) is the Fermi distribution function and E = ,/é? + Ag. At T=0
m(@=3(1-§):
At the same time, electrons with spin down are unpaired, and their energy distribution
m()=5(1~ 5)
has the shape of the Fermi step function. The spin magnetic momentin such liquid is
given by the equation
Mi = 24s [agN(E) (6) —my(6) © Za? In. (15.9)

Here N(E€)is the density of electron states, No is its derivative at the Fermi level, and €, is
the cut-off parameter of the logarithmically divergent integral due to the fact that the
order parameteris non-zero only within a narrow layer near the Fermi surface (Section 5).
Thus, the spontaneous spin magnetic moment is small by virtue of the smallness of
(T./€1)" In(e,/Te) and is non-zero only in the presence of the asymmetry between the
distributions of electrons and holes near the Fermi surface [3, 60].
The density of the internal spin momentis small owing to the compensationof the spin
moments of Cooper pairs composed of particles with spins pointing along the field by
unpaired particles with opposite spins. There are situations when such a compensation
does not occur. In this case, one should haveeither a giant pairing interaction for one spin
projection or an almost fully polarised Fermi liquid with a large spacing between Fermi
levels of spin-up and spin-down electrons. Both these options do not seem feasible for
superconductors. Creation of a strongly spin-polarised superfluid phaseis possible in the
electrically neutral superfluid Fermi-liquid (He).
Surface currents and magnetic moment of a sample
Magnetic superconducting states in crystals where the effects of crystal anisotropy and
strong spin-orbit coupling are essential have only one type of continuous degeneracy,
namely the degeneracy in the order parameter phase ¢, whichallowsthe presence of non-
dissipative currents. Currents unrelated to the phase gradient can flow onlyin a layer of
thickness of about € near the boundaries of samples or magnetic domains. In order to
calculate these currents, let us use equation (15.5) for the gradient free energy and
substitute the order parameter with the phase factor in the explicit form, n — n(r)e*).
By omitting the terms proportional to K, and omitting the full derivatives in the inte-
grand, we obtain
Fgrad = [ &r{x, [?n? + tui(meVing — Vine) + (Vin (Vin)|

Ky +K . ;
4-203 32 [2Ivn/? + ivcurl(n xn) + [Vil + (Ving) (Vin)
a, xn) curl A}.

Ky — Ky Qn *
(15.10)
Here
v=Vo+ 2a
hic
is the gauge-invariant phase gradient (cf. equation (14.6)). The corresponding expression
for the current density is as follows:
OFed 2¢ 6Fgas
bAté«<@YR@ SSS’
— 2e 2 fan, * ay . Ky + Ky *
7 {x [2¥In| + i(niVn; 0; vn)| + [2 (vn)
* . *
+ (vn*)n) + icurl(n* x n)| +iKo —
SG Ky curl(n* * x n)}. (15.11)
Inhomogeneous distributions of the magnitude or direction of vector i(n* x 1) near the

boundaries of samples or magnetic domains (within a distance of the order of the cor-
relation length €(7)) giverise to the persistent surface currents creating a magnetic moment
M=5- [ ar(r x3) (15.12)
The magnitude and direction of M depends on the distribution of components of the

order parameter 7;(r) near the sample boundary.
Consider a cylindrical sample of radius R and the Z-axis directed along the hexagonal
crystal axis. Let us assume for simplicity that the order parameter throughout the sample
volume is expressed as] = no(r)(1, i), where 79(r) smoothly decreasesin the surface layer
from the bulk value 7 to zero at r = R. In this case, even in the absence of an external
magnetic field, i.e. at v = 0, the expression for the current density has the form
de One(r)
Jj = c ccurlM = ~—K,-2“¢
hi 2 or Y,
where ¢ is the unit vector in the azimuthal direction. Performing integration in

equation (15.12), we obtain an estimate (equation (15.4)) for the magnetic moment of a
cylinder of volume V:
8
M= -_KomVe x Bryn, V2. (15.13)
Here we have used the fact that Ky ~ fi’n, /mnp (see equation (14.7)).
To complete the discussion of the spontaneous magnetic moment of magnetic super-
conductors, we emphasise that the last term in equation (15.11) for the current density,
corresponding to the density of spontaneous internal moment, is structurally un-
distinguishable from the last but one term, corresponding to the surface moment, in the
same equation. For this reason, formulas for the current density derived from the
microscopic theory have led many authors to the conclusion that there is a ‘large’
(~ fugn,) spontaneous internal density of magnetisation (see, for example, Ref. 61). In
order to give a correct interpretation of different contributions to the current, one should
calculate the gradient energy on the basis of the microscopic theory.
Electrodynamics of magnetic superconductors
In the presence of an external magnetic field H parallel to the cylinder axis, the London
equation has the form
4nj A
curl B = =— + 4mcurlM, (15.14)
where 6 is the London penetration depth. Since the contribution to the current due to the
term ¢ curl M is non-vanishing only in a surface layer with thickness << 6 < R, the
magnetic field magnitude decays in the sample volume:
B(r) = B(R) exp (- ; ") (15.15)

However, owing to the superconducting currents flowing near the surface, the boundary
condition for the London equations takes the form
B(R) =H+40M. (15.16)
Thus, even in the absence of an external magnetic field, there is a magnetic field at the
superconductor surface created by the magnetisation of Cooperpairs:
eh, A
Bo = 40M = 40> ns = Atppns i, (15.17)
which decays in the sample bulk, and the magnitude of Bo is of the order of the lower
critical field:
®o 6 6
Ae = an62 me = 2TLips Ing . (15.18)
Onecan seethat it is easier to achieve the lowercritical field if the applied field is parallel
to [i than in the case whenit points in the opposite direction. Moreover,if the surface field
(15.17) in a superconductor is higher than H,1, the Meissner state is impossible. Flux
lines will penetrate in the superconductor in an arbitrarily weak external magneticfield.
A field of the order of H,, and decaying with distance like the field of a magnetic
dipole should be generated near the surface of a single-domain magnetic superconductor.
Magnetism in p-wave superconductors
In superconductors with weak spin—orbit coupling, the situation is different from that
discussed above. In this case, not only the phase degeneracy, but also the degeneracy in
the order parameter orientation is space is essential. So, in a charged superfluid Fermi
liquid with the structure of the A-phase of helium-3, the order parameter has the form
Aai ~ Va(A; + iA/), (15.19)
where V, A’, A”are unit vectors such that A’ 1 A”, and A’ x A” = | defines the direction
of the orbital angular momentum of Cooper pairs. The gradient part of the Ginzburg—
Landau free energy in p-wave superconductors is expressed by
Fgrad = [ are, (D;Aqj)" (Dj Aaj) + K2(D; Aci)” (Dj Aaj)

2e , k
+ K3(DjAqj)" (DjAci) + Ka 5 ilaBaAlyAni + B?
=}. (15.20)
The A-phase states are degenerate with respect to rotations of the vector V and thetriad
(A’, A”, 1). Therefore, non-dissipative currents in the superconductor volume are
determined not only by the gauge invariant velocity v, but also by the space distribution
(texture) of the vectors that define the order parameter (cf. equation (15.11)). The results
obtained above about the spontaneous magnetisation in such a superconductorstill hold,
but the allowed types of flux lines and the structure of the mixed state are more com-
plicated than in multicomponent superconducting phases in crystals with the orientational
degeneracy suppressed by strong anisotropy and spin—orbit coupling.
The term proportional to K, in the expression (15.20) describes the interaction between
the spontaneous spin magnetic momentin the superconducting state and an externalfield.
The expression for unitary phases (the definition of unitary phases was given in Footnote 6
to Section 5), in particular, for A- and B-phases, does not contain such a term. In non-
unitary phases the spin moment is non-zero, which leads to the splitting of the phase
transition to the superfluid state in >He into two transitions. First, the transition to the Ay-
phase takes place, followed by the transition to the A-phase (Figure 3.1) [64]. The
splitting of this transition, however, is small because the coefficient K, is non-zero only
by virtue of a small electron-hole asymmetry (see Section 18).
Superconductors with the p-wave pairing and structure of the A- or A;-phase are not
known at this time. Some topics in the theory of such superconducting states were
discussed in Refs 31, 65, and 66.
16 Josephson Effect
A generalisation of the phenomenological theory of the Josephsoneffect to the case of a

junction between two superconductors with different symmetries can be based on the
approach developed in Section 13 in analysing the surface superconductivity. The
simplest example is a plane junction between two superconductors in different super-
conducting states with one-component order parameters
m=Imle*, mm = |mle. (16.1)

For uniaxial (hexagonal and tetragonal) and cubic crystals, the free energy is deter-
mined by the expression
F=Fy+Frt+Fy, (16.2)
where
Fix / @rF; (i=1,2) (16.3)

rn >0
are the free energies (12.2) of superconductors occupying the left and right half-spaces
separated by a plane interface that passes through the origin of a coordinate system, n; are
the outward normal vectors (nm; = —mn), and F;is the surface (Josephson) energy, which
phenomenologically describes coupling between the superconductorsdueto the tunneling
of Cooper pairs:
Fy =A f dSeu(m)galma)[nim +n) (16.4)

Here integration is performed over the interface. Generally speaking, the Josephson
junction energy is expressed by an infinite sum of terms like the right-hand side of
equation (16.4):
Sf dsaf(mehms)+ mB
P»q
ill
where each productgf (im; 7 and g4(mp)7should be invariant underall operations ofthe
symmetry group of the respective half-space. In what follows, however,it will suffice to
consider only one componentof this sum.
The energy F; is invariant underall operations of the symmetry groupsofthe crystals
in both half-spaces in the normalstate. For crystals with strong spin-orbit coupling, there
always exist combinationsbilinear in 7 and 7and satisfying these symmetry conditions.
This meansthatthere are no principal limitations on the existence of Josephson coupling
between two superconductors with one-component order parameters, including two
superconductors with singlet andtriplet pairing. At some surface orientations, such that
one of the functions g;(n;) goes to zero, F; also vanishes. In this case, one should take
account of Josephson energies of higher orders in 7;.
The symmetry of g(n) is identical to that of the corresponding superconducting class.
Forsinglet states, this means that g(m) = 0 for the normal directions corresponding to
nodes of the order parameterat the Fermi surface (see Section 4), i.e. at S = 0 functions
g(n) can be considered asthe basis functions of the respective irreducible representation.
For the case of triplet pairing, functions g(m) were given in Ref. 67.
In the same manner, Josephson energies F; for multicomponentsuperconducting states
in the case of strong spin-orbit coupling can be obtained by making up invariant com-
binations of the vectors n; and the order parameter components TN.
In the absenceof spin-orbit coupling, one cannot compile a scalar linear function from
the spin vector 1 of the order parameter andthe normalvector n in a superconductor with
triplet pairing, therefore a Josephson coupling like that described by equation (16.4) is
impossible. One can, however, consider a coupling (Josephsonenergy) of higher orders in
N [68]. This also applies to the surface orientations for which the right-hand side of
equation (16.4) goes to zero for symmetry reasons.
By varying the gradient component of equation (16.2) with respect to A, we obtain
expressions for the current density in the left and right half-spaces:
. éF 2nC *
j= os =~] Reni [Ku(Dy + Dy) + KiDz|m,
or ,° (16.5)
j=
.
—o ee
2,grad
=- aR
AC
15* [Koi (Dy + Dy) + Kx2D_]m.
As in Section 13, the boundary conditions for the Gunzburg—Landau equations at the
junction interface are obtained by varying the full energy (16.2) with respect to a and 73:
[K11(711,.Dy + 1,yDy) + Kiam, Dm , = —Ag;(m)g2(m2)>, (166)

i[Ko1 (n2,xDy + N2,yDy) + Koon, Dm |. = —Ag)(m;)g2(m2)m|5.
From equations (16.5) and (16.6), we derive the current density through the Josephson
junction:
1= Gi falm|=“F* eu (m:)eo(me)mlnalsin(de 41). (16.7)

JOSEPHSON EFFECT 113
FIGURE 16.1 Alteration of the sign of function g(n) for the representation Bi, on side faces of: (a) tetragonal
and (b) hexagonalcrystals.
According to equation (16.7), the temperature dependence of the maximal Josephson

current is determined by the productof the absolute values of the order parameters on both
sides of the junction. If the left and right half-spaces are occupied by superconductors
with equal critical temperatures and the absolute value of the order parameter at the
boundary equals the bulk value, the maximal Josephson current is proportional to T — To.
But, as we know already, the magnitude of the order parameter at the boundary in an
unconventional superconductor can be considerably smaller than in the bulk because of
the surface energy contribution, which is the case when f(n) # 0, where function f(n)
describes the surface energy as a function of orientation of the normal (see Section 13). In
this case, the following estimate holds:
nls ~ gayn(D
b(n
(16.8)
~1/2
where b(n) is the healing length given by equation (13.7), (7) ~ (1 — T/T.) is the
correlation length, and m(T) ~ (1 — T/ T,)\!* is the order parameter magnitude in the
bulk. By substituting equation (16.8) into (16.7), we can see that the Josephson currentis
proportional to (JT; — TY if the order parameters in both superconductors are suppressed
at both boundaries forming the junction, and is proportional to (T, — T)°? GF the order
parameter is suppressed only on oneside.
In a conventional superconducting state, g(m) transforms as a basis function of the
identity representation A,, which is invariant under all operations of the crystal point
group. Traditionally, g,, (i) is assumed to be isotropic, therefore the Josephson currentis
independent of the junction interface orientation with respect to the crystal axes.
In unconventional superconducting states, on the contrary, g(n) is a function of the
direction of n. Thus, for all one-dimensional non-identity representations, g(n) changes
its sign when a line of the gap nodes is crossed. For example, gz,(n) ~ n2 — ni and
changesits sign as the interface orientation turns from one side surface of a tetragonal
crystal to another (Figure 16.1a). A similar alteration of the sign occurs in a hexagonal
ma IN
FIGURE16.2 A two-junction SQUID built on adjacent side faces of a tetragonal crystal with different signs of
the order parameter.
crystal in the superconducting state B; (Figure 16.1b), since gg, ~ n>? — 3n,n;. Therefore
expression (16.7) for the current in the case of a junction between a conventional super-
conductor and a side surface of a tetragonal or hexagonal crystal in the superconducting
state B; can be rewritten as
I =Ipsin(¢; — ¢2 + 7), . (16.9)

where n is the numberof the side surface.
This result has allowed researchers to determine the symmetry of the superconducting
state in yttrium-based high-temperature superconductors. The most reliable data derive
from the measurements [69, 70] of the current through a two-junction SQUID, whose
Josephson junctions were formed by conventional superconducting leads connected to
two side surfaces of the YBayCu307_, superconducting tetragonal crystal (Figure 16.2).
If the two junctions are identical, the total current through the SQUID is determined by
the equation
I = In(sin Ad, + sin Ado) = 21 sin PF ogg — OP.

