M. S.

Shell 2009 1/19 last modified 4/10/2012

Ab initio and electronic structure methods ChE210D
Today's lecture: the structure of atoms, how atoms interact to form molecules,
and how molecules interact with each other all at the "first principles" leel,
i.e., no empirical constants or e!perimentall"#deried information.
Basics of quantum theory
$e%lectin% relatiistic effects, all matter is descri&ed at a fundamental leel &" 'uantum theor".
(he central feature of this theor" is the multi#&od" wavefunction:
(r
1
, r
2
, , t)
)ere, r
1
, r
2
, , etc. are the positions of all fundamental particles in the s"stem *electrons,
protons, neutrons+ and each r is a ector (x, y, z). (he waefunction eoles in time, t.
(he waefunction ta,es on comple! alues, of the form o + bi.
(he physical si%nificance of the waefunction is that

(r
1
, r
2
, , t)(r
1
, r
2
, , t) is propor#
tional to the -oint pro&a&ilit" that particle one is at r
1
, particle 2 is at r
2
, etc, all at the time t.
)ere denotes the comple! con-u%ate, i.e., o bi. (he 'uantit"

therefore is alwa"s real

and positie, o
2
+ b
2
.
(r
1
, r
2
, ; t)

(r
1
, r
2
, , t)(r
1
, r
2
, , t)
.or a sin%le particle, such as a sin%le electron, we hae/
(r; t)

(r, t)(r, t)
0uantum mechanics determines the waefunction up to an ar&itrar" multiplicatie constant.
(herefore, we can normali1e the waefunction &" demandin% that the pro&a&ilities sum to one
when inte%rated oer the entire space of coordinates aaila&le to eer" particle. .or a sin%le
particle,
(r; t) =

(r, t)(r, t)
]

(r
i
, t)(r
i
, t)Jr
i

Sometimes the notation is used instead of r to indicate inte%ration oer all space/
(r; t) =

(r, t)(r, t)
]

(r
i
, t)(r
i
, t)J



M. S. Shell 2009 2/19 last modified 4/10/2012
(he waefunction descri&es the eolution of probabilities. (his is er" different from $ewtoni#
an mechanics, in which each particle has an e!act position at time t, and not a distri&ution of
pro&a&le positions. 0uantum mechanics sa"s that this distri&ution is the most we can possi&l"
,now a&out the s"stem2 we cannot predict the position of the particles to more accurac".
(here is some inherent randomness in nature, and the &est we can do is predict the pro&a&ili#
ties of different possi&le outcomes.
(his ma" sound a &it stran%e, &ecause we are not used to this ,ind of &ehaior at the macro#
scopic scale. 3ndeed, for lar%e o&-ects, these pro&a&ilit" distri&utions are er" narrowl" pea,ed
relatie to the o&-ect si1e, such that we can usuall" sa", from a macroscopic scale of measure#
ment, e!actl" where an o&-ect lies in space. .or small o&-ects, li,e atoms and electrons, these
distri&utions &ecome si%nificant.
(he waefunction is determined &" the Schrodinger equation, the 'uantum#mechanical analo#
%" of $ewton4s e'uations of motion. .or a sin%le particle traelin% in a potential ener%" field,
Schrodin%er4s e'uation reads/

2
2m

2
(r, t) + I(r)(r, t) = i
o(r, t)
ot

= b2n where b is 5lanc,4s constant, a fundamental constant that, in a er" loose sense,
%oerns the scale of 'uantum randomness. 6lassical deterministic &ehaior *i.e., $ewton7s
e'uations+ are recoered in the limit b - u.
m is the mass of the particle.

