K Thursday, august 22, 2013

KAM office hours = T at 2 PM, or T 3-4.

KAM became interested in thermoelectricity in Saclay, France. Europe is very interested in thermoelectricity.
You use a temperature-difference to make a voltage. If you know something about thermoelectricity that KAM
does not know, bring it to class!

Old textbooks on thermoelectricity = not useful; they do not take the nano approach.

Current application: space travel. Desired application: as common as being in your car.

C. Goupil, Ch. 13; DOI 105772/12988 - SSP - thermodynamics of thermoelectricity.
2003 - Caltech - Snyder and Ursell - Thermoelectric Efciency and Compatibility.

Thermodynamics of thermoelectricity

Theremoelectric engines are currently inefficient. Associated with TE engine is figure of merit.
0 [figure of merit] ; 1 ;
C
C
H
T
ZT ZT
T
q q s = < = = = (1.1)

Consider an ideal gas in a box of volume V. pressure of gas can be computed. However, if gas-particles are
charged, you will have chemical potential. Chemical potential then becomes related to the bias across the gas.
( , ); ( ) ;
e e
P P V T eV eV = = = + (1.2)

Problem: Qualitatively describe how a temperature-gradient (maintained by a hot and cold reservoir
separated by a thermoelectric junction) elicits a voltage-gradient. Solution: You have hot vs. cold reservoir,
and the thermoelectric junction, appearing as,
(1.3)

The temperature-gradient elicits a density gradient. You have a compressible Fermi-gas of electrons that is hot,
and a similar gas of electrons that is cold. The resulting density-gradient, in turn, elicits a number-current
(diffusion).

Problem: find an order-of-magnitude estimate for the current across the junction (1.3). solution: Consider
transmission of a particle of energy c to be an event with probability ( ) T c . Consider left-center hopping to
have a parameter
2
L
W
L W
I = , and center-right hopping to have a parameter
2
R
W
R W
I = . Let the density of states
dN
dc

for left-right transmission be a Lorentzian function,
2 2
1
~
f
dN
d
f
c
c
t

+
, in which ( , ) ( , )
L R R L
f f f = I I = I I , the
license to switch the variables being a consequence of time-reversal symmetry. We realize the simplest f
satisfying this symmetry is
R L
f = I + I . Then, the left-right transmission function (which has no dimensions),
using the pi-theorem, is approximately,

( )
1
, 1 ,
0 deg , deg , , 0 2 2
2
~ 2 ~ ( );
( )
L R L R L R
L R L R L R
L R
dN dN
T T
d d
|
o
o c
c c t c
I +I | | | |
I = I = I
| |
+ I +I
\ . \ .
(1.4)

The non-interacting transmission function is subsequently computed using the series-conductor-addition-law,
1 1 1
1 2 eq
o o o

= + , and this appears as,

1 1
0 0 2 2 2 2
0 0
1 1 1 1 2 2
( ) ~ ;
( ) ( )
L R L R
L R
L R L R L R
T T
T T
e
t c t c

| | | | I +I I I
= + = + =
| |
I I + I +I + I +I
\ . \ .
(1.5)

Finally, the thermodynamic probability is given by
, ,
( ) 1
,
( 1)
L R L R
L R
f e
| c
= + , which implies that we treat the
electron gas as a grand canonical ensemble. By Kirchoffs rule, we subtract left-center and center-right currents
to constitute the net current,

2
, , ( ) ( ) 2 2
2
2 1 1
( , ) ;
( ) 1 1
R R L L
W
L R
N R L N L R L R
L R W
d
I I I I T
e e
| c | c
c

t c
+

I I
| |
= = =
|
+ I +I + +
\ .
}
(1.6)

That the number-current is a function of the indicated thermodynamic variables allows us to establish
derivative-relations, if we wanted to.

Problem: Show that for
L R
= , you have zero number current. Solution: Let the chemical potential gradient
be entirely due to a temperature gradient. Then,
L R L R
T T = = , and (1.6) immediately yields 0
N
I = .

Note, also, that 0
L R
= = causes the following integral
1
to vanish,

2
, , 2 2
2
1 1
0 , ;
( ) 1 1
R R
W
R L L R
L R W
d
e e
| c | c
c
|
c
+

| |
= I
|
+ I +I + +
\ .
}
(1.7)

Equilibrium: when left and right chemical potentials balance out. That is when the thermoelectric effect ceases.
So, you are basically making a A out of a T A . These are encapsulated by
( ) 1
( , ) ( 1)
E
FD FD
f f T e
|

= = + .



1
This is not because the Lorentzian
2 2
1
c +I
is an even function; replacing
2 2
1
c +I
with a cosine-function yields nonzero current.
Problem: Let
R
= + A and
L
= , and similarly
R
T T T = + A and
L
T T = . Series-expand the
R L
F f f =
about 0 A = and 0 T A = , truncating at 1
st
order. Solution: we shall need the derivatives, in which
B
k T
x
c
= ,

2 2
( )/
1
2
( )/ ( )/ 2
( )/ ( )
2
( )/ ( )/ 2
1 1
sech ;
1 ( 1) 4 2
0
1 1
sech ;
( ) 1 ( 1) 4 2
B
B
B B
B
B
B B
k T
k T
k T k T
k T
k T
B B B k T k T
B
e
f x x f
e e
e
f x x f f
k k k x
T k T e e T T
c
c c
c c
c c
c c c
c
c c

c c c
= = = =
c c + + c
+
c c c c
= = = = =
c c + + c c
(1.8)

We shall also need the fact that the 1
st
term of any series expansion that is between the difference of two
functions always vanishes,
( , ) ( , ) ( , ) ;
f f f f
f f x y f x x y y f x y f x y f x y
x y x y
c c c c
= + A + A = + A + A = A + A
c c c c
(1.9)