2
(16.10)
Here Ay, and Ay»are the phase jumps across junctions 1 and 2. The difference between
them, i.e. the total change in the order parameter phase after the round trip over the
SQUID closed circuit, is composed of the phase difference due to the applied magnetic
field, (2e/hic) $ Adr = (27@/®p), and the ‘internal’ phase jumpatthe interface between
junctions 1 and 2:
2n@
Ad; — Ady a 4b hy. (16.11)
Do
From equations (16.10) and (16.11) we derive an expression for the maximal current as a
function of the applied magnetic field:
md 6
Imax = 2p cos (E+), (16.12)
JOSEPHSON EFFECT 115
In the case of conventional superconductivity, the result in YBa,Cu307_, would have

been 6,2 = 0, so that the current would have had the maximum value Ipax(® = 0) = 2 Jo
in the absence of magnetic field. The experimental results [69, 70] indicate that
Tnax(® = 0) = 0, which meansthat 6,2 = 7, as it should be in the case of unconventional
superconductivity corresponding to the representation By.
The existence of the internal difference in the order parameter phase between different
side surfaces of YBayCu307_, crystals was also demonstrated by a direct measurement of
the half-integer magnetic flux captured by a superconducting ring of three yttrium-based
superconducting single crystals with different orientations [19].
Since the simplest function of the irreducible representation B, has the form
g(k) ~ k?x —k?‘y 3 (16.13)

the superconductivity in YBa,Cu3;07_, is usually referred to as the d-wave super-
conductivity (or d,z_,:-wave superconductivity). Sometimes (see references in Ref. 18)
the so-called “s + id-pairing” is discussed:
g(k) = Ay + iAa(k? — ky), (16.14)

in which case 6) can be different from 7 as longas the ratio A,/Aq is non-zero. As was
noted in Section 4, a system can go to the superconducting state described by equation
(16.14) through a direct phase transition from the normal state only if the phase transi-
tions temperatures to the superconducting state (when the gauge symmetry is broken) and
to the ferromagnetic state (the time-reversal symmetry is broken) coincide, which seems
highly improbable. Therefore the state described by equation (16.14) should result from
two consecutive phase transitions from the normal state, which, to the best of our
knowledge, have not been detected in experiments. Thus, the interpretation of deviations
of 6). from 7 in terms of the mixture of s- and d-wave states is rather speculative.
Part I
In the second part of the book, we develop the theory of unconventional super-
conductivity using the quantum field theory approach. The formulation of the theory in
terms of Green’s functions not only makes the derivation of basic results more transparent
and concise, but also allows one to solve a wider range of problems, which could not be
solved using the methods described in Part I. We do not intend to give a comprehensive
introduction to the method of Green’s functions in the theory of condensed state, in
particular, in the theory of conventional superconductivity (see Ref. 71), and presumethat
the reader is familiar with the basic ideas and concepts of this method.
17 Gor’kov Equations
Let us consider an electron gas with an effective attraction between the particles de-
scribed by the following Hamiltonian:
H = Ho + Him = >(ker|Holk’Bax, ax
kk’
1
(17.1)
+ 2 »— Volk, Ka"4g), Oe4/2,8 My! 44/2, Fk! +4/2, 1°
kk’,
1 . é
Hy = =-( iV+ “A(r)) 2 4+U(t) ~ ep.
Here we have used a more general expression than (5.1) by including in the one-particle
Hamiltonian Hy the term responsible for spatial non-uniformity of the system (due to
impurities, surface, external fields etc.). The pairing interaction V have the form (5.3),
(5.7) or (5.8).
The superconductor Green’s function at finite temperatures is defined as follows:
(17.2)
Gag(k, Th; K, T2) = xT, Ata (71) Ay (72)
where the angular brackets mean Gibbs averaging with the Hamiltonian (17.1) (see Foot-
note 4 in Section 5), dxa(T) = exp(TH)aq exp(—TH) are fermion operators in Matsubara
representation, and 7; is the operator ordering with respect to imaginary time 7. Many
physical properties of the system can be expressed in terms of the Green’s function (17.2).
Similarly to the theory of conventional superconductivity, let us introduce another two
Green’s functions, which are called anomalous:
Foa(k, 71; K’, 72) = (Trdxa(t1 )a_xa(72)), 17.3

FyA(k, 71; k', 7) = (Tr(Ti) Qi(72))- ( )
119
G F Ft
>—__—__ >—___-____~~<¢ ——_—
k, 0 KB ke -KB —k,o kB
FIGURE 17.1 Graphic representations of the normal and anomalous Green’s functions.
Thatthe averages on the right-hand sides of these equations are non-zero follows from the
fact that creation or annihilation of an electron pair in the presence of the Bose-
condensate of Cooperpairs haslittle impact on the state of the system (see Section 5). In
the diagram technique,the normal and anomalous Green’s functions (17.2) and (17.3) are
denoted by lines with arrows (Figure 17.1).
In static problems, Green’s functions depend only onthe difference between imaginary
times, 7,--7—=7, and it is convenient to go over to the momentum-frequency
representation:
Gog(k,k’;7)
B =T Gyo(k,
B k's w,)e™” ete.,
n
where w, = (2n + 1)aT is the fermion Matsubara frequency.

The functionsG and satisfy a system of differential equation whose derivation is the
next topic of this section. Let us use the equations of motion for the operators dq:
Ake,
= lH, Aker].
OT
Differentiation of the function G (17.2) with respect to 7 gives us
OGa(k, k’; 7)
= —(T,[H(7), axa(7)]a%{,4(0)) — 6(7)6(k ~ k’)bag.
Or
Substituting the Hamiltonian (17.1) into the latter equation and using the property (5.2),
we obtain
OGag(K, k's 7
wees= — Yay)Gall!)
I
-\S Vora (k, ky ) (T; Bran (7) Ak, +4/2,92 (7) 4_ky+q/2,73 (r) Ag (0))
king
~ &(r)6(Ie — K’)bag. (17.4)

Thenextstep is to transform the rigorous equation (17.4) by representing the two-particle
Green’s function on the right-hand side in the following form (the mean-field approx-
imation):
(T, aban (7) Oy +q/2,%2 (7) 4_ky+4q/2,73 (7) Org (0))

+
= (T, F_ktay (7) afr,(0)) (T; ey +-4/2,72(T) Ak, +4/2,75(T))+
Other terms in this decoupling only produce an additive correction to the chemical
potential in Hp, and so can be omitted.
GOR’ KOV EQUATIONS 121
Nowlet us introduce the function which is the superconductor order parameter:
Aca(k, @) = — Li Voooull Fae (K +5, vk’ -3,7)
—_T » >. Vira,(Kk, K’)Fay, (k’ +3,k-4;

q q wn); (17.5)
and also the function
At(k = PLY Vassa(lke)

K)F(kl — 3k +350).
After this, the equation for the Green’s function G in the momentum-frequency rep-
resentation finally takes the form
So (koi _ A|K1y) Gye (ki ) kK; Wn) + S> Aay(k, QF4(k —~ q, kK’; Wn)
ki q
= 6(k —k’)dag. (17.6)
A similar procedure yields the equations for anomalous Green’s functions:
So (-kiqlivn + Ho| — ka)F5,(ki, kK’ wn)

ky
+ S- Av (k, q)Gape(k + q, K; Wy) = 0, (17.7)

q
So (Kerlinn — Holy)Fya (ki, Kk’; wn)

k,
~~ Aay(k, 4)Gpy(—k’, -k + q5 -w,) = 0. (17.8)

q
Equations (17.6)-(17.8), which are differential in the coordinate representation, are called
Gor’kov equations and, in combination with the self-consistency condition (17.5), form
the basis of theoretical description of superconductors.
In what follows, we will often have to use an equation which determines the tem-
perature of the superconducting transition T, in various situations (for example, in the
presence of impurities or an external magnetic field). This equation is derived from the
Gor’kov equations in the following way. The order parameter is small near T, and, using
equations (17.6) and (17.8), one can expand the anomalous Green’s function F in powers
of A upto the first order and substitute it in the self-consistency condition. As a result, we
have the following equation:
/
Aaalk, q) = —T » a Vea, nul(k, kG) («+ 4k" + + i)

n kik" g
x GY (-« + ,, —k" + > ; un) A.6(k", q), (17.9)

q
k+— k+4
+5 44
k’+ m45
k"+
—k+44 —K49/
k+>5 KE
k 9
> pr
k"+ 5
FIGURE 17.2 Self-consistency equation.
where G©) is Green’s function of the normal metal taking accountof all external fields.
The corresponding graphical expression is given in Figure 17.2. The critical temperature
is defined as the temperature at which a non-zero solution of the linear integral equation
(17.9) first appears.
In practical calculations, it is important to know Green’s functions of a spatially
uniform system in the absence of external perturbations. In this case, the Gor’kov
equations can be considerably simplified, since
Gap (k, k's wn) = Gog (k, w,)6(k — k’) ete. (17.10)
Hence, the order parameter only depends on the directions of momenta k on the Fermi
surface, but not on the coordinates in space:
Aap(k, q) = Aap(k)6(q),
moreover,
Aag(k) = —Aga(—k).
It is clear that the anomalous averages introduced in Section 5 are expressed directly
through Green’s functions of a uniform system when the temporal arguments coincide:
Fraps = Fua(k, Tk, T) = TY) Foa(k, Wn);

n
Fibyg =T Y— F3s(k, wn)-

n
Substituting (17.10) in equations (17.6)-(17.8) and taking into account that the one-
particle Hamiltonian is diagonal with respect to momenta andspins:
(ka|Ho|k’B) = &.6(K _ k')6a9;
and, in addition, & = €__%, we obtain
(iw, _ &)Gag(k, Wn) + Aay(k)Fja(k, Wn) = baB;
(iy + &)Fig(k, wn) + OE, (K)Gy9(k, wn) = 0, (17.11)

(iwy — €)Fap(k, wp) — Aan(k)Gp,(—k, —w,) = 0.
The solution of these algebraic equations has the form
Gog (K, Wy) = —(ity + &) [v2 + 2 + A(K)At(K)]

ap?
4 (17.12)
Fop(K, Wn) = Aay(k) [wry + & + A*(k)A(k)] 4
For all superconducting phases with singlet pairing, and also for unitary phases with
triplet pairing, the condition (AA*) 46 ~ dag holds, and Green’s functions take the
form
IW, + x
Gop (Kk, Wy) = — +42 bop
A rm (17.13)
Fy
pe) EEE AL
k, in) = i.
where
1
Ai = 7 SPA* (K)A(K).
Hence we obtain for Green’s function of the normalstate (i.e. for A = 0)
0 6
Gk, Wn) = oe, (17.14)
tun — Ek
For non-unitary phases with triplet pairing
(AA*)9g = A?(dd* 6a + mOgg),

where m(k) = id(k) x d*(k) 4 0, and the expressions for the superconductor Green’s
functions are more complicated:
(wi + & + A?\d(k)|’) dae + A’m(k) 609

Goa(k, Wn) = —(iw, + Ex)
(wa + Ex4(wr + Ee)
(17.15)
Foa(k, Wn)
— Ati
= A(idoy) x
(we + & + (w2
A?|d(k))’)d(k) — iA?m(k) x d(k) )
+ Ez)(w? + Ez)
where
Ex = VG + A?(\d(k)? + fm(k))). (17.16)

An equation that determines the temperature dependenceof the order parameter can be
obtained by substituting expression (17.12) for function F into the self-consistency
equation (17.5):
Ays(k
_ PY DL Voansl(k, k’) ao
Acp((k) = w? ae (17.17)
(similarly a corresponding equation for non-unitary phases can be derived (see Ref. 13)).
In order to calculate the sum over frequencies in equation (17.17), let us use the formula
2 1 1 x
——_.———— = — tanh-. 17.18
n=-0o (2n + 1)? +2 2x 2
From equation (17.17) we obtain
Aos(h) = = Yo VinalKAR) setamh () ; (17.19)

hence, given that tanh(E,:/2T) = 1 — 2f,:, where fy: is the Fermi distribution function,
we have once again obtained equations (6.5) and (6.6). The equation for the critical
temperature 7, is obtained by substituting A =O (ie. by replacing Ey: —> |é-|) in
equation (17.19).
The Green’s functions technique for superconductors can be formulated in a more
compact form, which is formally similar to the diagram technique for normal Fermi
liquids if we combine G, F, and F + in one matrix Green’s function G using the vector
operators (5.23) in Matsubara representation. By definition,
\/T
G(k1, Ko; w») = / dre!" (TAy, (T)Ay, (0))
0
_ ( Gog (Ki , Ko; wy) _ ‘a6 (K1 , Kz; Wn) (17 20)
—F¥4(K1, 2302) —Gpo(—Ke, ki; wn) ]
The matrix elements of G are, in turn, 2 x 2 matrices in the spin space. In the spatially
uniform case, we have (see equation (17.22))
G (k ) _ 1 (iw, + Ex) bap Aog({k)
TURF ELAR Adg(k) (tun — &)bap

lwyTo + &,73 + A(k) ,
= 21
w+ G+ AR” (17-21,
where 7; are Pauli matrices in the particle-hole “space.”
Spectral Representation and Energies of Excitations
In solving specific problems, one should know how to calculate the sums over Matsubara
frequencies. To this end, it is convenient to use the so-called spectral representation of
Green’s functions, which is expressed in the matrix notation as
+00
* dz p(k, z)
O(n) = / Om iw 2
—cO
nt
After this, sums over the fermion Matsubara frequencies can easily be calculated using
the identity (cf. equation (17.18))
T aia, 1=z =xtanh=.

1 z
2. 2T 17.22
(17.22)
The real spectral density 6 is expressed in terms of the Fourier transforms of the retarded
and advanced Green’s functions! as follows:
A(k, w) = —21mG*(k, w) = i(G* (k, w) — G4(k,w)).

The retarded (advanced) Green’s functions are derived from G(k, wW,) by means of ana-
lytical continuation to the upper (lower) half-plane of complex w:
GF(k,w) = G(k, w»)| iw, w+ i0° (17.23)
The spectrum of elementary excitations in a superconductor is determined by the poles

of the function G*, Performing analytical continuation in equation (17.13), we obtain the
equation that determines the spectrum:
det ||E* — & — A(k)A*(k)|| = 0. (17.24)
Substituting expressions (5.18) and (5.20) in the latter equation, we obtain the following
formulas for the energies of excitations:
Ey = G+ A?|g(Kk))?
for singlet pairing, and
Ex =& + A?|d(k)/?
for unitary phases with triplet pairing, i.e. equations (5.33) and (5.34) are recovered.
For non-unitary phases the spectrum of excitations is split into two branches, as is
usual in traditional magnetic materials, since non-unitary phases have a non-zero internal
magnetisation:
Exa = 6 + A?(\d(k)? + [a(k) x €(h)). (17.25)

Henceit follows that the positions of nodes in the excitation spectra in all phases with
triplet pairing are determined by the equation detA(k) = 0,ie. d°(k) = 0.
' Let us recall that the functions G* (G4) differ from the Matsubara function G (Eq. (17.20)) in that the
time-ordered product of operators is replaced by their retarded (advanced) anticommutators.
Density of states
The density of quasiparticle states is, by definition,
= > 5(E — Ey). (17.26)

ka
In terms of Green’s functions, this quantity is expressed as
1
N(E) = ap(k, E) —— Im)> G(k,w,) (17.27)
TK ity > E+i0
Taking account of equation (5.29) for the excitation spectrum, we obtain from
equation (17.26)
NE)=2 fo 5(E — Ex) = 2[Sf agote- Ex)
=m [F
dQ dE'E!
E'
6(E — E'
4n [min
/EI2 Ae )
=m [F
° An es
AR
(17.28)
where No is the density of states at the Fermi level in the normal metal per one spin
projection, and the integration over angles is performed within the limits A? < E’.
It follows from equation (17.28) that for a conventional isotropic s-wave super-
conductor (g(k) = 1)
0, E<A,
N(E) = 2No E ESA (17.29)
[F2 _ We ? 1
i.e. at small FE the density of quasiparticle states identically goes to zero.