2
is the 8aplacian operator, which in 6artesian coordinates is %ien &"
2
=

2
x
2
+

2

2
+

2
z
2
.
I(r) is the potential ener%" function, or -ust the 9potential:, which returns the potential ener%"
of the particle as a function of its position within the field
$ote that the Schrodin%er e'uation is a differential e'uation that is first order in time and
second order in position. (o sole it, we can use the separation of aria&les techni'ue, where
we write the wae function as the product of a spatiall"#dependent function and a time#
dependent function/ (r, t) = (r)I(t). Ma,in% this su&stitution, we hae,

2
2m
I(t)
2
(r) + I(r)(r)I(t) = i(r)
oI(t)
ot

;earran%in% so that all the spatial terms are on the left and the time#dependent terms on the
ri%ht, we %et

M. S. Shell 2009 </19 last modified 4/10/2012

2
2m
1
(r)

2
(r) + I(r) = i
1
I(t)
oI(t)
ot

(he onl" wa" this e'uation can &e satisfied is if &oth sides e'ual the same time# and position#
independent constant. 8et this constant &e E. 3t turns out that the constant is a possi&le
ener%" of the particle, which is the reason for our choice of notation. Settin% the 8)S of this
e'uation e'ual to the constant, and doin% some sli%ht rearran%ement, "ields

2
2m

2
(r) + I(r)(r) = E(r)
(his particular e'uation is called the time-independent Schrodinger equation. 3t %ies the part
of the Schrodin%er e'uation that depends onl" on position. 3t is common to rewrite the left
hand side as an operator called the Hamiltonian, E, such that
E(r) = E(r) where E =

2
2m

2
+ I(r)
=n operator is simpl" a mappin% of one function to another function. 0uantum mechanics
ma,es e!tensie use of operators, as all o&sera&les *li,e ener%", momentum, elocit", etc+ are
formulated as operators.
(he e!pectation *aera%e o&sered+ alue of an" operator A is %ien &" an e!pression of the
form/
]

AJ
]

J

.or e!ample, the e!pected ener%" for an ar&itrar" waefunction and %ien )amiltonian E is
found &"/
E =
]

EJ
]

J

(he potential ener%" operator is/
u =
]

IJ
]

J

(he ,inetic ener%" operator is/
K =
]

_

2
2m

2
] J
]

J


M. S. Shell 2009 4/19 last modified 4/10/2012
Eigenfunctions and eigenvalues
(he )amiltonian operator, when applied to the waefunction, returns the ener%" times the
waefunction. (his is a ,ind of ei%enalue pro&lem/ an operator applied to a function "ields a
num&er times that same function.
Such pro&lems %ie rise to a discrete set of solutions/ a set of ei%enfunctions possi&le for and
ei%enalues possi&le for E, &ut not a continuous ran%e of alues. 3n other words, for a %ien
potential field I and hence a specific )amiltonian E, the ener%" of the particle can onl" ta,e on
certain, discrete alues.
(his is an important, ph"sical aspect of 'uantum mechanics/ ener%ies are discreti1ed. = particle
cannot hae an" ener%", as in $ewtonian ph"sics. 3nstead, it must hae one from the list of
ener%" ei%enalues. 3n fact, the o&seration of discrete ener%etics in the stud" of h"dro%en
spectroscop" was one of the initial motiations that led Schodin%er to discoer this e'uation.
(he solutions and E to the Schrodin%er e'uation form an infinite famil" of ei%enfunctions and
ei%enalues, respectiel". >e can notate them with the su&script n/
E
n
= E
n

n

3mportantl", the ei%enfunctions form an orthonormal &asis set. (hat is, an" ar&itrar" wae#
function can &e e!pressed as a linear com&ination of these. =ssumin% the
n
are all normal#
i1ed, an ar&itrar" waefunction can &e written as/
= c
n

n
n

where the c
n
are coefficients %ien &"/
c
n
= _
n

J
(his is analo%ous to ector mathematics/ an" three#dimensional ector can &e e!pressed as a
linear sum of unit ectors alon% the !, ", and 1 a!es. (he coefficients in the linear sums are
%ien &" dot products.
?ecause the ei%enfunctions are orthonormal, the followin% identit" holds/
_
n