Thus, the series-expansion appears as,

( ) ( )
2 2
2
( ) ( )
1
sech
4 2
B
B B
f f f f
F T T k x T
T
f x x
k x T k x T

c c

c c
c c c c
= A + A + A + A ~ A + A
c c c c
c
= A + A = A + A
c
O O
(1.10)

Plotting the prefactor/dimensionless-scaling function of
2
1
4 2
( ) sech
x
scale
f x x = , we have,
(1.11)

Problem: write down the units of number-flux, and energy-flux. Solution: the units of flux of [stuff] is [stuff]
per unit time per unit (normal) area, so we have,

2 2 2 2
1
[ ] ; [ ] ; [ ] ; ;
Q N E E Q N
J W W
m s m m s m
= = = = = +

J J J J J J (1.12)

10 5 5 10
x k
B
T
0.2
0.1
0.1
0.2
f
scale
x 0.25 x Sech x 2
2
Problem: consider a quasi-static system. Write an expression for the entropy flux. Solution: write,

quasi-static
2 2 2
( / ) entropy
1 [heat-flux]
;
-flux [temperature]
qs qs qs Q
s
dQ dQ d Q T dQ
dS
dS
T T dt d x dt d x T dt d x T
(
= = = = = = =
(


J
J (1.13)

Problem: introduce so-called thermodynamic forces: ( / )
N e N
T = V F J and (1/ )
e E
T = V F J , which
elicit the indicated currents. Let there be coupling between the forces. Write a linear constitutive relation;
e.g., Ficks Law of diffusion, for each current. Solution: since there is coupling between the forces, we will
have terms making each current which is due to the other elicitor of the force. Specifically,

, , , ,
, , , ,
( / ) ; (1/ ) ;
; ;
N E e NE N N N E N EN E E E
N N E N N E E N E E
T L T L = V = = V =
= + = +
J J J J J J
J J J J J J
(1.14)

Together, we have the linear relations,

( / ) micro-
;
(1/ ) reversibility
NN NE N e
NE EN
EN EE E
L L T
L L
L L T
V ( ( ( (
= =
( ( ( (
V

J
J
(1.15)

Problem: consider
E Q e N
= + J J J , and consider the new constitutive relations,

11 12
12 21
21 22
( 1/ ) Onsager-
; ;
(1/ ) relation
N e
Q
L L T
L L
L L T
V ( ( ( (
= =
( ( ( (
V

J
J
(1.16)

Find the
ij
L in terms of the , , ,
NN NE EN EE
L L L L . Solution: Writing ( / ) (1/ ) (1/ )
e e e
T T T V = V + V , we
compute
N
J of (1.15) and then (1.16) as,

( )
( )
1 1 1 1
1 1 1 1
12 11
( ) ( ) ( ) ( )
( ) ( ) ;
e
N NN NE NN e e NE T
NE NN e NN e e
L L T L T T L T
L L T L T L T L T

= V + V = V + V + V
= V V = V V
J
(1.17)

From (1.17), considering the variations
1
( ) T

V and
e
V as independent, we read off the relations,

1 1
12 12 11
; ;
e e
NE NN e NE NN NN
L L L L L L L L

= = = (1.18)

Carrying out the same procedure for
Q E e N
= J J J (favouring occurrences of
Q
J ), we have,

( ) ( ) ( )
( ) ( )
1 1 1 1 1
1 1 1
21 22
( ) ( ) ( )
( ) ( ) ;
Q E e N EN e e EE e NE NN e NN e T T T T T
e NN EN
e EN e EE e NE NN e e T T T
L L L L L
L L
L L L L L L
T

= = V + V + V V V

= V + + V = V +V
J J J
(1.19)

From (1.19), we read off,

21
21 12 22
; ( ) ;
EN NN e
EN NN e EE NN e EN NE e
L L L
L L L L L L L L L
T T

= = = = + (1.20)

Problem: Write the inverse-transform of the expressions (1.18) and (1.20). solution: The
11 NN
L L = is already
solved for, so we just need to invert a 3x3 system. However, be careful to make sure all elements of the column-
vector have matching-dimensions, or else the coefficient-matrix wont make sense,

2 2 2 2
11 11
1 1 1 1
12 12
1 1 1 1
21 21
1 1 1 1
22 22
1 0 0 0 1 0 0 0
1 0 0 1 0 0
1 0 0 1 0 0
1 1 1
1 1
1 1
1 1 1 1 1
e e e e
e e e e
e e e e
NN NN
EN EN
NE NE
EE EE
L L L L
L L L L
L L L L
L L L L



( ( (
( (
( ( (
( (

( ( (
( (
= =
( ( (
( (
( ( (
( (
( ( (


2
11
1
11 12
1
11 12
1 1
11 12 22
;
2
e
e
e
e
L
L L
L L
L L L

( (
( (
+
( (
=
( (
+
( (
( ( + +

(1.21)

Problem: Ohms Law is
e N
e o = = J E J . Compute the isothermal ( T V = 0) electrical conductivity in the
system described by (1.16) (where we have the symmetry
12 21
L L = ), realizing /
e
e = V E . Solution:
computing
N
J from (1.17),

1
2
11
11 0
/
e e N T
e e
eL T
e e L
e
e T

V =
V
= = = =
V V
J J
E
(1.22)

Problem: Fouriers law is
Q
T k' = V J . Compute the iso-electric thermal conductivity
2
k' . Solution: using
(1.19) in which
e
V = 0,

1 1
/ 21 22 22
2
( )
;
e
Q
e T T
E
L L L
T T T

k k

= =V
+V
' = = = =
V V
E 0
J
0
(1.23)

Problem: Fouriers law is
Q
T k = V J . Compute the thermal conductivity k , this time using
N
= J 0. Solution:
the condition
N
= J 0, using (1.17), allows us to eliminate
e
V in favour of
1
( )
T
V . Repeating (1.23),