Nowlet us investigate the effect of the gap nodes on the excitation spectrum. Consider
as an example a superconductor with the A-phase structure, in which the order parameter
has the form (3.8), i.e. the gap has nodes at the north and south poles of the Fermi surface.
From equation (17.28) we obtain
E
N(E) = 2m | F = Ny [sina oom
4n
E? — Ar(e, +) ,/E2 — A? sin? 6
and in the integrand sin@ < E/A. As E — 0, the main contribution to the integral comes
from the polar regions, 6 < E/A and x — 6 < E/A,hence
E/A
E 2
rw No | 6d9————___.
ap ~(Z):
a (17.30)
Thus we have obtained a non-zero density of states.

One can verify that, if the gap has line nodes (which is the case, for example, in a
superconductor with the polar phase structure), then
E
N(E) ~ No 7A: (17.31)
Such a power-law energy dependence of the density of quasiparticle states results in
power-law (not exponential) temperature dependences of thermodynamic and kinetic
characteristics of unconventional superconductors.
18 Ginzburg-Landau Functional
The equations for the superconductor Green’s functions, or Gor’kov equations, derived in
the previous section allow one,in principle, to describe all properties of superconductors.
There is, however, a wide range of practical problems that can be solved without direct
involvement of these rather complicated equations. In particular, near the critical tem-
perature, where both the order parameter (A ~ (To. — tT)"*) and its gradient are small
(i.e. A(r) changeslittle on the characteristic length of the theory of superconductivity,
namely the Cooperpair dimension &), it is more convenientto use the Ginzburg-Landau
equations (see Section 12). The easiest way to derive these equations is to use Green’s
functions technique for calculation of the superconductor free energy Fs as a functional
of the order parameter, and then find its minimum with respect to A.
Weconsider as an example a p-wave superconductornear the critical temperature in
the absence of impurities [72], when the pairing potential in Hamiltonian (17.1) has the
form
k-k’
V(k,k’) = -3V—-, (18.1)
ke
where the coupling constant V is non-zero only in a narrow band of width ¢) near the
Fermi level (see equation (5.4)).
The free energy is determined by the formula F = —TInZ, where Z = Tr(e~°*) is
the partition function.' We express the Hamiltonian H using equation (5.22), which
! This definition is more appropriate to the thermodynamic potential ©, but, according to the general
thermodynamicprinciples, the difference 2, — , equals the difference between the free energies, F, — Fy.
129
corresponds to the mean-field approximation, in the form containing only the super-
conducting order parameter A and the fermion creation and annihilation operators:
i
He fe tin tha +79 2 TA"(ks @)A(K, 4)
oq
1
+5 (Aco (K, 4) 4644/2, e+4/2,9
kq
+ Avs (k, q) a_k+q/2,0 dx4/28) . (18.2)
In contrast to equation (5.24), the latter equation takes into account the possible in-
homogeneity of the order parameter.”
Treating the terms containing A in equation (18.2) as a perturbation Hj, and switching
to the Matsubara representation, let us expand the difference between the free energies in
the superconducting and normal states
WT
—Tin (<x — far fi(r) )
0
in powers of A up to the fourth-order term. We have
Foon = Fs — Fn = 5y [er /- TrAt(k,r)A(k,r) + Fo + Fs. (18.3)

Here
dq iqr . a
Ay, (K, r) = [ashe = (ia Oy)y,, Aai(t)ki (18.4)
is the order parameter of a p-wave superconductor and
Fr= = farnana,i(¥1) Sijap(E1,2)Agj(t2), (18.5)
where the kernel S' is expressed as
T O O O 0
Syop(t1,%2) = lim —)°(—-———] — —-—
uy: alr 2) raya Ak? » (2. srr] (2. ser]
x (0500)yy GO (15 825 Wn) (0p)45 GG) (1,14; wy). (18.6)
2 In the general case, the second term on the right of Eq. (18.2) has the form
— 5p A*((k,q)V1 (k, k’)A(kK’, q),

where V—! satisfies the equation > V~!(k,k”)V(k",k’) = 5(k —k’). By using the orthogonality and com-
a
pleteness of the set of basis functions, we obtain Eq. (18.2).
GINZBURG-LANDAU FUNCTIONAL 131
The functions Gin this equation are Green’s functions of the normal metal taking into
account the interactions of electron spins, as well as charges, with the external magnetic
field. The fourth-order term in the free energy expansion has the form
Fi REET Naaes na {qj} k
x A\(k, q,)G (—k, —w,)A*(k, q3)6 (k, Wy)
xA(k, q,)G(-k, —wn)6(q) + 43 — G2 — G4): (18.7)
All momenta q; in the Green’s functions here are put equal to zero since keeping them
would be essential only in calculation of the gradient terms of fourth order in A, which
are not interesting at this point.
If the interaction betweenelectron spins and the magneticfield is neglected (this issue
will be discussed below), then
co (11,12; Wy) = Go (r1 2; Wp Ory:
In the case of quadratic dispersion at H = 0, the Fourier transform of equation (17.14)is

N, :
Go (r,W,) =— me exp ( keryfi+ “signs)
ker EF
Ne
x te exp ( kpr sign wy, — tel), (18.8)
For A = 0 but H ¥ 0, wederive the following equation for the Green’s function G from
equation (17.6):
wl .d e .
i am (ign + <ain)) + €F GO (r,, P25 wn) = 6(r} _ rp).
In the calculations to follow, we will use the system of units in which fh = 1, (the Planck
constant will be restored in the final results when necessary), e is the absolute value of the
electron charge. Let us seek a solution of this equation in the form
rr
< fac) dr + ib(ry _ 12, Wn) . (18.9)

GO(ry, 12; Wy) = GOr, _ 12, Wn) exp
YT)
Integration in the exponentis performed alongthestraight line connecting points rj, ro.
The function 7 is determined by the equation [73]
OT, wn) 1 eo
kp ¥ sign w,
or Ac? (Axx) =0,
Henceit follows that, even in fields of the order of Hy2(0) ~ ®o/ne, the correction to the
phase is small as ~ (kp&))', as compared with the first term in the exponent in
equation (18.9). Therefore we can approximate the Green’s function as
G) (1,19; wa) = G(r, — 12} W,) exp < fac) dr

YY
4%; —ew)erp(EAln)ie—n)). (1810)

The validity of the latter equation is based on the fact that the characteristic length on
whichthe vectorpotential changes (the London penetration depth) near T, is considerably
larger than the length of decaying the Green’s functions (18.8).
Substituting expressions (18.8) and (18.10) in equation (18.6), we verify that the main
contribution to the kernel comes from the differentiation of the factors like
exp(ikp r sign w,), which change on the atomicscale, and the corrections ofthe first order
in magnetic field are due to the differentiation of the field-dependent phase factors in
equation (18.10), We have [31]
Si,aa(¥1,¥2) = Si (T1502) bap
amNo 2lwnl p a 2 ie
Sy(ti,¥2) = (me
ras) dex0 (72 iRj + pee Cue Me
x exp (=A(eR), (18.11)

where R = r, —r; and R = R/|R\.
Let us estimate the second term in the brackets on the right-hand side of equation
(18.11):
eH 1 A
ke (kp £0)? He2(0) "

It can be neglected in the zero order in the quasiclassical parameter (kpéo) | so that
2ie
Si(E1, Yr.) = so) (R) exp (=acur), (18.12)
where
scr)
a
=~ 7(
kpeR
D oxP — Zeal2
UB
2,
or
One can see that the kernel Sdecays exponentially when the separation between the
points r; and ro is larger than
UR
&0 ~ nT,’
Thereby a characteristic microscopic scale, namely the Cooper pair dimension (or the
coherencelength) €p is introduced into the theory. On the other hand, the superconducting
order parameter changes on the scale of the order of the correlation length (7), where
E/fo~ (1-T/ T.) 1! 5 1 (see Section 12). Therefore we can expand both the order
parameter and the phase factor in the integrand in equation (18.5) up to the second order
in r, — Yr, = R at temperatures around T,. We have
Fy =- |@rAt(r) [d?RSo(R)
x r + “a(R + ; (2)cone c
* [Asi+ Ooi
Or p 120ndn
Acip
O° Ri,
Explicitly separating the terms of zero order in R and integrating the second-order terms
by parts, we obtain
F2 = Funiform + Fgrads (18.13)
where
Funiform = — /BrA* (rv) Agj(t) /RS” (R), (18.14)
1 * (18.15)
Fgrad = 5 [frida (DiAqj) [érs? wr,
and D = —i(0/Or) + (2e/c)A(r) is the covariant derivative.

Let us calculate the integrals over R in equations (18.14) and (18.15). In the uniform
part we have
2 00
3 (0) _ mNo 2|wr| DP
Qn aNo 2 1 an 1
= 5p (2) TSS — = Soy MOTI. (18.16
(18.16)
3 (Fe) ju) 3 8 n>0 Aw
n
After cutting off the logarithmically divergent sum at the boundary frequency €1, we have
Lyle 1 Th (18.17)
ont So = Int + Indy = NoV i— = — —
A4u, nT T Nov Te
Here we have used equation (6.10) and the identity

N
lim = InN +1n4y.
slim, Da 1/2
Substitution of expressions (18.16) and (18.17) in equation (18.14) yields
Fiten = 3 (=o E") [aratte)Aeit).

i i T-T,
c
(1818)
After substitution of equation (18.18) into (18.3), we can see that the spatially uniform
terms containing the coupling constant cancel out.
For the gradient part we have
/AR SO (R)RR) = T
(2)y |[arr oxo(—2
Alenl
R) feORRRR,
is (Sibu + ijt + bi dik) Ve Nolc rr

noo ©
1)) ( On + 6x6 + Oi8j.) SoS (18.19)

Novg
WT2°
The comparison between this result and the phenomenological expression (15.20) for the
free energy of a p-wave superconductoryields the final expressions for the coefficients
[72]:
Ki= 7¢(3)Novg _
= 19)
7¢ yy
No &. (18.20)
=F = 949 mT?
Nowlet us consider the fourth-order term in the free energy expansion. After sub-
stitution of expressions (18.4) and (17.13) into the equation for F and calculating the
integral over the angles and the trace with respect to spin indices, using the identity
Tr(od,)(0d2)(od3)(od,) = 2(d;d2)(d3d4) _ 2(d, x dy) (ds x da),
we obtain
B
Fu= > {AnAa AL AD + 2Aq Aai Ag Apj — 245; Api Agi Agy
Gi
+ 27; Api Ag Aaj + 24%, Agi Ab Ag b8(qy +3 — G2 — Gy), (18.21)
where all summands in the braces depend on the momenta in the following manner:
Au Ag Aa Ag = PAA) etc., and
Nol ~ [eq = _ 60
dé——_, 763) N
TE
By transforming equation (18.21) back to the coordinate representation and comparing
the result with equation (11.1), we obtain for the coefficients [34,74]:
—261 = po = —B3 = By = Bs = Da (18.22)

Thus the density functional (18.3) finally takes the form
NoT ~T, Te Agi Ani* + 7¢(3) No

No 1 x
Frond = 3
1200? T? (- 2 Agi Acil” + (A*; Aci)”
— Ab, Api At; Ag + Agi Api Ajj Aaj + Agi Aaj Ajj Agi)
0D) nD,ay)" (DiAaj) + (DiAci)"(DjAay) + (DrAci)(DyAat)- (18:23)

4 7¢(3
The calculated parameters of the Ginzburg-Landaufunctional correspond to the weak-
coupling approximation (see the final part of Section 10).
Corrections to the quasiclassical approximation. Orbital magnetism
Comparing equation (18.20) with (15.7), one can see that in the approximation described
abovethere is no spontaneous magnetic moment in the bulk of a p-wave superconductor
since K> = K3. Let us investigate the contribution of the second term in the brackets on
the right-hand side of equation (18.11), which is antisymmetric with respect to indices i
and j and is a correction of the second order in the quasiclassical parameter.
By omitting the field-dependent phase factor in equation (18.11), we obtain the fol-
lowing correction to the free energy density:
00
_e [{mNo\? 2|w|
6Fyy = "Fe (=) Cije At Aaj Hk 2n Te » [as exp (-*tHe
. € El
= azo Insp Ck Nai Aci Ay.
From this equation, restoring the Planck constant f, we obtain an expression for the
orbital magnetisation in the bulk [75]:
1Ny
Ake ° Ina ei At, Aok-
Ont, Re
The comparison between the latter equation and (15.7) leads us to the conclusion that the
difference K, — K3 and, hence, the bulk orbital magnetisation are non-vanishing if we
take into account the corrections to the quasiclassical approximation proportional to
(kp £0).
Spin magnetism
Nowlet us consider the effect of interaction betweenelectron spins and a magneticfield.

If the orbital effects are neglected, the kernel in equation (18.6) is a function of the
difference between coordinates. The order parameter can be assumed to be independent

of r, and we derive the following expression for the free energy density from
equation (18.5):
1
Psy = — FAG Si,ap Ap: (18.24)
The matrix S in this equation is conveniently calculated in the momentum representation:
Sip = 1.[Osfiky(0500)y, OO), 0) (090))yp 6O)(—K,wy). (18.25)

By directing the quantisation axis (the magnetic field vector H) along the Z-axis, we can
write the Green’s functions as follows (cf. equation (17.14) at H = 0):
GOm7(0) (k, wy) = (ion

— — iw,
&)°— (up) by
—&
(up(%2)ay»
bp
"(iy — GY— )? (18.26)
where ju is Bohr’s magneton (or the nuclear magnetic momentin helium-3). Substitution
of expression (18.26) into (18.25) and calculation of the trace with respect to spin indices
yields a correction to the matrix S linear in the magnetic field:
6S)a8
; = —ie —leap: LB HT
, fi(
soan
h in — Ek (ity + &)”
ms
— 516)eapebin HT 1
= Ja
st£) E +ee
(iw, |
where N(€)is the density of electron states. By expressingit in the form of the expansion
N(E) = No + Ng near the Fermi energy andintegrating over €, we obtain
signWy, sign wy,
bSijap = — 55 Capzlip HNo Te ay . (18.27)
Tv
~ 15 6y Cope bn H NG Te »
Wy
Thefirst term on the right-handside is identically equal to zero, and the divergent sum in
the second term is cut off at the boundary frequency ¢). Substituting this result into
equation (18.24), we finally obtain
.W E] *
OFsy = 17 bos No Ine Cay Agi Api Hy. (18.28)
Comparison of this expression with equation (15.20) indicates that the coefficient K,, and
hence the spontaneous spin magnetization, is small due to the asymmetry in the
distribution of electrons and holes near the Fermi surface.
Exercise
Calculate coefficients in the Ginzburg-Landau expansion for an anisotropic d-wave

superconductor in the weak-coupling approximation.
19 Upper Critical Field in a p-wave Superconductor
The upper critical fields for superconductors with unconventional order parameters in
the region where the Ginzburg-Landau theory holds were calculated in Section 12, As the
temperature drops, the correlation length €(T), which determines the scale on which the
order parameter changes, decreases, and at T < T, it becomes comparable to the co-
herence length &). Under these conditions, the gradient expansion of the free energy
cannot be used, and methods of the microscopic theory should be employed in calcu-
lations of H.2(T). In this section, we will perform calculations for an anisotropic p-wave
superconductor. In this case, as in the case of a conventional isotropic superconductor,
analytical expressions for the upper critical field at T = 0 can be obtained. For most of
the other unconventional superconducting states (even those with one-component order
parameters) which are not eigenfunctions of an equation like (19.5) (see below), for
example, for a tetragonal superconductor with A(r) ~ A(k? — k?), the upper critical
field can be calculated only approximately.
In orderto calculate the upper critical field H..(T) in a p-wave superconductor, let us
use equation (17.9). In the coordinate representation, taking account of the expression
(18.4) for the order parameter and the expansion (18.1) for the attractive interaction, we
obtain a linear integral equation [76]
Aai(¥1) = [aera Kulera)Arten), (19.1)
whose kernel has the form (cf. equation (18.5))
K; ; = ii
3VT 0 —
o 0 —
0
iF r) ryt 4k? ¥ (2 er] (se 2
n
X G(r], 12; Wy) G(r}, 13; —Wy). (19.2)
137
By repeating all the reasoning of the previous section which led to equation (18.12), we
obtain
r2
~ « (tNo\" 2\w, 2i
Kyleista) =3V RR (72) Yew (-7lR) exp Ae [Ateyae , (19.3)
Tl
where R = (ro —11)/|r2 — 14].