m
J = ]
u m = n
1 m = n


M. S. Shell 2009 @/19 last modified 4/10/2012
Electronic structure and the Born-Oppenheimer approximation
>e would li,e to use the Schrodin%er e'uation to compute the electronic structure of ar&itrar"
atoms and molecules. ?" electronic structure, we mean the wae function for all of the elec#
trons in the s"stem, for a fi!ed set of nuclear coordinates. 3n other words, we place the nuclei
at fi!ed locations in space and sole the time#independent Schrodin%er e'uation for all of the
electrons interactin% with them.
(he electronic structure proides the ener%ies associated with the electron#electron and
electron#proton interactions. Alectrons can e!ist in an" num&er of e!cited states, which corre#
spond to different ei%enfunctions of the waefunction, &ut t"picall" we are interested in the
one with the lowest ener%", the so#called ground-state of the s"stem.
3n principle, a molecule is determined &" a complete waefunction that includes &oth electron
and nuclear *protons, neutrons+ de%rees of freedom. )oweer, the masses of nuclei are much
%reater than that of electrons. =s a result, we can thin, of the electrons as much faster de%rees
of freedom that ad-ust rapidl" to chan%es in the positions of the nuclei. Mathematicall", we can
write the total waefunction as a product of nuclear and electronic waefunctions. (his is the
so#called Born-Oppenheimer approimation/

tot
(nuclei,electrons) = (nuclei)(electrons)
= conse'uence of this appro!imation is that the total ener%" of the s"stem is a sum of the
nuclear ener%" *electrostatic repulsion of positiel" char%ed nuclei+ with the electronic ener%"
*electrons with each other and with the nucleus+/
E
tot
= E
nuc
(nuclei-nuclei) +E(elections-nuclei anu elections-elections)
>e will use E hereon to descri&e the electronic ener%" alone.
(he &asic idea of electronic structure calculations is to map out the ground state energy
surface, that is, the %round state electronic ener%" as a function of the positions of the nuclei.
(his inoles seeral steps/
1. .or a fi!ed set of nuclear coordinates R, sole the time#independent Schrodin%er e'ua#
tion for the electrons to o&tain the ei%enfunctions (r
1
, r
2
, )! where r

denote the
electron positional de%rees of freedom.
2. 6ompute the %round#state ener%" E
0
from the lowest#ener%" waefunction.
<. 6han%e to a new set of nuclear coordinates.

M. S. Shell 2009 B/19 last modified 4/10/2012
The hydrogen atom
(he h"dro%en atom is the onl" neutral atomic s"stem for which the electronic structure can &e
found e!actl" *anal"ticall"+. (his is a classic pro&lem in 'uantum mechanics.
(he )amiltonian for one electron or&itin% one proton is/
E =

2
2m

2

c
2
4ne
0
r

)ere, the last term is the 6oulom& potential ener%" of an electron or&itin% a proton at the
ori%in, and r is its radial distance from it. c is the electron char%e and e
0
is the permittiit" of
free space.
(he wae function can &e soled &" a transformation of the electron position to spherical
coordinates and the use of the separation of aria&les techni'ue. (he final solution is of the
form/

nIm
= R
nI
(r)
Im
(0, )
)ere, there is a radial part %ien &" R
nI
(r) and an an%ular part %ien &"
Im
(0, ). (he e'ua#
tion descri&es an infinite famil" of functions *the ei%enfunctions+ that all satisf" Schrodin%er7s
e'uation for the h"dro%en atom. >e refer to these different waefunction solutions as or"it-
als.
(he inte%ers n, l, m are 'uantum num&ers and hae the followin% ran%es/
n = 1,2,S, is the principal 'uantum num&er. Cies the shell of the electron.
l = u,1, , (n 1) is the a1imuthal 'uantum num&er. Cies the t"pe of or&ital,
u = s, 1 = p, 2 = J, S =
m = l, l + 1, ,u, , l 1, l is the ma%netic 'uantum num&er.
(he ener%" ei%enalue associated with an ei%enfunction is dependent onl" on the principal
'uantum num&er/
E =
pc
4
8e
0
2
b
2
n
2
with p =
m
p
m
c
m
p
+ m
c

(he functions R
n
contain so#called 8a%uerre pol"nomials. (he first few are %ien &"/
R
10
(r) = 2
3
2
exp(r)