12
11
1 1
1 1
21 22
21 22 12 21 11 22
11 22 12 21
2 2
11 11
( )
( )
;
N
L
Q
T L T
e T T
e
T L L
L L L L L L
L L L L
T T T L T L T

k k

=
+ V
V +V

= = = = = =
V V V
J 0
J
(1.24)

Problem: the Seebeck coefficient
3
is defined as
1
( / )
N
e e e
S T o

=
V V =
J 0
; re-express this in terms of the
ij
L .
Solution: the condition
N
= J 0 allows use of (1.17) to eliminate
e
V in favour of
2
1
( )
T
T T

V = V . Repeating
(1.24), it is trivial to write,

12 12
11 11
1
12
2
11
( ) Seebeck- thermo-
1 1 1 1
;
coefficient power
L L
L L e
e
T T T
L
S
e T e T e T eT L

V V ( (
= = = = =
( (
V V

(1.25)

Problem: the Peltier coefficient is defined as
1
0
( / )
Q N T e

V =
H J J ; re-express this in terms of the
ij
L .
Solution: using (1.17) and (1.19), we effect direct computation and obtain,

1
21 22 0 12 12 12
0
1
11 11 11 12 11 0
1 1 1 1 1 1
| ;
Q
Q e e T T
T e
N N e e T
L L
L L L
T T S
e e e e L e L eT L L L T

V =
V =

V =
V + V

H = = = = = = =
V V
J
J 0
J J 0
(1.26)

2
Actually, there are two different thermal conductivities, since you are holding different thermodynamic variables constant.
3
The symbol for the Seebeck coefficient in

Interlude: By (1.22), (1.23), (1.24), (1.25), and (1.26), we can write,

11 22
12 21
2
2 2 11 22 12 21
11 22 2 2
11
3
2 2 12 12 11 22
22 2
11 11 12 21
; ; ; ;
1 1 1 1
; ; ; 1; ;
1
e T
E e
e
e e e e L L
L L
S L L L L T
L L T T Z
e L T
L L L L T
S TS L S T ZT
eT L e L e L L
o o
k k k k
k
o k o
o

' = = = = = =
= H = = = + = =

(1.27)

Problem: Compute the entropy flux density, re-expressing
e
V in terms of the
ij
L . Solution: we write,

1 1
21 22 21
21 22 22
11
( ) ( ) 1 1 1 1 1 1
( )
number thermal entropy per thermal
;
entropy entropy carrier entropy
e T T
S Q e e
N Q
S S
L L L
L L T L
T T T T eT L T T

V + V | |
= = V + V = = + V
|
\ .
( ( ( (
= + = + = +
( ( ( (

J J J
J J
(1.28)

Problem: Assume a continuity equation for the entropy flux density (1.28), and compute ; this is computed as,
. Solution: let the continuity equation appear as
S
s V- = J ; we directly compute, and use the continuity for
particle-number and energy, 0
E N
E N V- = = = = V- J J , and we get,

( ) ( ) ( ) ( )
( ) ( ) ( ) ( )
( ) ( ) | |
1 1 1
1 1 1 1
1
0
1
( ) forces fluxes Onsager-hypothesis ;
Q
S Q Q E e N E e N
e N
E e N E e N e N
e
E N
S T T T
T T
T T T T
T
S
T T

| |
= V- = V- = V - + V- = V - + V-
|
\ .
V -
= V - + = V - V - V -

| |
= V - +V - = -
|
\ .

J
J J J J J J J
J
J J J J J
J J
(1.29)

The thermoelectric engine: consider engine: a device between a hot and cold reservoir. A load is put between
the hot and cold reservoirs. It is equivalent to a battery V
0
, a resistor R
in
, and a resistor R
L
, all in series,
assuming the linear/quasi-static
4
regime. These resistances are the internal and load resistances, respectively,
(1.30)

Limits: you have
load L N
R R = = = J 0, the broken-circuit limit, where the maximum voltage V
0
is across the
load. The opposite limit is
0
0 /
load L C in
R R I V R = = = , the short-circuit limit, where the maximum current
flows through the entire loop.


4
Completely-unrealistic; a battery is manifestly a non-equilibrium object.
IV (current-voltage) characteristics: We are interested in power: ( )
in C
P VI R I I I = = . Maximum power occurs
when
load in
R R = , by maximum-power-transfer. We have,
( ) 0 [maximum-power];
load in
P
P P I R R
I
c
= = =
c
(1.31)

Problem: The thermoelectric figure of merit is defined as /
N
Q Q
ZT
A = =

0 J 0
J J . Write this in terms of the
ij
L ,
and also show that
2
( / ) 1 /
E e e e
ZT S T k k o k = = . Solution: directly computing, we have,

( )
11 22
12
12 21
11
1 1
???
0 21 22 11 22
1 1 1
12 21 11 22
21 22
( )
1
;
1
( ) ( )
N
Q
T T
L L
L
L L Q
T L T T
L L L L
ZT ZT
L L L L
T L L

A =

=
+V
= = = = =
+
V +V
J 0
J
0
J
(1.32)

Having established (1.32), we can begin from the LHS of
2
/
e e
ZT S T o k = , and use (1.27) throughout, as,

11 22
12 21
2
2 2 2 2
12 11 11 12
11 11 22 12 21 11 22 12 21
1 1
;
1
e
L L
e L L
S T L L e L T L
T ZT
eT L T L L L L L L L L
o
k
| |
= = = =
|

\ .
(1.33)

We also write,

12 21
11 22
12 21 12 21 11 22
11 22 11 22 12 21
2
2 11
22
11 22 12 21
1 1
1 1
1 1 1 ;
1 1 1
L L
L L
E
L L L L L L
e L L L L L L
L T
T L ZT
L L L L
k
k

+
= = = = =

(1.34)

Making (1.32) as large as possible, even so were in the linear/equilibrium-regime, is equivalent to maximizing
the non-equilibrium efficiency (1.1).

Result: In (1.32), we immediately see that we want a high electrical conductivity and a low thermal
conductivity.