Given the identity
T2
2ie
exp “= fac) dr f(r2) = exp (i(r, - r1)D(r1)) F(), (19.4)
ry
where D(r) = —i(0/0r) + (2e/c)A(r) is the operator of covariant differentiation, we

transform equation (19.1) to
Aewo =sv7(™)farrin yrexp(-#

AwlR) expGRD(A))An(t). (19.5)
Note that equation (19.5) is a differential equation of infinite order [77], and the line-
arised Ginzburg-Landau equations can be obtained by expanding the exponential func-
tion on the right-hand side up to the terms of the second order in D.
Let the external field H be directed along the z-axis. In this case, we seek a solution of
equation (19.5) in the form
Aci(t) = e”“Aai(p),
where p = (x,y).
It is a natural assumption that the maximal value of the uppercritical field corresponds
to p, = 0. After transforming the integral in equation (19.5) to spherical coordinates with
the polar axis pointing along the z-axis, one can easily find out that the equations are
decoupled, ie. the z-components of the order parameter Aj, can be calculated in-
dependently of the x- and y-components.
Polar phase [76]
Let us start with the calculation of H..(T) for a superconducting state of the form
da = Aark:.
Since equation (19.5) is diagonal with respect to the spin indices, the same value of
the upper critical field corresponds to all components of the vector d. After setting
d, =d),=0, we check that this case corresponds to the polar phase.! Thus, let
' This statementis valid only if we neglect the interaction between spins and the magnetic field, jug H. If this
interaction is included, the transition leads to the {-phase (see Section 3) [31].
UPPER CRITICAL FIELD IN A p-WAVE SUPERCONDUCTOR 139
Az(p) =f(p). The method of solution is similar to that applied to the corresponding
problem for an isotropic s-wave superconductor [77].
Weintroduce the raising and lowering operators:
_ Dy+iDy
Ds V2 > (19.6)
whichsatisfy the commutationrelation [D_,D] = 21H/®po, where ®o is the magnetic

flux quantum. Then equation (19.5) transforms to
2 Co Wr
0
flp) p <3vr( Te
iF drexp(—2lr\
oe sindcos? oad
Javoo(t
n 0 0
20 R
x dp exp (:F sin 6(e”D, + *D.)) f(p). (19.7)
Now let us use the operator formula

eAtB eh eBe-(1/2)1A. 8)
which holds if the commutator of the operators A and B is a c-number, and rewrite th:
exponential function in equation (19.7) containing Ds as
R . .
exp| i—=sin@(e "YD, + e'?D_ )
nH 222 : R , i
= exp(- 2% R sin 0) exp (iFsinde PD,
26 V2
R .
x exp (:Zsinse*o_). (19.8)
2
If we expand the right-hand side in powers of D4. and substitute into equation (19.7),
then, after integration over the angle y, the expansion contains only the terms with
D}D", where the numbersof raising and lowering operators are equal. This means that
the solutions of equation (19.7) are eigenfunctions |N) of the operator D,D_, which is
nothing but the Hamiltonian of a harmonic oscillator:
27H
D,D_|N) =N=\y),
Bo
In the Landau gauge, A = (0, Hx, 0), these eigenfunctions are given by the expression
fivolp) mw ~e elPY o| _ TH
5? _ peJan
P®o 2nH
»—P80)),
_ P®o
ag)
where Hy(x) are the Hermite polynomials. Taking all this into account, we have
20
[ee exp ( x sin =D.) exp ( x sin 8 ep.) |[N )

J v2 v2
N ! H n
= on \> — (-FR sin? 8) |V)

AA (nl)’(N—n)!\ Bo
H
= InLy (Be sin? 0) IN), (19.10)
0
where Ly(x) are the Laguerre polynomials. The eigenvalue equation (19.7) takes the
form
1=6nvr(
=67 TX ° yu far exp
Te op Alen
0
x | sindc0s” 6 dB exp — TF sin? 9 Ly TH 2 sin? 9 . (19.11)

2B Bo
One can prove that the maximum value of the upper critical field corresponds to the
solution describing the harmonic oscillator ground state (V = 0), and the order parameter
in this case has the form
d ~ fo,p(x, yh. (19.12)

In orderto getrid of the logarithmic divergence in the sum over n in equation (19.11), we
subtract from both its sides the expressions for zero magnetic field. After this, taking
account of equation (18.17), we obtain the equation for H.2(T) for the polar phase:
T. = S*{ —_—_
1 ~~
6nT (=)
(nNo\? f dRexp{| 2|w,,|
In= -——"R
“5 n
|2n +1] No (=) exo( Up
0
WT
x | sind cost adeno (— 27 resin?) . (19.13)
In deriving equation (19.13) we have used the equation for the critical temperature 7, in
zero field:
1
mV NoT. ))— = I,
wr| n | it
where the sum over frequencies is cut off at the boundary energy ¢, (see the previous
section).
A- and Scharnberg—Klemm phases [76]
Nowlet us considier the x- and y-components of the order parameter. Let us introduce the
notation A,;(p) = f;(p) and the new functions
felp) = ll +if),
then equation (19.5) transforms to
(72) PSGe)anon)
oo
0
T 2n
1
-3 040 f ae( ete
x [sis 1 )
0 0
x exp (‘5 sin O (e?D, + *D.)) (i ) . (19.14)
If we use equation (19.8), expand the exponential functions in powers of y, and integrate
over , then the diagonal elements of the matrix operator on the right-hand side contain
summandsproportional to D/D", the superdiagonal element contains Dt2Dn and the
subdiagonal element contains D'p*?, For this reason, we seek a solution of equation
(19.14) in the form
@) _ (hy N>O, (19.15)

f- qn\N)
where |N) is given by equation (19.9).
We have
20
1 etl? R R N+2
[ee & exp{ i—= sinde? D, exp{ i—= sin @e’? D_ PylN +2)
J ee V2 qn|N)
Ss
aH m+1
OTNYoalle
(N+1)(N+2) FON
Sal (-=
— R? sin” 8) |N + 2)
H
+ pyLnso (Re sin? 0) |N + 2)
0
= 27
qnLn (=R°sin? 0) |N)

m+1
+ py (N+1)(N+2) ymca 8) \N)
m ®0
We haveobtained a linear uniform system of equations for the coefficients py and qn,
whose solvability condition is
(1 — ay)(1 — awy2) — By = 9, (19.16)

where
ay(H,T) = ovr Y /arexp(— Belg

i
x / sin? 6 dO exp (-F.
35," sina)o( R’ sin? 0) ;
H
0
mNo 2|wa|
Wal p
By(H,T) = 30vr(™)& [aeoo(—24
‘43 pddexp(— FER

x si TH 2) sin
«2 0) (N + 1)(N +2)
0
N N! 3 n+l
x ee _TH sin? 0 )
oral+2)= my ( Bo )
and it follows from the equations that py = ({1 — aw)/Gy)¢n.

Thus, we have obtained the equation for the uppercritical field for the solution of the
form (19.15). One can prove that the maximum value of the uppercritical field is
achieved at N = 0. The corresponding order parameter
dn {os )by + ih) 42Oey)be

Fi
— i} (19.17)
describes the so-called Scharnberg—Klemmphase. In the absenceof spin effects, the upper
critical field is the same for all components of vector d.
()-(), wn
The only remaining state to be analysed is
whichis also a solution of equation (19.14), but does not belong to the set defined by
equation (19.15).? Substituting (19.18) into (19.14), we can see that the equation that
determines the uppercritical for the order parameter
d ~ fo,p(x, 9) (kx — iky), (19.19)
2 Equation (19.14) has another solution of the form (‘:) = (”) , but one can show that this solution yields
a lowervalue of the uppercritical field.

which corresponds, as one can easily show, to the A-phase,’ has the form
1—ap =0. (19.20)
Thus, we have cometo the following conclusion: in a charged p-wave Fermi liquid, the
transition from the normal to superconducting state can lead to one of the three phases:
the polar phase, the A-phase, or the Scharnberg—Klemm phase. In order to determine
which of them has the highest uppercritical field, one should solve equations (19.13),
(19.20), and (19.16). Although the problem can only be solved numerically in the general
case,it is possible to obtain analytical expressions for H.. as T — T, (see Sections 12 and
18, and Exercise at the end of this section) and at zero temperature.
Calculation of H,2(0) [76]
Let us begin with the polar phase. In order to simplify the formulas, it is convenient to
introduce the following dimensionless variables:
2H rVh T
h= sa) pHa, t=a,
A £ To
where Hy = ©o/7€%, and T,o is the critical temperature at H — 0. From equation (19.13)
we derive
a
Int= {4
wid/ap [sindoow 6dé@
(19.21)
x ex tpjan+1| prsin’@\ 1
P Vh 4 jan +1] {"
The limit ¢ — 0 in this equation is calculated in the following way. Let us rewrite the sum
over frequencies as
Sot . } _— 2lim Yo y7"*1{. . }.

n a" n=0
After introducing the notation x = cos @ and summing over n, we obtain
CO 2y exp
t
_tp pil)
2(1 —
Int = lim
f° ax | ap Vh 4 —In
I+y
yol Vh 1 yexp (-=£) 1l-y
0 Vi
3 In the superconducting A-phase the orbital angular momentum of Cooperpairs is directed opposite to H.
HA 1
HP? ar
T. T
FIGURE 19.1 Sketch of the temperature dependences of the uppercritical field for different p-wave phases.
Nowlet us expand the exponential functions in the integrand in powersof ¢ as t — 0 and

rewrite the right-hand side in the form
lim feel aa) 2

+ Y=») l-y
where C = In is Euler’s constant. Finally, we obtain
4y
Calculations for the A-phase and the Scharnberg-Klemm phase are performed sim-
ilarly. Returning to the dimensional variables, the results can be summarised in the
following form:
2/3, polar phase,

_@ Oo
e'/3, A-phase, (19.22)
mG
e¥3-4/3 Scharnberg-Klemm phase.
For convenience in comparing the results, we have singled out the value of the upper
critical field for an isotropic s-wave superconductor at T = 0. Wesee that the polar phase
has the highest value of the uppercritical field. The temperature dependences of H.2(T)
for p-wave states are shown in Figure 19.1.
Exercises
(1) Prove identity (19.4).

(2) Using equations (19.13), (19.16), and (19.20), calculate H.. for a p-wave super-
conductor near the critical temperature.
20 Boundary Conditions for the Order Parameter
It follows from the phenomenological analysis of Section 13 that, because of the inherent
anisotropy of the order parameter, boundary conditions for the Ginzburg-Landau equa-
tions, which determine the surface properties of superconductors, are also essentially
anisotropic. The topic of the present section is the derivation of boundary conditions for
the order parameters corresponding to non-trivial types of pairing based on the micro-
scopic theory. Werestrict our analysis to superconductors with weak spin-orbit coupling
and spherical Fermi surfaces.
Specular scattering surface [79, 80]
In the applicability region of the Ginzburg-Landautheory, the problem is reduced to the

linear differential equation (17.9), which includes the Matsubara Green’s functionsof the
normal metal in the half-space x > 0 goingto zero at the interface (i.e. at x = 0), which
can be expressed in the absence of impurities and external magnetic fields as follows:
F (x X2)
(x1, x23%23 ky,Ky, w, wn) =
GO(21, din,
ee — a) (20.1)
20.1
where
Feq(x1, 2) = O(x1)O(%2) sin gxsin gx2,

and
_ ji, forx>0,
Ax) = 10 for x < 0.
Here we have used the mixed coordinate-momentum representation in which the Green’s
functions are diagonal in the momentum components parallel to the interface.
147
Let us consider as an example a superconductor with singlet pairing, whose order

parameter corresponds to a one-dimensional non-trivial representation of the crystal point
symmetry group (see Section 4). Generalisation to other cases is straightforward. The
order parameter in equation (17.9) is expressed in the mixed coordinate-momentum
representation as follows:
Acp(k, r) = (ioy) ag n(r) p(k).
Substituting expansion (5.7) into equation (17.9) and going over to the coordinate rep-
resentation with respect to x, we obtain a linear integral equation for the order parameter:
(x1) = /dhe K(x1,.22)n(22), (20.2)

whose kernel has the form
K(x,,22) =- VT, > sS> exp(igix — igzx2)

n ky, K,41,42
x Pes akve (4+

i z ; kj, n)
x GO (-h,.+4
+>5 ? kp, x 42
a;—k, ns) : (20.3)
where V > 0 is the coupling constant, and the basis functions ~ depend onthe directions
of vectors k; = (k;,x, ky).
Taking the Fourier transform of equation (20.1) and then substituting it in
equation (20.3), we obtain after integration over the absolute values of k; and then over
41,2 the following expression for the kernel!:
K(n) = MES [fao(- “etl,~ mF-(s)
+ exp (- 2 (x1 + mn)FO (| ; (20.4)

where s = cos @ and
20
M6) = |Zr%,9)
d
The functions f *)(k) =f) (s, p) are defined as follows. For fixed angles 0 < y < 2x
and 0 < @ < 2/2 we introduce two unit vectors:
ki. = (£c0s 9, sin cosyy, sin @ sin y) = (+s, V1 — s? cosy, V1 — s? sing),
! This expression is valid in the quasiclassical approximation. This meansthat, since the typical distance on
whichthe kernel changesis the coherence length £, which is considerably larger than the interatomic distance
~ ke!, we can neglect rapidly oscillating contributions to K(x;,x2) proportional to e2#r*,
BOUNDARY CONDITIONS FOR THE ORDER PARAMETER 149
which are related by the reflection in the surface plane. Then
f= 5 (WGUhs) + 4k(ks).
Thus the form of the kernel K(x1,x2) is determined by the symmetry properties of the
basis functions underreflection in the superconductor surface.
In the case of an infinite homogeneous superconductor, the kernel of the linear integral
equation, which determines the order parameter, has the form
1
VNol- ds 2|wy, _
K(x; — x2) =" mn > | Se(- BAe ~ mi) F' (s). (20.5)
"90
From the critical temperature definition,
it follows that
/ de, K(x; — x9) = 1. (20.6)
In comparison with an infinite unbounded superconductor, the effect of the surface is the
emergence of the second summand on the right of equation (20.4), which decaysat the
distance of about & from the surface and is responsible, as was indicated in Section 13,
for suppression of superconductivity in the surface layer.
Boundary conditions for the Ginzburg—Landau equations can be derived from the
asymptotic solution of equation (20.2) for x >> &. Direct substitution in equation (20.2),
with the help of equation (20.5), proves that a linear function (x) = yo(1 + x/b) with
real b is the sought-for asymptotic solution. The effective boundary condition in this case
has the following form:
on
Ox eg bo
1
(20.7)
The parameter b is identical to the healing length introduced in Section 13.