M. S. Shell 2009 D/19 last modified 4/10/2012
R
20
(r) = 2
3
2(1 r) exp(r)
R
21
(r) = _
4
S
]
1
2

5
2
r exp(r)
)ere, 4n
2
m
c
c
2
b
2
n.
(he functions
Im
are the so#called spherical harmonics. (he first few are/

00
(0, ) =
1
V4n

1-1
(0, ) = _
S
8n
]
1
2
sin0 c
q

10
(0, ) = _
S
8n
]
1
2
sin0 c
-q

11
(0, ) = _
S
4n
]
1
2
cos 0
3n an" case, these functions are ,nown anal"ticall" and thus the full spectrum of waefunction
ei%enfunctions is ,nown.
Polyelectronic systems
.or multi#electron s"stems, it is impossi&le to sole the Schrodin%er e'uation e!actl". (here are
seeral challen%es here/
the three#&od" pro&lem E no solutions can &e found for more than two interactin% par#
ticles
electron spin E electron or&itals can either hae up or down spin, la&eled as o and [.
Aach spatial or&ital can accommodate up to two spins. >e must account for this fact
in our solutions.
indistin%uisha&ilit" E the waefunction must chan%e si%n upon swappin% the identities
of two electrons &ecause the" are indistin%uisha&le fermions.
(he com&ination of a spatial waefunction or&ital with a spin waefunction is called a spin
orbital and notated &" the s"m&ol _.
_
nIms
=
nIm
s wheie s = o oi [

M. S. Shell 2009 F/19 last modified 4/10/2012
.or an" ar&itrar" atom or molecule with H nucleii and N electrons, the )amiltonian can &e
written as
E =

2
2m

2

N
=1

c
2
4ne
0

Z
k
R
k
M
k=1
N
=1
+
c
2
4ne
0

1
r
]
N
<]

)ere, the first term a%ain corresponds to the ,inetic ener%" operator. (he middle term %ies
the 6oulom&ic interaction of electrons with nuclei, where Z
k
is the char%e unit of nucleus k.
(he final term is a pairwise sum oer electrons that accounts for electronic repulsion.
Variational theory
(hou%h we cannot sole for the waefunction e!actl" %ien the pol"electronic )amiltonian, a
remar,a&le theorem allows us to find appro!imations to it. (his ariational theorem sa"s that
the e!pectation alue for the ener%" of an" trial waefunction will %ie an ener%" %reater than
or e'ual to the %round#state ener%" of the true solution to Schrodin%er7s e'uations. (hus, we
can find appro!imate solutions to Schrodin%er7s e'uation &" minimi1in% the e!pectation ener%"
with respect to a trial solution.
(he proof of the ariational theorem is actuall" 'uite simple. 6onsider an ar&itrar" trial wae#
function written as a sum oer orthornormal &asis functions that are true solutions for the
)amiltonian of interest/
= c

(o find the e!pectation alue of the ener%" E for the trial wae function,
E =
]

EJ
]

J

Su&stitutin% the e!pression a&oe,
E =
_ _ c

c
]
]

E
]
J
]
_ _ c

c
]
]

]
J
]

=
_ _ c

c
]
]

E
]

]
J
]
_ _ c

c
]
]

]
J
]

=
_ _ c

c
]
E
]
]

]
J
]
_ _ c

c
]
]

]
J
]

Gsin% the orthonormalit" condition, the inte%rals anish for all &ut i = ],

M. S. Shell 2009 9/19 last modified 4/10/2012
E =
_ c

2
E

_ c

Su&tractin% the %round#state ener%" E
0
from &oth sides,
E E
0
=
_ c

2
(E

E
0
)