Wiedemann Franz law is a problem: The problem is that we have the correlation
2 2
1
3
/ ~ ( / )
e B
T k e LT o k t = ,
in which we have the Lorenz number
8 2
2.44 10 W K

O . This requires 3 possible approaches (1) use non-
Fermi liquids (2) use the Kondo-regime, (3) use nano-systems. All three of these approaches are the topic of
intense research.

Thermodynamic potential: G. Snyder and T. Ursell, Phys Rev. Lett 91, 148301 (2003),

Problem: compute
Q
V- J for a non-radiating closed system. Solution: that the solution is closed means we
have the following statements of mass and energy conservation,
0; 0 ( ) ; ;
N E Q e N Q e N e N
N E e V- = = V- = = =V- + =V- +V - = J J J J J J J J (1.35)

Poyntings theorem (another statement of conservation) for a non-radiating electromagnetic system says
e
P = - J E, in which, for a chemical voltage /
e
e = V E and
e N
e = J J , the conservation laws (1.35) imply,
( ) 0 ( ) ;
E Q e N Q e N N N e
e e V- =V- + = V- = V - = - = - = - J J J J J E J E J E J (1.36)

Problem: compute the relative efficiency for the thermoelectric device (1.3). solution: Using
e e Q
E = - =V- E J J (from (1.36)), /
S Q
T J J ,
H
Q TS = , and considering a quasi-static/reversible/linear
thermoelectric device so that
S
S V- = J , the relative efficiency
5
is computed as,
;
( ) ( ( ) ) ( )
Q Q
e e e e e
r
C C H e Q Q S S S
E E E
Q Q Q E T S TS T T T
q
V- V-
- -
= = = = = = =
V- V- + V- V- -V
J J
E J E J
J J J J J
(1.37)

Problem: introduce a new thermodynamic potential, / / ( )
N
e Q e e
u T k
=
= V
J 0
J J J , and use this to define
another thermodynamic potential,
1
e
u TS

u + . Show that
Q e S
T = u = J J J . Solution: using Fouriers law
(1.24) for
Q
J , we have,

1 1
; ;
( )
e e e e
Q e e e e S e
Q e e Q
J J J
u J TS J u J J TJ TS u
J T T k k

=
=

= = = = + u = u +
V V
E 0
E 0
J
J
(1.38)

Problem: re-express the entropy current in terms of the potentials u and
1
u

, and subsequently compute

S
V- J . Solution: using (1.38),

( )
1
1 1 1
( / ) ;
S Q e e e S e
S u T
T T T

= = u = + V- = V u - J J J J J J (1.39)

Problem: compute the relative efficiency, /
r e Q
P J q , in which
e e
P - E J (the electric power), and in
which
Q s
J T -V J . Solution: Using (1.38) in (1.37), and using /
S Q
T = J J , and
e Q
- = V- = -Vu E J J J , and
/
Q
= u J J , we have,

( / ) ( ) / /
;
( / ) ( ) ( / ) / /
Q Q
e
r
S Q Q Q
J
T T T T T J T T T T
q
u - Vu Vu u Vu u - -Vu
= = = = =
-V -V - V V V
J
E J J
J J J
(1.40)

Problem: Re-write the relative efficiency (1.40) in terms of the thermodynamic potential u of (1.38). solution:
recalling that ( ) u u= u , we solve the definition of u, (1.38), for
r
q by inserting ( )
e
e
e Q E
J J J

= (see (1.35))
and
2
e T
S
e Z
o
k (see (1.27)), yielding,

1
1
( )
(1 ) (1 ) ( ) ( )
1 ( ) ;
( ) ( 1)
e e e
e
e
e uS uS uS
Q E
e e e e e r Z Z Z
r uS
e e e e e Z ZT
J J
uTS S T Z uS S T Z uS Z
u u
T S S T Z Z TS u uTS

q
q q
k


| | u
= = = = = = =
|
V u + + +
\ .
(1.41)

Problem: Show that ZT corresponds to
max C
q q = , the Carnot efficiency. Solution: it is trivial to write,

max max
1 1
lim lim lim ;
1 1
C C C C
ZT ZT ZT
ZT ZT
ZT ZT
q q q q q q

+
= = = =
+ +
(1.42)



5
This is the efficiency relative to the Carnot efficiency: /
r C
q q q , in which 1 /
C C H
T T q = .


Not merely power and efficiency, but also compatibility for a good heat engine; we write,

???? ???? ???
( )
( ) 2 2
1
( / ) (1 ) / 1 1
;
( / ) / 1 ( ) 1 1 1
e
e
e
e
S
ZT TS
e e e e e
r ZT TS
S e e ZT S
S ZT S ZT
T T T T T ZT TS ZT
o
q
u
u

- - Vu u +
= = = = = =
-V u -V V + u + + +
E J J J
J J
(1.43)



1 1
max ;
e
ZT
U
S T
+
= (1.44)

Tuesday, august 27, 2013

Problem: draw a schematic of a thermodynamic engine, operating between a hot and cold reservoir. Solution:
just draw,
(2.1)

Problem: plot the Fermi functions for low and high temperature, but with matching chemical potential.
Solution: let the matching chemical potential be 0
L R
= = = . Then,
(2.2)

Problem: recall the order-of-magnitude estimate for current from the previous lesson, (1.6). Compute the
current resulting from
0 0
( ) ( ) T E T E E o = . Then, write down a thermodynamic condition for 0
N
I = . Solution:
by direct computation,

0 0
2
0 0 0 ( ) ( ) ( ) ( )
2
1 1 1 1
( ) ;
1 1 1 1
R R L L R R L L
W
N E E
W
I T E E d T
e e e e
| | | c | c
o c
+

| | | |
= =
| |
+ + + +
\ . \ .
}
(2.3)

The condition for the current to vanish is for the Fermi-function difference to vanish at
0
E ,

0 0
0 0
0 ( ) ( )
1 1
;
1 1
R R L L
R L R R L L L R R L
E E
B R B L R L L R
E E T T
E
e e k T k T T T
| |
| |
| |


= = = =
+ +
(2.4)

Problem: consider (2.1) as a single-loop electric circuit. Write a schematic illustrating the action of an
ammeter measuring current, and another schematic illustrating a voltmeter measurement across the load
L
R .
Solution: the current-measurement and voltage measurement respectively appear as,
vs. (2.5)

The
L
R measurement is indicative of the voltmeters infinite internal resistance.