Note two essential symmetry properties of the boundary conditions. If the basis
function is invariant underthereflection x + —x, i.e. o(k—) = o(k,.), then b = oo,ie.
On/Ox\,,) = 0. Actually, by continuing the order parameter to the ‘non-physical’ region
x <0 so as to generate an even function: 7(—x) = n(x), we transform the kernel (20.4)
into the uniform bulk kernel K), and equation (20.2) can be extended from the half-
space to the entire space:
(x1) = / dx, K(x1 — x2)(x2). (20.8)

This equation determines the superconducting transition temperature for an infinite

uniform crystal. By virtue of equation (20.5), the even solution of this equation is simply
a constant. Thus, the boundary condition takes the form (13.18):
an
xl, o> 0. (20.9)
Let us prove that in the opposite limiting case, when the basis function changesits sign
underreflection, we have b = 0. Now the order parameter should also be extendedto the
region x <0, but in this case to construct an odd function: 7(—x) = —n(x). Then
equation (20.2) is again transformed to the bulk equation, whose odd solution is a linear
function of x. As a result, we have boundary condition of the form (13.16):
nlpao= 0: (20.10)
In the general case, when the basis functions have no definite spatial parity under the
reflection in the interface, the integral equation that determines the order parameter does
not reduce to a simple form, and the boundary condition does not look like (20.9) or
(20.10). In this situation, we can use the following approximate expression for the healing
length b:
1 2
71¢(3) dss? (F Cs) - RO (3))

+ * (20.11)
2n2
[as(dss (FO)(s) — F)(s)
:
The derivation of this formula will be given at the end of this section.
For the identity representation Ajg, corresponding to the conventional s-wave order
parameter, the basis function ¢(k) ~ const does not change its sign under reflection in
the interface, and we have b= oo, which means the existence of surface super-
conductivity isotropic in the basal plane.
The situation is dramatically different in the case of non-identity representations.
Consider as an example the order parameter which transforms according to the repres-
entation By, of the group Dey. In the reference frame defined by the principal axes X, Y,
and Z (Figure 20.1), the basis function is expressed by
p(k) ~ kz (kg — 3kxk?). (20.12)

FIGURE 20.1 Orientation of the superconductor surface with respect to the crystal axes, The field H points
along the six-fold axis (the inward normalis directed along the %-axis).
If the crystal surface coincides with the X Z-plane, ie. y = 1/2, the reflection in the
surface corresponds to the change of variables Y — —Y. Under this transformation, the
basis function does not change its sign, and we have b = oo. Hence, the surface critical
field is maximal and determined by equation (13.22). We obtain the same result if the
angle y equals 7/6, 57/6 etc., since in all these cases y)(k) is invariant underreflection in
the boundary plane.
But if the superconductor surface coincides with the YZ crystallographic plane,i.e.
y = 0, the transform X — —X changesthe sign of the basis function (20.15). Therefore
b = and 7(0) = 0. In this case (and also when y = 7/3, 27/3 etc.) the surfacecritical
field is minimal and equals the uppercritical field in the bulk (see equation (13.17)).
The final result is
He3(T) _= {= 1.69, for y = tue
6 , (20.13)
H2{T) 1, for p =%,
where n = 0,1,...,5. Thus, both the boundary conditions and the surfacecritical field
are essentially anisotropic(in this case,it is the six-fold anisotropy.” It is noteworthy that
equation (20.13) derives from the general symmetry properties of the basis function of the
representation By underreflection in the boundary plane which meansthat this result is
independentof the choice of 4(k).
At intermediate values of the angle y one should use boundary conditions in the
general form (20.7), and in calculating b(y), which is a periodic function with period
n/3 varying between 0 and oo, the choice of the basis function is, of course, essential.
The curve of H.3(y) should have rather sharp peaks. The point is that there is a char-
acteristic scale on which the order parameter notably changes at temperatures near T,,
namely, the correlation length € >> &. If b(y) < €, which is the case almost every-
where, except for the narrow vicinities of width 6p around y= 7/2 etc., then the
effective boundary condition has the form (20.10), and H.3 = H.2. On the other hand,at
2 To avoid misunderstanding, we emphasise that the anisotropy of the surface superconductivity is inter-
preted as the anisotropy of the slope of the H.3(T) curve, given a fixed direction of external magnetic field,
namely, along a principal axis, and variable orientation of the surface normal with respect to the basal plane.
lp — (2n + 1)n/6| < dy we have b(y) > €, ie. effectively b = 00 and H.3 & 1.69H.2.
The peak width is determined by the specific shape of the function b(). For the basis
function (20.12) the calculation using equation (20.11) yields
b (1g
1 Qnt 2n+1)atn
ray cos’ 3y 6
hence dy ~ 1/£0/E.
In the intermediate range of angles, where b varies between 0 and 00, a superconducting
state near the surface is expected to emerge at some field between H..(T) and
1.69H.2(T), whose slope is a function of H. It is noteworthy that the anisotropy of the
healing length (20.11), and hence of the surface energy, cannot be described, generally
speaking, by the simplest functions f(n) allowed by the symmetry of the system (see
equations (13.12)-(13.14)). The nodes of these functions (i.e. the peaks of the healing
length), however, are determined by the symmetry elements.
Diffusely scattering surface
To determine the boundary conditions at a diffusely scattering surface, it is convenient to

use the method of quasiclassical trajectories (see Refs. 81 and 82). The starting point, as
in the case of a specular surface, is an integral equation like (17.9) for componentsof the
order parameter.
Taking into consideration the weak energy dependenceof the density of states near the
Fermi surface and retaining only the components slowly changing on the atomic scale, we
obtain the following expression for the kernel K(r1,r2):
K(r1,¥2) = nVNoT S_ ja exp(—2|w|t)(* (ii) di(i2)) ., ctassical’ (20.14)

nog
where 7(i) are the basis functions of the chosen representation. The angular brackets
denote averaging over all trajectories of a classical particle moving with the Fermi
velocity up which connect points r; and r2 and satisfy the condition r(0) = r;. In this
calculation, we should take into account both thetrajectories starting at t = 0 at the point
r, to end at the moment¢ at the point r2 and the time-reversed ones, i.e. those which start
at time —f at the point r) to end at ¢t = 0 at the point r, (the explicit expressions below are
given only fortrajectories of the first kind, since the time-reversed trajectories only make
a Hermitian conjugated contribution to the kernel). The unit vectors my = n(r)) and
ig = n(r2) denote directions of the particle velocity at respective points.
To derive equation (20.14), we start with the microscopic definition of the kernel K:
Vr 7 Ve! Vee _ Vr
K(r,%m)=VT ii * a) (“GE)
( ' 2) YY ot
—>r »¥ ( ike % 2ikp
: 12oon
x G6) (ri, Y2; wy )G (r}.053 —wWy) (20.15)

(cf. equation (19.2) for the case of p-wave pairing). Here G) is the Green’s function of
the normal state which can be represented in the following form:
(0) (r; »2;‘w) Wn) = d Wipoe

(1) Wilra) ;
iw, — ( 20.16 )
where W; are eigenfunctions of the one-particle Hamiltonian Hp (Section 17), and ¢; are
the corresponding eigenvalues. Hereafter we omit spin indices.
By substituting (20.16) in “a (20.15), we obtain
K(er) UEyyivdeLe Se, 0.17)

aie (iw, — €;)(—iw, — €;)
where J(r) is the current operator:

1, 0 O
S(r) = 5jim(5-505):
The next step is based on the fact that only the slowly changing parts of the wave
functions contribute to the superconducting kernel. Therefore, the quasiclassicai
approximation can be employed. One can prove [81, 82] that the product of the two
matrix elements in the numerator on the right-hand side of equation (20.17) can be
written in this approximation in the form
ainsi = ado faterte a)

00
x (A(n)BO()602—- 1) ér, classical

(20.18)
where the averaging is performed overall classical trajectories r(t) such that r(0) = ry.
Nowlet us divide the integration domain in equation (20.18) into two parts, (—oo, 0) and
(0, 00), and changethe variable in the former: t + —f. Thus, we have obtained an integral
over to positive t of the sum of two contributions, namely those from the ‘direct’ and
‘time-reversed’ trajectories connecting points r; and r2 (the time f in this case has the
meaningofa particle’s flight time alongits trajectory). After summation overi and j, we
obtain equation (20.14).
Let us analyse two types of quasiparticle scattering at the surface, namely the specular
and diffuse reflection. Moreover, we limit our analysis to the case of clean super-
conductors. Hence all quasiclassical trajectories in the bulk are straight lines, and all
contributions to the kernel can be separated into two classes: ‘direct’ and ‘reflected’
(Figure 20.2).
The first contribution is determined by the trivial trajectories: r(t) = r+ vet. Sub-
stituting them into equation (20.17), we have the following expression:
1
K(x1,x2) = HVoe
Nol ds
>/S 2|wy
exp (—“eH ny al) %), (20.19)
n 0
FIGURE 20.2 Direct (1) andreflected (2 and 2’) trajectories connecting the points r; and rz in the case of
diffuse scattering at the superconductor boundary.
where
Fs) = [Lveewee+¥esev-sy)). (20.20)

Asin the previous sections, we use the following notation: s = cos @, where @ and yp are
the polar and azimuthal angles, respectively (the polar axis points along the X-axis, i.e. the
surface normal). We also assume that all frequency sums are cut off at the boundary
frequency €).
Asregards the second contributionto the kernel due to all possible reflected trajectories,
its form essentially depends on the character of reflection of quasiparticles at the surface.
Tn the case of specular reflection, we deal with only one trajectory:
r(t) = r1 vet,
Vv;Ft; t<t 0 “1
== Up.’
Ve(t—t), t> to,
where fo is the momentof hitting the surface and ¥p = (—vp,x, Up,y, Up,z). Substituting
this expression for r(t) in equation (20.17) and integrating, we finally obtain the fol-
lowing result:
1
aV Nol ds 2|Wy
KP) (4,02) = oe > [Se0(-h + x)Fespec (s), (20.21)
n 0
where
rem(s) = f P (ur(-s,y)¥6s,9) + 06, 9)H-.9)). (20.22)

The sum of the expressions (20.19) and (20.21) coincides, as one should have expected,
with equation (20.4), which was obtained by direct integration of Green’s functions.
In the case of diffuse scattering, we should take into account contributions from all
possible trajectories like those described by the following formula:
*1
nt+vet t<p=-—,
r(t) = URx
2
vO (tt), t >to;
where vi) and vi) are the particle velocities on two linear sections of the trajectory, and
by integrating over all reflected trajectories with the weight factor (1/7) cos @ we obtain
K (Giff) (x1 , x2) _ TV Nol

UF
1 1
Qlwnl (x1 x2 ,
x > fas [as exp(——— (F +=) FO(51,52) (20.23)
n 5 0
where
2a 2a
F(A (5), 59) -| = f oe (v9, 91) 0(s2, 92) + ¥*(s1, 91)Y(—s2, p2)):
0 0
Finally, we have
K(x1, x2) = K(x1, x2) + K") (x1, x9). (20.24)

In the general case of anisotropic pairing and an arbitrary orientation of the surface,
equation (20.2) with kernel (20.24) cannotbe solved exactly,’ but a variational technique
can be used to calculate b. As a result, the healing length b is always of the order of £,
i.e. the effective boundary condition in the domain of applicability of the Ginzburg—
Landau theory has the form (20.10), and no surface superconductivity occurs for all
directions of the normal. One can prove [83] that in the case of s-wave pairing the
boundary condition has the form (20.9) irrespective of the character of the electron
reflection.
Thus, the surface superconductivity near a diffusely reflecting boundary is highly
sensitive to the inherent symmetry of the order parameter, since the random character of
electron reflection leads to its becoming isotropic, and this can be achieved only through
suppression of superconductivity near the surface.
3 If the order parameter corresponds to a non-identity representation of the crystal point symmetry group,
then for somespecific directions of the normalthe contribution K“(x, , x) is identically zero after the angular
integration. A similar situation occurs in p-wave states for all surface orientations [72]. The integral equation
(20.2) can be solved in this case using the Wiener-Hopf method.
Derivation of equation (20.11)
To calculate the parameter b in the linear asymptotic of the order parameter, we use a
variational technique.
Let us introduce a dimensionless variable X = x/& into equation (20.4). Then
1
1ds | 2n+1
K(Ki,%) = 50M fF FO )exp(-! : ly, - x2)
n 0
|2n + 1|
+ F)(s) exp (- (X, + %2)) , (20.25)
s
For X >> 1 let us seek a solution in the form (X) = C(X + q(X)), so that b/f =
yim q(X). The equation for g(X) has the form
oo
q(X1) = 5B(h) + [% K(X1,X2) q(X2), | (20.26)

0
1
E(X) = VNo > ap|aes[rO

(n+) +PFH (s)| exp _!
2n ,+1 XxX .
0
In order to formulate the variational principle, note that the integral equation for the order
parameter can be obtained by varying the functional: 6@/ég = 0, where
jo q(X) x - [xxx 20)

8[q] =2 CO
° 2 (20.27)
/aXq(X)E(X)
0
The extremal (minimal) value of the functional is
00 -l
Bain = |2 /dXE(X)q(X)
Now let us prove that the required limiting value of the solution of equation (20.26) is
expressed for X — oo through ®yjn. Let g(X) = b/& + Q(X), where Q(X) > 0 as
X — oo. Substituting g(X) in equation (20.26) we obtain an equation for Q(X), then we
multiply both its sides by X, and, after integrating with respect to X; from 0 to oo, we
finally have
j
1
bt lt5 |85 3 \F ele) (s) + FO(5)]
4)
BS
= +
oC
VN0 Onin
ds s°F)(s) °
The parameter ®y;, can be calculated using the variational principle. By selecting an
arbitrary constant as a trial function and substituting it in equation (20.27), we obtain
equation (20.11).
21 Effect of Impurities on Unconventional
Superconductivity
It is well known that non-magnetic impurities have no influence on the thermodynamic

properties of conventional superconductors. In particular, the critical temperature is in-
dependent of the concentration of non-magnetic impurities. Superconductivity is sup-
pressed only by magnetic impurity scattering, which destroys the coherence of the
electron spin states in Cooper pairs with S = 0. In unconventional superconductors, such
an effect can be caused by scattering on non-magnetic impurities, which destroys the
coherence of the orbital wave functions of paired electrons.
In this section we will consider two effects due to the presence of impurities in
unconventional superconductors: first, the decrease in the critical temperature caused by
non-magnetic impurities, second, the changes in the quasiparticle density of states and the
thermodynamic properties of superconductors as T — 0.
Gor’kov equations and the transition temperature
Green’s functions of a superconductorat an arbitrary temperature T < T, in the presence

of impurities are determined by solving Gor’kov equations (17.6)—(17.8). To this end, one
should add to the one-particle Hamiltonian the term responsible for impurity scattering in
the form
Himp = > Uaplk, k’) An AK B, (21.1)

kk’
where ua(k, k’) is the amplitudeof electron scattering in the field of impurities, which is
spin-dependent, in the general case.
Since the only interesting characteristics are those averaged overall possible config-
urations of the random potential (i.e. over the impurity positions), one should use
159
as mu
/ ‘ 7 \
/ \ / \
> a co =a
G(k, ©,) F (k, ®,)
a b
FIGURE 21.1 Impurity self-energy functions in the Born approximation.
equation (17.11) including the self-energy parts due to impurity scattering (Figure 21.1)
for calculation of Green’s functions. Averaging is performed in exactly the same manner
as in the theory of conventional superconducting alloys [71]. We do not take into con-
sideration the interference between the waves scattered at different impurities since the
weak disorder condition kg/ >> 1 is assumed to hold, where / = upr is the electron mean
free path. Moreover, we neglect the possibility of multiple scattering at one impurity,
whichis legitimate if the impurity potential is small in comparison with the characteristic
electron energy ép (Born approximation).!
Under these conditions, the diagrams for the averaged self-energy parts each contain
two impurity crosses connected by dashed lines (Figure 21.1). If the impurity scattering is
isotropic and spin-independent, the dashed line corresponds to the expression
2 1
Pimp?
P
= =——
2nNoT’
where nimp is the impurity concentration, u is the scattering amplitude in equation (21.1),
and 7 is the quasiparticle mean free time.
In an anisotropic superconductor, the impurity scattering amplitude is a function of
angles, and the dashed line corresponds to the expression #~!(k’), which transforms
according to the crystal point symmetry group (Section 4). It can be expressed as an
expansion in terms of the irreducible representations of the group G:
Tayo (K, k’) = (= aps + ——