_ c

?" the definition of E
0
, E

E
0
u on the ;)S, since E
0
is the lowest alue of the E

. (here#
fore, the ;)S is alwa"s 1ero or positie and we must hae
E E
0

(he idea of the ariational principle is therefore the followin%/
5ic, an appro!imate form of the waefunction for the pol"atomic s"stem. (hen,
find the optimal such form &" minimi1in% the e!pectation ener%" with the true
)amiltonian with respect to an" free parameters. 8ower e!pectation ener%ies
alwa"s indicate &etter solutions.
Hartree-Foc approach and !later determinants
(he )artree#.oc, approach posits a trial form of the $#electron waefunction and uses the
ariational theorem to o&tain an appro!imate solution. (he &asic idea here is to e!press the
waefunction as a product of indiidual spin or&ital solutions, the so#called Hartree product:
(1,2,S, , N) = _
1
(1)_
2
(2) _
N
(N)
)ere, the num&ers written are a&&reiations to the electron de%rees of freedom. Gnfortunate#
l", this form of the trial waefunction does not o&e" the indistin%uisha&ilit" re'uirement for
fermions, that the swappin% of two particles %enerates an identical &ut ne%ated waefunction/
_
1
(1)_
2
(2) _
N
(N) = _
1
(2)_
2
(1) _
N
(N)
since in %eneral all of the _ functions can &e different.
3nstead of the )artree product, we want to use a similar multiplicatie com&ination indiidual
spin or&itals, &ut ones that form the ne%atie upon swappin%. .or two electrons, we could
ma,e the choice,
(1,2) =
1
V2
|_
1
(1)_
2
(2) _
1
(2)_
2
(1)]

M. S. Shell 2009 10/19 last modified 4/10/2012
$otice that swappin% 1 and 2 returns the ne%atie waefunction and thus satisfies the indistin#
%uisha&ilit" criterion/
1
V2
|_
1
(1)_
2
(2) _
1
(2)_
2
(1)] =
1
V2
|_
1
(2)_
2
(1) _
1
(1)_
2
(2)]
(he s'uare root comes from the normali1ation condition.
.or an ar&itrar" num&er of electrons, formin% com&inations of or&itals such as this can &e
achieed usin% the determinant of a matri!, the so#called Slater determinant/
(1,2, , N) =
1
VN

_
1
(1) _
2
(1) _
N
(1)
_
1
(2) _
2
(2) _
N
(2)

_
1
(N) _
2
(N) _
N
(N)

(he determinant is a natural wa" to achiee the indistin%uisha&ilit" principle/ swappin% two
rows or two columns causes the determinant to chan%e si%n, e!actl" what we need for our trial
waefunction. Moreoer, if two rows or columns are &e identical, the determinant would &e
1ero. 5h"sicall", this would mean that two electrons were occup"in% the same or&ital and same
spin, for&idden &" the 5auli e!clusion principle.
(he )artree#.oc, appro!imation to the waefunction is e'uialent to a mean#field solution of
Schrodin%er7s e'uation in which each electron moes within an aera%e field due to the pres#
ence of all of the other electrons.
>e will now consider onl" closed#shell s"stems, i.e., s"stems in which all electrons appear in
pairs. (here are special methods for treatin% open#shell s"stems, &ut we will not coer these.
Su&stitutin% the Slater determinant as a trial waefunction into the pol"electronic )amiltonian
%ies the followin% e!pression for the e!pectation ener%", after simplification of inte%rals/
E = 2 E

coie
N 2
=1
+ 2
]
K
]

N 2
]=1
N 2
=1

E

coie
%ies the ,inetic and potential ener%" of the electrons moin% in the field of the nuclei/
E

coie
= _J
1
_

(1)
1
2

2

Z
k
R
1k
M
k=1
_

(1)

]
%ies the electrostatic repulsion &etween electrons/

M. S. Shell 2009 11/19 last modified 4/10/2012

]
= _J
1
J
2
_

(1)_
]
(2)
1
r
12
_

(1)_
]
(2)
K
]
%ies the so#called echange interaction. (his stems from the tendenc" of electrons with
the same spin to "aoid" each other, per the 5auli e!clusion principle/
K
]
= _J
1
J
2
_