2 1 0 1 2
W
0.2
0.4
0.6
0.8
1.0
f
FD
f
FD
,T
F
0.5
Hot k
B
T W 8
Cold k
B
T W 0.1
Problem: Let the loads resistance be constituted by a chemical potential gradient. Then, the condition of
dead thermoelectric battery ( 0
N
I ) is characterized by
0 R L
A = being a maximum:
0 0
0 max
N
I A = A . Note that 0
N
I also happens when the condition (2.4) is satisfied for the special
case of a delta-function potential, and when an analogous condition for other transmission functions is
satisfied. Plot
N
I vs.
0
A for a fixed temperature-difference. Solution: we use the following commands,

(-)/T -1
f[_,T_,_]:=(E +1)
Plot[{f[1.7,5,0]-f[1.7,1,d],0.26},{d,0,
;
[formatting cra 2}, p]];
(2.6)

This then yields,
(2.7)

One can also see,

0 0
case 1 case 2
; ;
0 0
L R L L N L R L L N
I I
( (
( (
< = + A s + A > > = + A > + A <

(2.8)

Without loss of generality, we can stick to case 1 of (2.8), which is less confusing.

Problem: Write down chemical potential and load-resistances for three separate conditions: (1) fresh battery,
(2) discharging/ operation, and (3) dead battery. Solution: write,

0 0
0 (connected) 0 (connected) (disconnected)
(1) ; (2) 0 ; (3) ;
"fresh battery" "operating battery" "dead battery"
L L L
R L R L R L
R R R

< < < < = | | | | | |
| | |
< < A = A + =
| | |
| | |
\ . \ . \ .
(2.9)

0.0 0.5 1.0 1.5 2.0
0
W
0.05
0.10
0.15
0.20
0.25
I
N 0
Fresh battery
I
N 0
Fresh battery I
N 0
IN= 0--> deadbattery
Problem: efficiency is defined as / /
L hot
W Q W Q q = = . Use the 2
nd
law of thermodynamics to derive the Carnot
efficiency. Solution: the 2
nd
law says,
0 ;
R L R L R R
R L cold hot
R L R L L L
Q Q Q Q Q T
S S S S S
T T T T Q T

A = A + A = A + A = + > > > (2.10)

Directly computing the efficiency, we get,
1 1 ;
L R R R
C C
L L L L
Q Q Q T W
Q Q Q T
q q q q

= = = s s (2.11)

Interlude: For a non-interacting system out of equilibrium
6
, you have number and thermal currents. The
following equations can be heuristically derived by using the reasoning discussed in (1.4) through (1.6),
although they are the correct expressions,

, ,
( ) 1
,
0
( ) ( 1) ; ( ) ( ) ( );
( ) ( ) / ; ( ) ( ) ( ) ;
L R L R
E
L R L R
N Q L
f E e F E f E f E
I T E F E dE W I E T E F E dE Q
|


= + =
= = A = =
} }
(2.12)

Problem: compute the power output and efficiency using (2.12). solution: write,

0 0
( ) ; ;
N
R L N N
Q Q
I W W P
P I W I
Q Q I I
q = = = A = = = A = (2.13)

Problem: compute
N
I and
Q
I for 0 T A and 0 A , and try integrating for a toy transmission function
2 2
( )
a
a E
T E
+
= . Solution: looking at (1.10), and putting this into (2.12),
( ) ( )
2
4
2
2 2
0
sech
( ) ;
4
B
E
t
k T
N B B
B
f a
I k x T T E dE k x T dE
a E k T

c
= A + A = A + A
c +
} }
(2.14)
( )
2
4
2
2 2
0
sech
( ) ;
4
B
E
t
k T
Q B L
B
a
I k x T E dE
a E k T

= A + A
+
}
(2.15)

Problem: write the coupled linear response formulae (1.16) in terms ( )( )
df n
n L dE
L T E E dE


}
. Solution:
write,

11 12 0 1
21 22 1 2
( 1/ )
;
(1/ ) /
N N e
Q Q
J At I L L L L At T
J At I L L L L At T T T
V A ( ( ( ( ( (
= = =
( ( ( ( ( (
V A

(2.16)

Interlude: In contrast to the dimensions that may be indicated in (2.16), the transport coefficients scattered
throughout (1.27), in terms of these new integral-functions, are,

2
0
1
;
/
N
eI I
G e L
R V e
= = =
A
(2.17)

( )
2
1
1
0
0 2
0 1
1
1 2
1 1 2 2
2 2
/
0
( / ) 1
1 ( / ) 1
;
1
N
L L
L
L L Q
e
L L T T
I
L L T T
I
L L T T L
L L
T T T T T ZT T
o

k

+
A = A
=
+ A
A + A
= = = = =
A A A +
(2.18)

6
Our system (2.1) is manifestly out of equilibrium, since a disparity in temperature and chemical potential is what drives the effect.