*t o.s0%s) Soul
5 (kK)*(K’) (21.2)
T f=1
in the case of weak spin-orbit coupling or
Talk) = SZ >(F)o(¥F"IS)
dp
T =1
in the case of strong spin-orbit coupling. Index I’ denotes the irreducible representations
of dimensionality dp of the group G, andi labels the basis functions ~? (k). The expansion
coefficients of 7~! are proportional to the impurity concentration, and the terms in
equation (21.2) containing 7 correspond to the spin-flip scattering.
! Some effects that occur beyond the Born approximation will be discussed below.
EFFECT OF IMPURITIES ON UNCONVENTIONAL SUPERCONDUCTIVITY 161
For simplicity, let us limit our analysis to isotropic scattering by non-magnetic im-
purities. Then the averaged normal self-energy part (Figure 21.1a) has the form
1 d*k
Xap (wn) = U(wn) bag = InNot esas Wn) bop. (21.3)
The anomalousself-energy part, represented by the graph in Figure 21.1b,
1 d*k
x 2, a, p(Wn)
n) =Zoaw.
2a Not OU
(2)?
Fap(K, wn) (21.4)
vanishes after integration over the angles defining the direction of k in the case of
isotropic impurity scattering for all superconducting states transforming according to
non-identity representations.
Now the Gor’kov equations can be written in the form
(wn, — & _ U(w,))G(K, Wn) bap + Aan (k)Fig(k, Wy) = Cah
(i, + & — E(wn))Faa(k, Wr) + Ava(k)G(K, wn) = 0, (21.5)
(iw, — &, — D(Wy))Fap(K, wn) — Aag(k)G(—-k, —w,) = 0.
Hence wederive the following expressions for the superconductor Green’s functions:
iW, + &
Coun) = Teas
“K (k) (21.6)
Fop(K, w,) =—— 3,
calls) ors a+ AE
where
IDy = iw, — U(wn). (21.7)
The self-energy part should be calculated in self-consistently. By substituting the
expression (21.6) for G into (21.3) and integrating over € in the assumption thatthere is a
symmetry between electrons and holes, we obtain the following equation:
id, dQ 1
E(w,) = — (21.8)
2r 4m /G2 + AR
For T < T, the solution of equations (21.7) and (21.8) is determined by the specific form
of the order parameter.
Near the critical temperature the order parameter is small, and the dependence of the
right-hand side of equation (21.8) on A, can be neglected. From (21.7), we obtain
~ 1...
Wy = Wy +> SIZN Wy.
27
Hence
Wy = Wy +
2r SIgN Wy,
Therefore, the self-energy part for A, — 0 has the form
i,
U(w,) = ~ 9, Signwn, (21.9)
ie. it is identical to the corresponding expression for the normal metal, as was expected.
The averaged anomalous Green’s function can be written as
= Aag(k)
Fop{Ke wn) = (wn + (1/27) sign wy)” + 2 (21.10)
Substituting (21.10) into the self-consistency condition (17.5) and integrating over € we
obtain
Aaa(k) = TMOVT+ (1/27)

signwnsignw, Vian
dQ’
4m
(K, k!)Ays(k’).
After substitution of the expansions of the attractive pairing potential V from Section 5
into the latter equation, we have
sign W,
1 = T —
mNoV ars + (1/27)signw,
1 1
= 2nNoVT | —
T+ av T(t - =). (21.11)
n>0 wn n>0 wy + 1/27 wn
The logarithmically divergent sum in the first term on the right is cut off at the boundary
frequency ¢;. Given the formulafor the critical temperature 7,9 in a clean superconductor
(equation (18.17)) and having transformed the second (convergent) term on the right of
equation (21.11) taking account of the definition of the digamma function w(x), we
obtain the final result [841]:
1 1
— =}. 21.12
Te2 =v (5+ 4n TT,-) - v (5) ( )
This equation determines the decrease in the critical temperature for an arbitrary
superconducting state with a non-trivial pairing due to isotropic non-magnetic impurity
scattering with respectto the critical temperature T,9 of a clean superconductor. Note that
equation (21.12) is identical to the equation describing the decrease in the critical tem-
perature of a conventional superconductor caused by paramagnetic impurities [85], albeit
with a different meaning of notations.
In the case of low impurity concentration, we have

wT
T. = Too — gr (21.13)
(here we have used the formula w’(1/2) = 1/2).

Thus, non-magnetic impurities in a superconductor with a non-trivial pairing suppress
superconductivity. On the qualitative level, this effect can be interpreted as follows.
Doping leads to the order parameter becoming isotropic. If the Cooper pairing, however,
occurs in a state with broken spatial symmetry, the only way to make the order parameter
isotropic is to tum it to zero over the entire Fermi surface, which happens at a certain
impurity concentration at which 7A~ 1, where Aois the absolute value of the order
parameter at T = 0 in the absence of impurities.
Density of states
It is also interesting to reconstruct the process of suppression of the order parameter and
the evolution of the gap nodes with the increase in the impurity concentration. To this
end, let us calculate the density of quasiparticle states N(E) (see Section 17) for E — 0.
In doing so, we will not take into consideration the self-consistency equation for the order
parameter in the presence of impurities since it has no influence on the behaviourof the
function N(E) as E — 0, but only on the absolute value of the order parameter.
Let us perform the analytical continuation in equation (21.7) and introduce the notation
t(E) = (in) liu,+10 E—D*(E). (21.14)
Then the expression (17.27) for the density of states, taking into account (21.3), can be
transformed to
N(E) = —2NoT Im E(w) |j,,524 i0= 2NoT Im t(E). (21.15)
Thus, the problem has been reducedto calculation of Imt(E ). To this end, equation (21.8)
should be analytically continued to the axis of real frequencies. As a result, we obtain a
self-consistency equation for t(E) depending on the structure of the order parameter
A(k):
i
t=E+>a(t),
=E+— (21.16)
1.16
where
= | dQ
GE t
(21.17)
(the sign in front of the square root in the analytical continuation is selected such that
Im* < 0).
To illustrate the properties of the density of states in doped unconventional super-
conductors, let us find the solutions of equation (21.16) for different p-wavestates.
B-phase
As in the case of conventional superconductivity, in the B-phase A = A? = const, and

equation (21.16) has the form
i t
t=E+ Jp Ad
The imaginary part of the solution t(£) is non-zero (hence, the density of states is also
non-zero) only when E > E,, where the threshold energy corresponds to the maximum
value of the function E(t) = t — t/27V A? — #2 [85]:
1 \2/3\3/2
E, = a(t - (a) ) ; (21.18)
Onecansee thatat a sufficiently high concentration of non-magnetic impurities such that
T < 1/2Athe gap in the spectrum goesto zero. At the sametime,the critical temperature
determined by equation (21.12)is still non-zero, which meansthe existenceof the gapless
superconductivity, as in conventional superconductors with paramagnetic impurities (see
Exercise at the end of this section).
A-phase
The order parameter is expressed as A? = A?sin” 6 (we have chosen the same normal-
isation condition for A as in Section 7). By performing integration over the angles in
This equation can be solved in the limit E — 0:
E iE?
t= + +:
1—n/4rQ 27A2(1 — 2/4rA)
hence follows
N(E) = No aoweaF (2).

The coefficient in front of E* increases with the doping level, i.e. with decreasing the
mean free time 7, and at rA = 7/4 it becomes infinite. This determines thecritical
concentration of impurities, above which
N(E =0) = 2NorAtg ¢ - 2rd). (21.19)

The physical meaning ofthis result becomesclear after comparison with equation (17.30):
the gap nodes in the quasiparticle spectrum of the A-phaseare isolated points when the
impurity concentration is low and spread to become spots ofa finite size where the gap
width is zero [23, 86] only at concentrations higher than the critical value.
Polar phase
The order parameter has the form Ae = A? cos? 6. From equation (21.16) we derive
i _A
t= E+ 2—\tarcsin 7
27TA
One caneasily verify that at E = 0 this equation has the following solution:
iA
whence
2rA
N(E = 0) = No=RarA’ (21.21)
This means that, at an arbitrarily low dopinglevel, the line nodes spread to strips of a
finite width [23, 86]. This effect leads to changes in the thermodynamic properties of
superconductors with such a structure of the electron spectrum as T — 0, in particular,
the electronic specific heat becomes proportional to the temperature.
Exercise
Using equation (21.12), calculate the critical impurity concentration at which T, vanishes
and determine the range of existence of the gapless superconductivity in the B-phase.
Beyond the Born approximation
The analysis given above was based on the Born approximation,i.e. the possibility of
multiple electron scattering at the same impurity was neglected. If multiple scattering is
to be taken into account, the only modification to the theory is the replacement of the
self-energy parts calculated in the Born approximation bytheir exact expressions. In the
case of conventional superconductors, the basic conclusion that conventional super-
conductivity is not affected by non-magnetic impurities still holds. In unconventional
superconductors, impurity scattering leads to suppression of superconductivity, and the
behaviour of Green’s functions and also the physical properties of superconductors
beyond the Born approximation is considerably modified {87, 88].
Weconsider the case of weak disorder,i.e. a sufficiently small impurity concentration,
consistent with the condition kpl >> 1, which allows one to neglect the graphs with
crossing dashed lines. Physically, this means that the interference between wavesscat-
tered by different impurities can be neglected, and X(w,) is obtained by simply multi-
plying the contribution of a single impurity Lo(w,) by the impurity concentration:
¥ (wy) = imp&o(wn). The parameter Xo(w,) is directly related to the exact zero-angle
scattering amplitude at an isolated impurity, which is determined by the sum of diagrams
in Figure 21.2. In the case of an isotropic point-like impurity potential, the anomalous
self-energy part goes to zero for all superconducting states with the order parameters
HP = tS $$
FIGURE 21.2 Graphic representation of the equationforthe point-like scattering amplitude by a single impurity.
corresponding to non-identity representations of the crystal symmetry group.In this case,

the scattering amplitude is characterised by the single scalar function f(w,) so that
(Ww) = Nimpt (Wn). (21.22)
In the general case, the scattering amplitude depends on the momenta and is a 4 x 4
matrix (T-matrix) in the ‘spin times particle-hole space’ (see Section 17).
Summation of the diagram series in Figure 21.2 allowsone to express f(w,) in terms of
the bare scattering amplitude uw. It is more convenient, however, to express the exact
scattering amplitude in a slightly different way by introducing the phase shift 59 of the
scattered s-wave in the normalstate:
ky
(OST Gk)
R k
(21.23)
where k, = —tanéy/mNo, and G(k,w,) is the averaged Green’s function of the super-
conductor.” Substituting (21.23) into (21.22), including the real (even in w,) part of
the self-energy function in renormalisation of the chemical potential, and explicitly
separating the imaginary (odd in w,,) part, we obtain
Nimp K2 S> G(K, wy)

E(w_) = x (21.24)
1 — k2 (= Gk, ws) |
Here wehave used the fact that, in the case of electron-hole symmetry, 5+, G(k, ~w,) =
— dix G(k, w,) (see equation (21.6)). Substituting Green’s function (21.6) in equation
(21.24), we. finally obtain an equation for the function t(Z), which generalises
equation (21.26) to the case of a non-Bornscattering:
;
t= E+ i.—— _7__——
g(t) 21.25
cos? 69 + sin? 5p g? (t) , ( )
where
nj .
Tr =—*® sin? 6,
aNo
and g(t) is given by equation (21.17). In the limit of weak scattering (6) — 0), we obtain
? The derivation of equation (21.23) is given at the end ofthis section.

ro Nimp 62 2 1
+
aNo 0 = 1 NoNimpPp Uo = 3
2TBom
and equation (21.25) transforms to (21.16).

Expression (21.15) for the density of quasiparticle states is valid only in the Born
approximation. In order to calculate N(E) in the case of arbitrary phase shifts, let us
return to the definition (17.27):
1 1 (21.26)
N(E) = >» G(k, wn) = ~ Fie G(k, E).
fw, E+i0
Green’s function in the latter equation is obtained by the analytical continuation of

equation (21.5):
t(E) + &
From equations (21.26), (21.27), and (21.17), we finally have
N(E) = No Re g(t(£)). (21.28)
As was shown above, in the Born approximation, the isolated gap nodes in a super-
conductor with the structure of, for example, A-phase are stable against introducing a
small number or impurities. Let us prove that this is no longer the case for a sufficiently
strong scattering potential.
Consider the case of resonant scattering, which is opposite to that of Born scattering,
ie. the phase shifts are large: 59 7/2. By substituting into equation (21.25)
Az = A? sin? 0, we obtain the following equation for ¢(E):
-1
1
t = p+2r
; as= (ne
{In it ) , (21.29)
which has the following solution at E =0 andl <A:
t(E) = iy AS (21.30)
After substituting the latter expression in equation (21.17), we have
al
Re g(t(E = 0)) = 2N
Finally,
N(E =0) = oy [Ze (21.31)

Onecansee that the density of states at E = 0 is finite, but, naturally, goes to zero as the
impurity concentration decreases, i.e. at I‘ 0. This means that at an arbitrarily low
concentration of resonant impurities the isolated gap nodes in the superconductor spec-
trum spread to spots of finite size [88].
Exercises
(1) Calculate the decrease in the critical temperature of a p-wave superconductor due to
resonant impurity scattering. How is equation (21.12) modified in this case?
(2) Calculate the density of states at E = 0 for the polar phase due to resonant impurity
scattering (Yu. S. Barash, V. P. Mineev, and A. A. Svidzinskii, Pis’ma Zh. Eksp. Teor.
Fiz. 65 (1997) 606 [JETP Letters 65 (1997) 638]).
Derivation of equation (21.23)
The diagrammatic series in Figure 21.2 can be reduced, as one can easily prove, to the
following equation for the scattering amplitude:
fw) =u+uS— G(k,w)fw). (21.32)
Let us express the superconductor Green’s function in this equation as
G=G9+6-6%, (21.33)
where
alt) =1 (60+6)
is the real part of Green’s function for scattering at an isolated impurity in the normal
state. In accordance with the definition of Green’s function of the Schrédinger
equation,
1 1
G)(w) = ———, =P — ind(w—e€) = Gg") + G©
w—et+i0 wW—e on?
where ¢ is the energy of free electrons scattered by the impurity and P denotes the
principal value of the integral. The subscripts ‘off’? and “on” at the real (imaginary) part
of Green’s function indicate that the intermediate states are off (on) the mass surface.
Substitution of (21.33) in (21.32) and regrouping of the summandsyields
f(w) = (: +0 S~ GY} (kw) ++ | (: + S7(G(k,w) - Qk, rt)

k k
= ky + ky Y (Gk, w) — GY) (k, w))f(w). (21.34)