(1)_
]
(2)
1
r
12
_

(2)_
]
(1)
$otice that the onl" difference here is the swappin% of identities in the second set of or&itals.
=ll e'uations here hae &een written in atomic units, and fundamental constants hae &een
omitted for clarit".
"inear com#ination of atomic or#itals $"%&O'
$ow that we can use the Slater determinant to find solutions that o&e" the indistin%uisha&ilit"
principle, we need to specif" forms for the functions _

that %o into them. (he easiest solution

here is to use the anal"tic &asis functions that we determined for the h"dro%en atom. >e can
e!press each _

as a sum of these functions, with coefficients/

_

= c

=1
s

)ere, the

are the solutions to the waefunction ei%enfunction e!pansion for the h"dro%en
atom. (he s

%ie the spins. (he c

]
are coefficients that will &e determined *optimi1ed+ &"
ariational minimi1ation of the e!pectation ener%"/
oE
oc

= u
3t is important that the minimi1ation is constrained so that the or&itals _

are orthonormal to
each other. (his is accomplished usin% 8a%ran%e multipliers.
Gsin% the e!pression a&oe for the or&ital ener%", this minimi1ation can &e performed. =ssume
we use K &asis functions in our e!pression for _

. (he result %ies the #oothaan-Hall equations

and has the form of a set of matri! e'uations/
=
is the .oc, matri!2 its elements are %ien &",

M. S. Shell 2009 12/19 last modified 4/10/2012

= _Jp
1

(1)
1
2

2

Z
k
R
1k
M
k=1

(1)
2 _J
1
J
2

(1)

(2) _
1
r
12
]

(2)

(2)

=1

=1
N 2
]=1
_J
1
J
2

(1)

(2) _
1
r
12
]

(2)

(2)
(he matri! contains the coefficients to &e determined

= c

(he matri! %ies the oerlap &etween the or&itals/

]
= __

_
]
J
.inall", %ies the or&ital ener%ies for the K optimal or&itals that are determined/
=
e
1
u u
u e
2
u

u u e

(he ;oothan#)all e'uations are matri! e'uations that can &e soled usin% matri! al%e&ra to
%ie &ac, the optimal coefficients and or&ital ener%ies. )oweer, these e'uations must &e
soled iteratiel" &ecause elements of &oth and depend on the coefficients themseles.
(he ;oothan#)all procedure iteratiel" operates in this wa". >e won7t %o into details here.
(he minimum num&er of &asis or&itals that can &e used K is e'ual to the num&er of electrons.
More will allow the treatment of unoccupied ener%" leels and can enhance the accurac" of the
calculations. Hften, howeer, one can reach the Hartree-$oc% limit where the ener%" no lon%er
decreases with the addition of more &asis functions.
Basis sets
Most of the time spent solin% the ;oothan#)all e'uations numericall" is deoted to computin%
the inte%rals in the .oc, and oerlap matrices. ("picall" so#called Slater-type or"itals &STOs'
are used in the &asis functions

, which are inspired &" the form of the solutions for the
h"dro%en atom to first order in the 8a%uerre pol"nomials/
R
n
(r) = (2)
n
1
2|(2n)]
-
1
2
r
n-1
exp(r)

M. S. Shell 2009 1</19 last modified 4/10/2012
Gnfortunatel" this functional form for the or&itals, while ph"sicall" inspired, results in computa#
tional challen%es. >hat ma,es the use of S(Hs challen%in% is that the inte%rals inolin%
or&itals sittin% on different nuclei can &e er" difficult to compute.
= simple solution has &een to appro!imate S(Hs with Caussian functions insteadIso#called
(aussian type or"itals &(TOs'. (hat is, one uses multiple Caussians to appro!imate the form of
the S(Hs. (he adanta%e of Caussians is that the product of two Caussians centered at two
different locations is another Caussian *and can computed anal"ticall"+ such that the or&ital
inte%rals can &e computed er" fast.