0 1
2
1 2 2 1 2 1 2
0 0 1 1 0 1 0 2 1
/
/ 1 1 1 1 1
;
/ 1
N
e
I
L L T T
L L L L L L L ZT
S
e T eT L eT L L L eT L L L eT L ZT

=
A = A
A
= = = = =
A +
(2.19)

1 2
0 1
0
1 1 1
;
1
E
e
N
T
I L L ZT
TS
e I e L e L ZT
A =

H = = =
+
(2.20)

2 2 2 2 0
1
2
0 2 1
... ;
ph
e e e
e ph e
TGS TGS TGS L
ZT
L L L
k
k k k k
=
= = = = =
+
(2.21)

Interlude: target ZT for commercial viability,
[currently] ~1; [commercially viable] 3; ZT ZT > (2.22)

Problem: compute the chemical potential difference
0 L R
A = s A in the case 0
N
I = . Solution: the zero
current condition, from (2.16) (e.g., from (1.16)) says
0 1
0 /
N
I L L T T = A = A ; we then write,
( )
1
0
0
/ ;
L R
L
T T
L

= A = A s A (2.23)

Problem: consider the case 0
N N
I I o = , so that there is an arbitrarily-small (but nonzero) number current.
In this case, compute the quasi-static efficiency. Solution: we can use
0 1
0 /
N
I L L T T = A = A to simplify
the definition of efficiency (2.13); using the abbreviation
0
0 1
L R
x

A
< = < , we write,

( )
( )
0 0 0 1
0 0
1 2 1 0
(1 )
( ) ;
(1 ) 1
T
N T
C
T
Q T
L L L I T x x
f x
I L L L T x

q q
o o
A
A
A A A A + A
= A = A = = =
A + A A + +
(2.24)

Problem: maximize the efficiency (2.24) with respect to x. State the large-o and small-o of the extreme-value
of ( ) x x o = you find. solution: extremize (2.24) by taking a derivative of the relative
7
efficiency;

1 2
1 1 2
2 8
2
1
( )
(2 1)(1 ) ( )( 1)
1 (1 ) ;
(1 )
1 ( )
r
r
C
x x x x
x
x x
o o
q q o
q o o o
q o
o o

+
c +
= = + + =

c +
+

O
O
(2.25)

Then, the efficiency in all cases is,

( )
1 (1 ) ( (1 ) )
1
( ) ; ( 1) ; ( 1) 1 ;
4 2 (1 )
r r r r
o o o o o o
q q o q o q o o
o o o o o
+ + +
= = >> <<
+ + +
(2.26)


Thursday, august 29, 2013

thermodynamic efficiency at maximum power, C van der Broeck, PRL 95, 190602 (2005)
thermodynamic bounds on efficiency for systems with broken TRS, C. Benenti et al, PRL 106, 230602 (2011)
Strong bounds on onsager coefficients and efficiency for 3 terminal thermoelectric transport in magnetic field
K brandner et al., PRL 110 070603 (2013).

7
Efficiency scaled to the Carnot efficiency; this is simpler.
Dubi and DiVentura, RMP, 83, (2011)
Rego and kirezenow, PRL 81, 232, (1998).
Schwab et al, Nature, 404, 974, (2000).
1996 - Tennesee - Mahan and Sofo - The best thermoelectric

Claim: increase efficiency if time-reversal symmetry broken?

3-terminal transport is also way to increase TE efficiency.

Preliminaries: Efficiency is work done (electricity) divided by heat flow associated with this work,

(1 ) (1 ) 1
; ; ;
1 1
R L
c
o
T x x x x
x
T x x ZT

q q o
o o
A
= = = =
+ + A
(3.1)

Thermodynamic efficiency at maximum power: you have,

max
( ) ;
2
C
ZT
P
ZT
q q =
+
(3.2)

Problem: rewrite all thermodynamic forces and fluxes in such a manner that one can write power as
proportional to
1
( / )
d
dt
J x T = = A . Solution: write the linear relations (2.16) (or (1.16)) as,

1 1 11 12 1
1
2 2 21 22 2
/
; ;
( )
T
x T J L L x x
x J L L x Q
= V
( ( ( (
=
( ( ( (
= V

(3.3)

Then, the power appears as,

1 1
W Fx J xT P = = = (3.4)

Problem: consider the condition 0 x = . Compute the condition on
1 1
stop
x x = resulting from this. Solution: you
have
11 1 12 2
0
stop
x L x L x = = + ; this is rearranged as,

12
1 2 1 1 1 1
11
; ( ) ( ) 0 ;
stop stop
L
x x J J x J x x
L
= = = (3.5)

Problem: relate
1
stop
x to the
1
x which maximizes the power (found in 1
st
homework). solution: write,

max 2 12
1 1 max
11
1 1 1
; ( )
2 2 2 2 2
ZT
stop
C C C
x L ZT
x x P
L ZT
q q q q
=

= = = = =
+
(3.6)

You cant reach the Carnot efficiency, even with the maximum figure of merit.

Interlude - Curzon-Ahlborn limit: Not possible to reach Carnot efficiency, 1 / 1 ( / )
CA R L R L
T T T T q . In
fact, if you maximize power, you do not
8
maximize efficiency, and vice versa.


8
Recall: you can have
max
0 P q q = = . We are in nano-systems, where Wiedemann-Franz law is no longer valid
Non-linear efficiency: the following is not a very rigorous definition, but check to see if you agree. Let our
engine operate between two temperatures
0 1
, T T , as,
(3.7)

Now: let temperature be a function of the spatial coordinate y, ( ) T T y = , which runs between the limits
indicated in (3.7). Rewrite the schematic (3.7) as,
(3.8)

Let an infinitesimal of heat energy produce an infinitesimal of work energy, for all time. Then, dQ dW = ,
which in turn implies dQ dW = . Series-expanding the function ( ) Q Q y y = + A for y dy A ,

2
( ) ( ) ( ) ( );
dQ
Q Q y dy Q y dy Q y dW y
dy
= + = + + + O (3.9)
Integrat,e

0
( ) ( ) ( )
( ) ( ) ( )
( ) 2 ( )
y
dW y T y T y dy
Q y dy Q y dW y
Q y T y
+
+ = =
}
(3.10)