Here we have introduced the parameter k,, which describes impurity scattering in the
normal metal and satisfies the equation
ky =u+uG ky.
In the general case, the scalar function k, should be replaced by a 4 x 4 matrix (K-matrix)
[88].
The function k, is parametrised in terms of the phase shift of scattered waves in the
following way:
tan do
ky =- . 21.35
" aNo ( )
The sum of GO (k, w) over the momenta on the right of equation (21.34) is zero, and we
obtain equation (21.23).
22 Electronic Thermal Conductivity of
Unconventional Superconductors
The presence of nodes in the spectrum of elementary excitations leads, as was demon-
strated in previous sections, to considerable changes in the thermodynamic properties of
superconductors at low temperatures. Nodes in the spectrum also play an important role
in the kinetic properties of unconventional superconductors.
The simplest technique for describing non-equilibrium properties of superconductors
is based on the Boltzmann kinetic equation for the distribution function of excitations.
In fact, the Boltzmann kinetic theory applies only to a gas of well-defined elementary
excitations, whose energy is larger than their inverse lifetime. This condition is, un-
doubtedly, violated in unconventional superconductors with nodes in their spectra of
elementary excitations, which have a finite density of states at zero energy. Therefore the
relaxation processes can only be described by the Boltzmann equation in the region of
sufficiently high temperatures, where the average thermal energy of excitations is large in
comparison with their decayrate -y. In clean superconductors, this region includes almost
the entire temperature range, except for very low temperatures, therefore the Boltzmann
equation applies to this case. Note, however, that even in this case the calculation of the
lifetime of excitations as a function of energy, through which the kinetic coefficients are
expressed, cannot be performed without the microscopic theory. At T < y the kinetic
coefficients can be calculated only using the field-theoretical methods. This section
presents both these approachesto the kinetics of superconductors, taking as an example
the electronic thermal conductivity.
Kinetic equation method
Let us recall the definition of thermal conductivity «. The thermal flux carried by non-
equilibrium excitations is given by the equation
171
3
a0) =2 | aeyvnlnyi
(2m)
(22.1)
where E is the quasiparticle energy, vy = OE/Ok is the quasiparticle velocity in a su-
perconductor', and f(r) is the non-equilibrium distribution function of excitations in-
teracting with impurities. The thermal conductivity « is the proportionality coefficient
between the thermal flux and the temperature gradient:
Q=-«KVT. (22.2)
Thedistribution function f(r, ¢) satisfies the Boltzmann kinetic equation, which has the
form
ae! Ea Fr) 23)

oe OF Of On
—=(— 22.3
where the right-handsideis the collision integral due to impurities.” This equation can be
simplified in the case of a stationary thermal flow and the distribution function closeto its
equilibrium value. Since the collision integral vanishes when the locally equilibrium
distribution function fiity) =f(Ex(r)/T(r)) is substituted into the kinetic equation (here
f is the Fermi function (6.2)), we can replace f by fon the left of equation (22.3) in the
approximation which is linear in the small difference between the non-equilibrium and
locally equilibrium distribution functions. We have
BE (0) af dB AF E of.OE
dk 7k ak Ok OE. zVE pi!) ~ VEoe
_ _ Fafa
=—T oe SLY. (22.4)
Note that the terms containing gradients of the gap width A cancel out.
The collision integral in the case of weak disorder is obtained by multiplying the
(8)a[Zonmen-sn
contribution of a single impurity by their concentration:
where w(k,k’) is the rate of the elastic quasiparticle scattering and éf is the deviation
of the distribution function from its equilibrium value, which should be substituted,
according to equation (22.1), in the expression for the thermal flux:
d*k
Q=2 [Gap teonien. (22.6)
' A coordinate dependenceof E and v is due to the temperature dependenceof the gap width A, since the
temperature is a function of r. We assume that T changeslittle on the scale of the correlation length.
? Derivation of kinetic equations for superconductorsis a fairly complicated problem, since the dynamics of
the order parameteritself should be taken into account properly. Equation (22.3) holds provided that the
excitations travel in a time-independent, weakly inhomogeneouspotential A(r), and Ey(r) = \/€? + A2(r).
ELECTRONIC THERMAL CONDUCTIVITY OF UNCONVENTIONAL SUPERCONDUCTORS 173
In the Born approximation, the scattering rate w is calculated using the Fermi ‘golden
tule’:
Qn
w(k, k’) = 5 |(K'|Himp|k) |6(Ex — Ex).
Performing the Bogoliubov transform (5.25) in Hamiltonian (21.1), which describes
interaction between electrons and nonmagnetic impurities, we obtain
w(K, k’) = 2C(k, K')5(Ex — Ey), (22.7)

where the so-called coherence factor is given by the expressions
1
a (1 +
Ex&u — Re A’g(k)g(k’) »,
ByEy
_
atS=0,
C(k,k’) =
1 f,€y — Re A*d(k)d(k’) _
5 (1 + BE », atS=1.
Onecan see that in the case of anisotropic pairing the probability w dependson the angles
even in the case of an isotropic scattering amplitude u(k, k’) = u = const.
Let us rewrite equation (22.3), taking into account equations (22.4) and (22.5), in the
form
Of — Tk la
ki, ofVI
(k, k ofg => TREKV “OE T’ (22.8)
where
7'(k,k’) = nimpw(k, k’),
—— ak! Tk, k’) = Qn d°k! k')6(Ex — Ey!

Tk los (k, k’) i= Himp
nimp U v2 lee
——C(k, ) ) ( k Kk’): ( 22. 9)
and 7, is the mean free time. Since 7~" 1 is invariant under the particle-hole exchange
&, — —& and spatial inversion, but the right-hand side of equation (22.8) changesits
sign, it follows that 6, should be odd under these operations. For this reason, the second
term on the left of equation (22.8) goes to zero, and
Offic = Tk AV OfVT
OE T
Substituting this solution of the kinetic equation in equation (22.6) and taking into
account the definition of the thermal conductivity coefficient (22.2), we finally have
2 Bk af©
Ry = aloe aE EYUk,i Uk,j Ths (22.10)
where the quasiparticle velocity is defined as follows:
_ OF
Ko TUpk #+0(E).
poe (22.11)
Of all the parameters in equation (22.10), the only unknownis the lifetime 7 of
quasiparticles. In the case of singlet isotropic pairing, we derive from equation (22.9):
1 Qn >» aek' A?
mo pti [Eas (I By)Pe Fe)
11 ER-A? fdtk’ 1 N(Ex) &
6(E, — Ey) =— ze 22.12
~ 7 No ER lo ( k ’) Th No ER’ ( )
where
2
n= = imp Now (22.13)
is the mean free time in the normal state,? and the density of states N(Ex) =
f dk'S(Ex — Ex)/(2m)’ (see equation (17.26)). Substituting equations (22.11) and
(22.12) into (22.10) and taking into account (17.28), we obtain the expression for the
thermal conductivity coefficient [89, 90]:
oo
tae| dé Epe™/T No = nie f dE E? (22.14)

372 (e&/T +1)? N(Ex) 37? cosh?(E/2T)
A
For T<A
2
A(T) = suet, No (3) exp (- 7) ,
yeas. a
which can be transformed to
where the thermal conductivity in the normalstate is

1
Kn(To) = guF TmNo Tel, (22.16)
and
-+co
I / dev 2n?*
J cosh?z/2 3
0
3 Given the expression for the velocity of excitations v = OE/Ok = upé;/E,, and equation (17.28), it follows
from equation (22.13) that the mean free path in the s-wave superconducting state equals the mean free path in
the normalstate.
In the case of anisotropic pairing, the order parameter transforms according to a non-
identity representation of the symmetry group, and the integral of the coherence factor
over directions of k’ in equation (22.9) is unity. Hence it follows that
1 2m dk! AN(Ex)
a= atime? |7 OE — Eye) = 22.17
Tk (2m)? Tr No ( )
Substituting this expression into equation (22.10) and taking into account (22.11), we
obtain
, i= Zravh fk ek/T No
kikj
T? ( 2m)? (eP/T +1)? N(Ex) *
_ Noka EdE Me (Bing
= kj/E? — A2, 22,18
cosh?(E/2T) N(E Kk ( )
0
where the integration over angles is performed within the limits defined by the condition
Ap < E?.
In superconductors with the B-phase structure the thermal conductivity is isotropic and
exponentially small as T — 0 (see equation (22.15)).
On the contrary, in superconductors with the gap nodes at the Fermi surface, the
temperature dependence of thermal conductivity is not described by an exponential
function, but follows a power law, like many other physical quantities (Section 7).
Moreover, owing to the gap anisotropy, one should expect that the thermal conductivity
depends on the thermal flux direction. Consider as an example a superconductor with the
A-phasestructure, where the order parameter has nodesat the poles of the Fermi surface:
A? = A*sin? 6. Dueto the uniaxial anisotropy of the excitation spectrum, the thermal
conductivity is described by two coefficients: Ky =k, and K, = Ky = Kyy. From
equation (22.18) we derive
Nove f N Q
m= ae| dE E 0 [GBH isin? G05%0
T? J cosh*(E/2T) N(E) a
5 E/A
wy na NovR / _aBENo
| 6d0VE? — 26?
T? J cosh?(E/2T) N(E)J
cat dEE Ny ES
T? cosh?(E/2T) N(E) A?’
0
Using expression (17.30) for the density of states in the A-phase, we finally have
~= nw z (22.19)
The transverse thermal conductivity is calculated similarly:

Oo
a Nove dEE Q
KL =_ ref No [GV EPA Asin? sin? 0
T? / cosh?(E/2T) N(E)
Ta Nove T?
Hence it follows that
Ki(Z) (7). (22.20)

When the gap in the excitation spectrum has line nodes at the Fermi surface, as is the
case, for example, in superconductors with the polar phase structure, A? = A?cos?6,
calculations based on equation (22.18), similar to those given above, yield the following
results:
It follows from equations (22.19)—(22.21) that in superconductors with the gap nodes both
at the poles and on the Fermi surface equator, the maximum thermal conductivity is a
linear function of temperature, i.e. «(T)/T — const as T — 0.
Resonant impurity scattering [87, 91]
Expression (22.10) for the electronic thermal conductivity derived from the kinetic
equation also applies to the case of resonant impurity scattering. The difference from the
case of the Born approximation is that the energy dependence of the mean free time 7(E)
is essentially different and should be derived from the self-consistency equation for the
self-energy part given in Section 21. In this section, we obtain r(Z) and determine the
range of parameters in which the relaxation phenomena in unconventional super-
conductors can be described by the Boltzmann equation. In the presence of impurity
scattering, quasiparticles have finite lifetimes determined by the imaginary part of the
retarded self-energy function:
— = —2ImD*(E) = 2Im¢(E). (22.22)

T(E)
Here we have used the definition (21.14). The function f(E) satisfies equation (21.25).
In the case of resonant scattering (69 — 7/2), equation (21.25) takes the form
1
t=E+il—,
g(t)
where
In the normal state, g(t) = 1, and
i,(E) = E+il.
By comparing this expression with equation (22.22), we find that I‘ is related to the
quasiparticle lifetime in a normal metal doped with resonant impurities as follows:
1
—= 20, (22.23)
and the equation for function ¢(Z) in the superconducting state can be written in the form
i i
t=E+
mm al (02.24)
22.24
From equations (22.22), (22.24), and (21.28) we derive
1
= 1 1
_ LN)
1N(E 1
(22.25)
T(E) tm 8) tm No |g(@)P
Thus, the quasiparticle lifetime calculation, generally speaking, requires a self-con-
sistent calculation of the self-energy part using equation (22.24). But if the disorder is
sufficiently weak, the problem can be simplified for energies above a certain critical value
(the exact criterion depends on the specific type of the superconducting state, see below).
Actually, if for E — 0
Imt(E) — y = const 4 0, (22.26)
then it follows from equation (22.22) that for E < y the lifetime does not depend on
energy and
= = 24. (22.27)
The quasiparticle energy becomes smaller than its decay rate, and for T < y the Boltz-
mann kinetic description does not hold. But if E > y, we can limit our calculation of
the small imaginary correction to t(E) to the lowest order of the perturbation theory in the
impurity potential. This means, in particular, that we can neglect the difference between
t(E) and E in equation (22.25), Then
1 _ IME) 1
T(E) a i, “No |g(E)E ’ (22.28)
wherethe right-hand side should contain the density of states for a clean superconductor.
In calculating the thermal conductivity for the case of resonant impurity scattering
using the kinetic equation, one must use expression (22.28). Let us perform such cal-
culations for various p-wavestates.
For a superconductor with the A-phase structure, we derive from equations (22.26) and
(21.30)
y= | ja (22.29)
From equation (21.17) we obtain the function g(E£) (for y < E< A):
-(—s
A?sin” 3
Substituting this expression into equation (22.28) and taking account of (17.30), we
obtain
T(E) ~ T. (22.30)
For a superconductor withthe polar phase structure, the solution of equation (22.24)
yields at . < A with logarithmic accuracy
y= Senay” . (22.31)
From equation (21.17) we obtain (for y < E < A):

E. 2A
g(E) = ADS
E
Then we derive from equation (22.28)
r(B) ~ 751m,EZX: (22.32)

As one should have expected, the quasiparticle lifetime due to resonant impurity
scattering is considerably shorter than in the Born approximation. Substituting (22.30)
into (22.10), we find that the expression for the thermal conductivity in the A-phase
contains an additional factor proportional to the temperature squared:
nin (a): Ba Ce) ma

Similar calculations using equation (22.32) for the polar phase yield
Ky(Z) (Z)wz; wilZ) (F)wz. (22.34)

Kn (Te) Te Te’ Kin(Te) Ty Ts
The temperature dependences (22.33) and (22.34) are in agreement with the thermal
conductivity measurements in single crystals of UPt3; [92-94], which indicate that
K(T)/T ~ T? for all directions. The accumulated experimental data demonstrate that the
superconducting order parameter in UPt; transforms according to the representation Ej,
(or E>,) of the group Dg, (Section 4). In this case, the longitudinal thermal conductivity
(along the six-fold axis) is given by equation (22.33) and the transverse conductivity by
equation (22.34).
We emphasise once again that calculations based on the kinetic equation are only valid
at sufficiently high temperatures, y < T < A. For T < ¥ the kinetic coefficients can be
calculated only on the basis of the linear response theory, which is presented below.
Exercise
Derive equation (22.7)
Green’s functions method: the linear response theory
An alternative technique for calculating the thermal conductivity and many other thermo-
dynamic and kinetic characteristics of superconductors is based on the linear response
theory in terms of Green’s functions [95]. According to this theory, the response of a
system to a small perturbation of its parameters (in this specific case, to the temperature
gradient) is described by the retarded correlators of conjugated fluxes.
The thermal conductivity in this formalism is calculated as follows. Let us first in-
troduce the Matsubara correlation function of thermal fluxes:
Ky(t1, 71582, 72) = (T,Qi(1, 71) Q;(t2, 72), (22.35)

where Q; is the thermal flux operator. In the real time representation, we have
1 (ee t) Owa(r,t) + Opt (r,t) Ovda(r, 2),

Oit, 1) = F(a, Or; ar, at (22.36)
This definition follows from the operator continuity equation for the Hamiltonian density
h(r,t) (H = fd?rh, where H is the BCS Hamiltonian (17.1) in the coordinate rep-
resentation):
- + divQ=0.
The Fourier transform of equation (22.35) has the form Kj(q,w,), where w, = 21T is
the boson Matsubara frequency. The retarded correlation function of thermal fluxes
K; (q,w) is obtained by analytic continuation of the Matsubara function to the real
frequency axis, iw, — w+1i0. According to the linear response theory, the thermal
conductivity coefficient is related to Kj (q = 0,w) in the following way [95]:
1 Ki) -Kf@ a1dimKfw)

aare
j= —— li
Td w=0
.
2257
22,
After substitution of (22.36) in equation (22.35), we decouple the r-ordered productof four
fermion operators (two-particle Green’s function) using the mean-field approximation:
(Tver, M1) bolts, 71) 5 (4, T2)ba{¥2, T2))
> —Gop(E1, 71395, 72)Goa(t2, 7230]; 71) — Fop(¥1, 71582, 72)Fga(F1, 715 03, 72)
= —Gop ti, 7139), 72) Gpa(¥2, 7230], 71) + Foe (tt, 71502572)Fjy (83s 7250s T1)s
where the overline denotes averaging overall impurity configurations. After going over to
the momentum-—frequency representation, we rewrite the correlator (22.35) in the form
kk -<——————-—~
Ky (wn) =T S> le (2€n + Wn) ro (Goolk, Em + Wn) Gpa (k, Em)
m
_ — 4 Ks),
where €,, = (2m + 1)aT. The last summandonthe right-hand side contains the singular
contributions like (7; — 7) due to the time differentiation of r-ordered products. The
inclusion of such contributions allows one to cancel the divergences which occur in the
sum over m in the first term on the right-handside.
It is more convenient to get round this difficulty using the spectral expansion (17.22)
for Green’s functions. One can obtain the following analytically continued expression for
the correlator [96]:
K;Ri.) Ww) —
= dodn
dw dw (wy + w)?
2a 27 wy —W2—-—w—i0
(
tah wy +w
2T
— gh)
‘a 2T.
a°k kikj
x loy 4m?
mmt (Im Gaalk, Wy + w) Im Gga(k, wr)
—ImFap(k,w1 +0) Im Fp (k, wa).

Substituting the expression (17.23) for the spectral density, one can verify that the integ-
rals over € of the terms containing G*G* etc. vanish. Then one obtains the thermal
conductivity coefficient in the form
ngs[OE
4m?T? 2x cosh?(E/2T)
d*k
kik;(GE, (k, E)GA(k, £) — FR(k, E)FZA(K,E)). (22.38)
(2m)’
The integral over momenta on the right-hand side is determined by the sum of graphs
shown in Figure 22.1, where the solid lines correspond to the averaged retarded and
advanced Green’s functions.
If we restrict our discussion to the case of isotropic scattering by point-like impurities,
then the dashedlines do not carry any dependence on momenta. Therefore, in the case of
a superconducting state which is even in coordinates, all diagrams in Figure 22.1 except
the first one yield vanishing contributions after integration over directions of momenta.
GR (KE) GR
‘ mS ae
: ck a
GA(IKE) Ga GA
FIGURE 22.1 Set of diagrams that determine the electronic thermal conductivity of superconductors due to
impurity scattering. GRA) are the averaged retarded (advanced) Green’s functions in the matrix form.
In the analysis of the superconducting states which are odd in coordinates, in particular,
p-wave states, the diagrams with transverse dashed lines (the so-called vertex correc-
tions), generally speaking, do not vanish, which considerably complicates the problem. In
this specific case, however, we are only interested in the maximum thermal conductivity
coefficient Kmax = Kj, Which is Kz, = «| for the A-phase and K,, = Ky = «1 for the
polar phase. A direct calculation showsthat in this case the vertex corrections vanish [88]
as a result of integration over the azimuthal angle. Hence
1
«=—— fLW),
dEE? 22.39
* set | cotea ) (
0
where
(8) =[Fs(GEOG) GLEE) — FEE) FEE)

d°’k
(22.40)
(in this formula no summation over repeated Latin indices is performed).
Averaged retarded and advanced Green’s functions are obtained as a result of analytic
continuation in equation (21.6) and have the form
—_ E)+
OE) = gyae
>= Aaalk
P(E) — Ae
GA(k, E) = G**(k,E), F4(k,E) = F**(k,E),
wheret(E) is derived from the self-consistency equation (21.16) (or (21.25)). Substituting
it in equation (22.40), we have [88]
He =
tae) = 20088 |TOR[A ea REM)
_ InNoke 40 F2 Re \t\? +1? ~2Az
(22.41)
~RetImt 47! /y2 — 2
Substitution of (22.41) in equation (22.39) yields the final result:
Nouk f dB E? 1
"~ 4T? cosh?(E/2T) Ret(E) Imt(E)
0
2 2 _ 2
x [Gitre 1) 2Ay (22.42)
tr (BE) — 4%
This expression determines the maximum thermal conductivity coefficient for odd phases
and all components of the thermal conductivity tensor for even phases.
Since the main contributions to the integrals in equation (22.42) come from the energy
E~T,the difference between Ret(E) and E can be neglected at sufficiently high
temperatures and low impurity concentrations. Then, introducing the quasiparticle life-
time given by equation (22.22), we have
i= Nov /—2 @ [2
dO»
i2,/B2 ~ v2. 22.43 )
* T? cosh*(En" (
0
This equation applies to the Born impurity scattering as well as to the limit of resonant
scattering. In the case of the Born approximation, using equation (22.17), we recover
formula (22.18), obtained by solving the kinetic equation.
Universality of kinetic coefficients at very low temperatures [97]
If T < y (ie. Ret(£) < 7), then, substituting (£) = Ret + iy in equation (22.41), we
obtain
Ly(le 0) = “Moke
Noké
[agapeRet
dQ.
Os
iyRet — Az
T :
Y 4/2iyRet — 7? — Az
dQ. » 2
=4nNok? kh? ——_..
4m" (oP + Af)
Hence
dQ » yy
Ki =4Noug
= Up TI ee
dn (ep 4 A2)3?? ’ ( 22.44 )
where
-+oo
r= [
cosh? z
0
Therefore, in superconducting phases with non-trivial pairing, the thermal conductivity
is a linear function of temperature at very low temperatures, and the proportionality
coefficient in this linear function is determined by the specific form of the order para-
meter.
So, for the polar phase (Az = A* cos” 6) we obtain from equation (22.44) (provided
that y < A)
2
rT
Ky = 4 Nou; rf snoae [foe g——__1____

° (72 + A? cos? 6)?/
2A
ww 4Noug 11m
— (22.45)
T 2a 2
_ 2 Y
Kk, =4Noug nwa] sin? 6 cos* PCa
Taco
2 AcooP
~ DNR= (1 +0(2)). (22.46)

For the phases with isolated gap nodesofthe first or second order, similar calculations
yield
Ky = 4 Nove "Ia ; KL = tNovz ri, Ay = A’sin’ 6;

A (22.47)
Ky = 2NoueI x, KL = Noug T1535) Az = A’sin’ 6.
Thus, we have cometo the conclusion that, if the thermal flux is parallel to the plane in
which the order parameteris zero, or directed along the line connecting the point-like gap
nodes of the second order, the thermal conductivity is independent of the impurity
concentration. A similar property is characteristic of other kinetic coefficients [98].
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82 . E.A. Shapoval, Zh. Eksp. Teor. Fiz. 47 (1964) 1007 [Sov. Phys.-JETP 20 (1965) 675].
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Index
A correlation length, 74, 133

anisotropy of the uppercritical field Coulomb blocade transistor, 47
for multicomponent
superconducting D
states in crystals, 79 density of states
anomalous average, 31 in normal metal, 5
A-phase, 15 in superconducting phases, 126, 127
Aj-phase, 15 in the presence of impurities, 163
in the mixedstate, 99
B density of superconducting
Bardeen—Cooper—Schrieffer electrons, 95
Hamiltonian, 29 diamagnetic limit of
boundary conditions for superconductivity, 57
one component, 83 diffusely scattering surface, 88, 152
multicomponent superconducting
states, 87 E
Bogoliubov transformation, 34 electrodynamics of magnetic
Boltzmann equation, 172 superconductors, 107
B-phase, 13 electron-hole asymmetry, 105, 136
Born approximation, 160 energy distribution of superconducting
electrons, 105
Cc energy spectrum
coherence factor, 173 for unitary phases, 35, 125
collision integral, 172 for nonunitary phases, 125
conventional superconducting under magnetic field, 96
state, 20 Euler constant, 39
Cooper pair dimension, 6
spin, 11 F
orbital momentum, 11 Fermi golden rule, 173
Cooper’s theorem, 3 flux quantum, 74
189
190 INDEX
G Meissner effect, 95
gauge symmetry breaking, 19 multicomponent order
gauge invariance, 148 parameter, 19
ground state energy, 36 multicomponent superconducting
Ginzburg-Landau equation, 74 states in crystals, 69
Ginzburg—Landau functional, 73 multicomponent Ginzburg—Landau
Gor’kov equations, 121 equation, 76
Green’s function, 119
anomalous, 119 N
spectral representation, 124 nodes in spectra, 20
matrix, 124 nodes position equation, 125
retarded, 125 nonlinear Meissner effect, 98
advanced, 125
for unitary phases, 123 P
for non-unitary phases, 123 paramagnetic limit of
self energy, 160 superconductivity, 57
linear response theory, 179 parity (spatial inversion
symmetry), 17
H parity breaking, 81
healing length, 84, 150 phasetransition splitting
helicoidal phases, 80 under magnetic field, 77 .
high temperature under crystal symmetry
superconductors, 21 breaking, 78
planar phase, 14
I polar phase, 14
irreducible representation, 18 Pauli exlusion principle, 9
pseudospin, 19
J
Josephson energy, 111 R
resonant impurity
K scattering, 165, 176
Kramers degeneracy, 19 resonant impurity scattering mean
Knight shift, 57 free time, 178
L S
Lifshits invariant, 81 Scharmberg—Klemm
localisation condition, 53 phase, 142
London equation, 95 singlet and triplet superconducting
London penetration depth, 95 States, 19
s+ d-pairing, 22
M s+ id-pairing, 23
magnetic superconducting specular reflection, 85
classes, 22 spin-orbit coupling, 19
magnetic moment of magnetic SQUID, 114
superconductors, 107 strong coupling, 64
magnetism superconductor order
in p-wave superconductors, 108 parameter, 10, 19
orbital, 135 superconducting class, 20
spin, 136 superfluid velocity, 94
INDEX 191
surface superconductivity for U

one component, 87 unconventional superconducting
multicomponentstates, 90 state, 20
symmetry nodes, 25 unitary phases, 34
universality of kinetic
T coefficients, 182
time reversal symmetry, 22
topological nodes, 25 Y
transition temperature, 39 Yosida function, 56
INTRODUCTION TO UNCONVENTIONAL
SUPERCONDUCTIVITY
V. P. Mineev, L. D. Landau Institute of Theoretical Physics, Moscow,Russia
K. V. Samokhin, Cavendish Laboratory, University of Cambridge, UK
Unconventional superconductivity (or superconductivity with a non-trivial Cooper pairing)is

believed to exist in many heavy-fermion materials as well as in high temperature superconduc-
tors and is a subject of great theoretical and experimental interest. The remarkable progress
achievedin this field has not been reflected in published monographs and textbooks and there
is a gap betweencurrent research and the standard educationofsolid state physicists in the
theory of superconductivity. This book is intended to meetthis information need and includes
original results of the authors.
About the authors

Professor V. P. Mineevis Vice Director of the L. D. Landau Institute of Theoretical Physics,
Moscow.Heis a well knownspecialist in superfluidity and superconductivity and has published
extensively in this area.
Dr K. V. Samokhin hasa post-doctoralresearch postin the Theory of Condensed Matter Group
at the Cavendish Laboratory, University of Cambridge.
Titles of related interest
Topologically Stable Defects and Solitons in Ordered Media
V. P. Mineev
Physics Reviews
edited by I. M. Khalatnikov
TheFirst Landau Institute SummerSchoolJuly 1993
edited by V. P. Mineev
ISBN 90-S699-209-0
ISBN 90-5699-209-0 . | | | |
97890 6"99 2095

f
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Introduction to

Gordon and Breach Science Publishers

Translated from the Russian by A. V. Malyavkin

GORDON AND BREACH SCIENCE PUBLISHERS

All rights reserved.

Originally published in Russian in 1998 as BBEJ[IEHWE B TEOPMIO HEOBbIYHOM

British Library Cataloguing in Publication Data

Coverillustration by Liouba Mineeva.

Preface 2. ee eee eee ee eens vii

Cooper Pairing ©... ee ne eee

Spin Structure of Paired States ....... ee cee ee eee

Phases of Superfluid Helium-3 2.2.2.0... ee eee 13

Superconducting States in Crystals... 6... eee 17

Energy of Elementary Excitations in Superconductors .............. 29

Gap in the Spectrum of Elementary Excitations and Critical Temperature . 37

Temperature Dependence of Thermodynamic Quantities forT—-+0O .....

Effects of Electron NumberParity in Superconductors .............. 47

Paramagnetic Susceptibility and Knight Shift .................44. 55

10 Landau Expansion of Superconductor Free Energy. ............0005. 61

11 Superconducting States with Multicomponent Order Parameters........ 67

12 Ginzburg-Landau Equations and Upper Critical Field. .............. 73

13 Boundary Conditions and Surface Superconductivity.............00. 83

14 Meissner and Mixed States in Unconventional Superconductors ....... 93

15 Magnetic Superconductors ....... 0.0... ee es 103

16 Josephson Effect... 0... ee te ene lil

PartIT .............. .. 117

17 Gor’kov Equations. 6... ene 119

18 Ginzburg-Landau Functional..................0.. . 129

19 Upper Critical Field in a p-wave Superconductor ................. 137

20 Boundary Conditions for the Order Parameter ............. oe 147

21 Effect of Impurities on Unconventional Superconductivity ........... 159

22 Electronic Thermal Conductivity of Unconventional Superconductors . . 171

References 6... eee eee teens 185

Index ........ Le 189

This book is based on a course of lectures devoted to conventional and unconventional

The bookconsists of two parts. Thefirst is an elementary introduction to the physics of

1. J. R. Schrieffer, Theory of Superconductivity, Benjamin W. A. Inc.; New York (1964).

Superconductivity, i.e. the complete disappearanceof dc electric resistivity of a material,

_PPye) + V(r)d(r) = (4 + “Ht (1.2)

In the momentum representation of the wave function,

V(k—k') = / Br ek Y(p), (1.5)

V(k—K!) = S°Vi(k,k!) 37 YinYE,(R'),

Vi(k, k’) — —V;,l fore F < HE

g(k) = gi(k) = S Am (k) Yim (is),

Cooper pair dimension .

gi(—k) = (—1)!g1(k). (2.1)

. g(—k)x21 = —g(k)x12. (2.2)

a= (4) =I") and a (9) =!

The eigenfunction corresponding to the spin-singlet state of a pair, in which S = 0 and

OB, ~~ BinO2, = a) ~~ | Lf) = (5, 0) = idy,

Woaic = k)ioy = > im Yim((k)ioy, (2.3)

aoo(r) = W(r) = |dle’*, (2.4)

S,=< 0, anPay + Brraay = It) +111) = (4

gi(k) go(k) ). (2.5)

! Let us recall the definition of the Pauli matrices:

8a(k) = > Ain Yin (kk (2.6)

are the amplitudes of states with S, = 1, 0, and —1, respectively.

_ (a tidj(k) (Xk) ) (2.7)

gi=—d,+idy go=d, 93> d, + idy,

can be expanded in terms of the spherical harmonics:

(a) the expectation value of the spin of a pair:

(b) the expectation value of the orbital momentum ofa pair:

L- in | a d*(k) (X x x) d(k). (2.10)

OB, BinO2, = a) | Lf) = (5, 0) = idy,

Uod(kz) = Uod(ke) = —2(—ke) = 2*(K) = d(k,). (4.26)

' —V), if ep —e, < k?/2m,k!?/2m < ep te,