Then write,

1
0
( ) 1 ln ( ) ( ) 1 (1)
; ( ) 1 ;
2 (0)
dW y d T y dW y T
Q dy dW y
dy dy dy Q T
q
' | |
' = = =
|
'
\ .
} }
(3.11)

Eventually, you will show in your homework the following functional form for the mazimized efficiency,

2
onsager onsager
12 21 12 21
max
12
1 1 1 1
; ; 1;
det det 1 1 1 1
C C
y L L L L ZT
x y ZT x
L L L ZT y
q q q
+ +
= = = = = = =
+ + + +
(3.12)




Breaking time-reversal symmetry using magnets

Problem: On turning on a magnetic field, you can increase the efficiency by breaking time reversal symmetry.
Draw a schematic of a thermoelectric junction with such an applied magnetic field. Solution: Both electric and
heat currents flow along the horizontal axis. The system is in contact with left and right reservoirs at
temperatures TL and TR and chemical potentials L and R.
(3.13)

Problem: Even though fluxes are one dimensional, the motion inside the system can be two or three
dimensional. Write the linear response equations for the particle and heat fluxes. Solution: write,

1 2 1
1 2 2
( ) ( ) ( )
;
( ) ( ) ( )
q q q
q q q qq q qq q qq
J J L L L L X L X L X
J J L L L L X L X L X


|
|
+ A ( ( ( ( ( ( (
= = = =
( ( ( ( ( ( (
+ A

B B B
B B B
(3.14)

In (3.14), J

and J
q
are the particle and heat currents, B an applied magnetic field or any parameter breaking
time
reversibility (such as the Coriolis force, etc.), and,

2 1
1 2
; / ; ; ; ; ;
R L R L R L
X X T T T T T T | | | | | |

= A = A = A A = = A = A = (3.15)

Under time-reversal, the Onsager reciprocity becomes broken
9
,
; ( ) ( ); ;
i ij j ij ij ji k i j ijk
I L f L L L B A c = V = + = = = V B B B (3.16)

Problem: here, the 2
nd
law of thermodynamics is,

2 2
1 2 1 2 2 1
( ) 0;
q qq q qp
S J X J X X L X L X X L L

= + = + + + > (3.17)

Write the conditions (3.17) places on the Onsager coefficients. Solution: the fluctuations | A and A are
independent, so we easily derive, for these respective cases,

2 2
2 1 1 2
0 0 0 ( ) 0 ; 0 0 0 ( ) 0 ;
qq qq
X S X L L X S X L L

| A = = = > > A = = = > > B B (3.18)

You also have,

( )
2
1
4
( ) ( ) ( ) ( ) 0
qq q q
L L L L

+ > B B B B (3.19)

Problem: prove that ( ) ( )
ij ji
L L = B B . Solution: the proof is given in SMT 06, and the final result is in SMT
06 367 [120.11].


9
Proof of this, and of the claim ( ) ( )
ij ij ji
L L L = + = B B in (3.16), appears in SMT 06 367 [120.11].
Problem: recall ohms law,
e N
e o = = J E J , the isoelectric ( / e = = V E 0 ) Fourier law
Q E
T k = V J , the iso-
number current (
N
= J 0) Fourier law
Q e
T k = V J , and the relation ( ) ( )
ij ji
L L = B B ; these constitute four (4)
equations which can be used to find the four ( )
ij ij
L L = B in terms of the constitutive coefficients , ,
E e
o k k . Do
this. Solution: The Onsager coefficients are related to the familiar transport coefficients , , S o k as follows,

2
2
( ) ( )
1 det ( )
( ) ( ); ( ) ; ( ) ( ) ;
( ) ( ) ( )
q q
L L
e
L S S
T T L eTL eTL

o k = = = = =
B B
L B
B B B B B
B B B
(3.20)

Note that the Onsager-Casimir relations,
( ) ( ); ( ) ( ); ( ) ( ); S S o o k k = = = B B B B B B (3.21)


Problem: compute the power from the linear response equations (3.14), rather than (2.16) (in other words, use
Benentis notation). Subsequently, extremize with respet to x1. solution: write,

( ) ( )
2
1 11 12 1 11 1 12 2 1 11 1 12 2 1
all of this needs to be adapted to the new notat
( ) ( ) ( );
ion
N
T
P I Tx L L Tx L Tx L Tx T x L x L x P x
T

A | |
= A = A + = + = + =
|
\ .
(3.22)

Problem: show that the efficiency /
q
J q e at maximum power depends on two parameters, x and y,
; (3.23)

You have,
= (3.24)

You write,

22
1 2 max
12
1 1 1 1
; ;
1 1 1
C
y y L
x x x x
L y y
q q
+ +
= =
+ + +
(3.25)

Problem: show that (3.19) implies a bound on y of (3.23). solution: the result is,

Now, define

2
*
max 2 2
0 ( ) 0
4
( ) ; ; ( ) ;
0 0 ( ) ( 1) 1
x h x y
x x
h x P
x y h x x x
q q
< s s
s s
> s s +
(3.26)

Writing efficiency,

2
2
1 11 1 12 2 22
1 2
21 1 22 2 1 21 11 22
needed physical
det
; | 0 1 ; 0 ;
fact
N
x Q
Q
I T x L x L x L L
x x I
I T L x L x x L L L
q
q
| |
| | + c
= A = = = >
|
|
|
+ c
\ .
\ .
(3.27)



2
*
max 2 2
0 0 ( );
4
sgn sgn ( ) ; ( ) ;
0 ( ) 0; ( 1) 1
x y h x
x x
x y h x P
x h x y x x
q q
> s s
= = s s
< s s +
(3.28)

Plotting h(x),
(3.29)
(3.30)


Extremize, and you find the following expressions for the power and efficiency,
10 5 5 10
x
1
1
2
3
h x
1
h x
4 2 2 4
x
0.2
0.4
0.6
0.8
1.0
x
C
M
x
x

2
2
max 12 12
1 11 12 2 1 2 max 2 max
1 11 11
1 1
| 0 2 0 ; ( ) ;
2 4 2 2
x C C
Q
P L L P xy
x L L x x x P x P
x L L I y
q q q
c
= + = = = = =
c +
(3.31)

This is the maximum efficiency without TRS. Something provocative about (3.31): it seems you want x > 1?



Figure of merit with magnetic field: you have,

2
( ) ( ) ( )
( ) ;
( )
e e e
S T S S
ZT ZT ZT T
o o
k k

= = =
B B B
B
B
(3.32)

Three terminal devices

Problem: Some people are excited about having a 3
rd
terminal in the thermoelectric junction. Draw a
schematic of such a device. Solution: Sketch of a thermoelectric device in the presence of a magnetic field B.
The entire dashed box represents the conductor C, which is connected to two reservoirs. For the special case of
the three terminal model, the conductor consists essentially of a scattering region and an additional probe
terminal.

(3.33)

Problem: the center-site retarded Green function for a 2-terminal junction
10
with a t-stub and an interaction
r
o appears as,

2 2 2
0
0
;0,0
1
;
( ) ( )
L R L R
r
W W W p p
C r E W W
G
E e e
e
e o e
'
'

=
+ +
i i
(3.34)

Write the Green function for the 3-terminal device shown in (3.33). solution: treating (3.34) as an isolated
Green function, while treating the coupling to the lead P as an interaction, we just need the Green function for
the lead P. Indeed, this is gotten from the work of SPH
11
,

10
See 2013 - nartowt - t-stub thermoelectric junction with e ph interaction.
11
See 1992 - OH State - Hershfield, Davies, Wilkins - Resonant tunneling through Anderson impurity current.

( ) 2 0
;1,1
( )
( , ) (1,1)
2 sin 2 sin 2 sin
P P P P P P P
p j j p j j p p p p p
P P P
r r r
P P P
e e e e e e e e
g j j g g
W p W p W p W
' ' +

' = = = = =
i i i i i i i
i i i
(3.35)

Then, using
0
0 1 0 1
1
(1 ) ( )
r r
G
G G G o o

= = , we have,

2 2 2 2
0
0
2 2 2 2
0
0
1 1 1
,0,0 ;0,0
(( ) ) (( ) ( ) )
1
;
( ) ( )
L R P L R P
L R P L R P
W W W W p p p prev
r r r C r E W W W
W W W W p p p
C r E W W W
g g E e e e
E e e e
e
e
o e o e
e o e
'
'
'
'

= = + +
=
+ + +
i i i
i i i
(3.36)

Phonons

Effect of phonons: Looking at
2
/ ( )
e e ph
ZT S T o k k = + , we see phonons are bad. However, in (3.33), the 3-
terminal device could allow phonons to carry a heat current. They could be tuned to actually be a good thing.

Seebeck coefficient: linearized inegrals,

2
0
1
0
( )( )
1 1
( ) ln ( ) | ;
3
( )
T
f
T
E
B
e B E E
f
E
T E E dE
L k d
S k T T E
eL L eT e dE
T E dE

t
c
=
c
=
c
c

= = =
}
}
(3.37)

Problem: d

Now, recall Dubi and DiVentura, RMP, 83, 2011. Write Lorentzian transmission function,

| |
2
2 2
( ) large efficiency, and 2 parameters to play with ;
( )
F
T E
E E
I
=
I +
(3.38)

However, we have the unphysical limit of 0 I = yielding a finite value of
e
S . Problem: if you go to a scale
where
B
k T I << , linear series-expansions break down.

How to get a high ZT (i.e., good thermoelectrics): (1) large variations of T(E) near Fermi energy. (2) violation
of Wiedemann-Franz law; i.e., / [Lorenz number]
e
o k >> (in appropriate SI-units), (3) phonon thermal
conductivity,

2 2
???
0
1 1
( ) ... ; ;
2 3 1
B B
ph B
f k T
d f
T h e
| e
t
k e e e
t

c
= = = =
c
}
(3.39)

Above = Rego and kirezenow, PRL 81, 232, (1998).
Schwab et al, Nature, 404, 974, (2000).

Problem: when integral (3.39) is done, you sum over all phonon modes. You have big K . You must take into
account
ph
k . That must be properly tuned for a good thermoelectric.

The best thermoelectric: 1996 - Tennesee - Mahan and Sofo - The best thermoelectric. Write the figure of merit
with phonon-contribution, using
( )
n
B
k T
n n h
L J = and
2
1
0 2
J
J J
, as,

2
1
0 2
2
1
2 0 2 2
2 2
1 1
2 2
0 2 1 0 0 2 1 0
( );
( ) ( )
(1 ) (1 )
ph ph
J
J J
J
ph ph
J J J J
L J
ZT ZT
L L L TL J J J J
k k


k k

= = = =
+ +
+ +
(3.40)

Its clear to see that you want 1 = to extremize (3.40). The thing that does this is a delta-function T(E),

( )
( )
2 2
2
1
2 2
0 2
( ( ) ( ) )
( ) ( )
( ) ( ) ( ) 1;
( ) ( ) ( ) ( ) ( ( ) ( ) )( ( ) ( ) )
xT x D x dx
b b D b
J
T E E b E
J J b D b b b D b T x D x dx x T x D x dx
|
o |
| |
= = = = =
}
} }
(3.41)

Howver, this would produce a very low power thermoelectric.

Advantages of nano-systems: (1) the ( ) T E can be nano-engineered, (2) no Wiedemann-Franz law, (3) phonon-
conribution to thermal conductivity can be made small, (4) you can have inherently sharp gradients at such a
tiny length scale, which mercilessly demands one discard the quasi-static approach we just finished discussing.
(5) in bulk, large efficeicny means large power, but these might become independent on the nano-scale. (6) You
have nano-currents and nano-powers; you can scale these up as ~ N = 6.02 x 10
23
.