= special notation descri&es the &asis sets used in common a& initio calculations.
S(H#<C E a minimal &asis set in which three Caussians are used to represent each Slat#
er#t"pe or&ital. Gseful for 'uic,l" computin% molecular %eometries, &ut not er" accu#
rate.
<#21C E three Caussians are used for the core or&itals. .or the alence electrons, a split
&asis set is emplo"ed where two Caussians are used for a contracted part of the wae#
function and one for the diffuse part. (his is important for atoms li,e o!"%en and fluo#
rine where the minimal &asis sets don7t allow for the alence or&itals to e!pand or con#
tract in response to the molecular enironment.
B#<1C E the same as a&oe &ut with si! Caussians for the core or&itals2 more accurate.
B#<1CJ E the same as a&oe &ut allowin% polari1ation *i.e., distortion+ of non#h"dro%en
or&itals to accommodate as"mmetr". (his &asis set mi%ht &e considered a standard
hi%h accurac" calculation, althou%h it is e!pensie.
r
S(H
< C(Hs
2 C(Hs
1 C(H


M. S. Shell 2009 14/19 last modified 4/10/2012
Hften, one wants to find an optimal molecular %eometr" for a molecule. (his inoles searchin%
nuclear confi%urations for the one with lowest ener%", and thus re'uires a complete electronic
structure determination upon each chan%e of nuclear coordinates. ("picall" fast, appro!imate
&asis sets li,e S(H#<C are first used in this %eometr" optimi1ation. (hen, when the %eometr" is
near the ener%" minimum, more accurate and e!pensie &asis sets li,e B#<1CJ are emplo"ed to
refine the calculations.
%omputing the electron density
Hne of the most important properties we can e!amine from an electron structure calculation is
the electron density, that is, the pro&a&ilit" densit" with which we e!pect to see an electron as
a function of spatial position. (he electron densit" %ies important properties of a molecule,
such as the dipole, and is the startin% point for deelopin% simpler, fi!ed#char%e models of
molecules that we will discuss in a later lecture.
.or a set of N orthonormal one#electron or&itals

, we can use the pro&a&ilistic interpretation

of the waefunction to deelop an e!pression for the electron densit"/
(r) =

(r)
2
N
=1

$otice that we hae
N = _(r)Jr
3f the or&itals are e!pressed as a sum of K &asis functions

, as in the ;ootham#)all approach,

we can rewrite the electron densit" as
(r) = c

N
=1
_

(r)

(r)

=1

=1

!ummary of Hartree-Foc
(he &asic conceptual approach to these computations is the followin%/
=ppro!imate/
(1,2, , N) =
1
VN

_
1
(1) _
2
(1) _
N
(1)
_
1
(2) _
2
(2) _
N
(2)

_
1
(N) _
2
(N) _
N
(N)


M. S. Shell 2009 1@/19 last modified 4/10/2012
A!pand each spin or&ital in terms of K * N+ h"dro%en#li,e &asis solutions

/
_

= c

=1
s

Model each

usin% a wei%hted finite sum of Caussian#t"pe or&itals *C(Hs+/

= o

1
o

V2n
c
-
r-r
i

2
2
i
2

)ere, the o

are chosen to reproduce the correspondin% Slater#t"pe or&itals *S(Hs+.

(o sole for the waefunction, one finds the optimal coefficients c

in its &asis e!pansion.

(here are K N of these. Gse the ariational principle/
oE
oc

= u
su&-ect to the constraint that the _

are orthonormal to each other. )ere,

E =
]

EJ
]

J

where is the waefunction defined a&oe, and the )amiltonian operator is/
E =

2
2m

2

N
=1

c
2
4ne
0

Z
k
R
k
M
k=1
N
=1
+
c
2
4ne
0

1
r
]
N
<]

.inall", compute the electron densit" usin% the optimal coefficients/
(r) = c

N
=1
_

(r)

(r)

=1

=1

(ensity functional theory
= complementar" approach to )artree#.oc, theor" for determinin% electronic structure is the
density functional theory *K.(+ of )ohen&er%, Lohn, and Sham. (his theor" has en-o"ed a
sur%e of success in the past 2#< decades. 3nstead of computin% the multielectron, multidimen#
sional waefunction, densit" functional theor" is concerned with computin% onl" the electron
densit" (r).

M. S. Shell 2009 1B/19 last modified 4/10/2012
K.( is ena&led &" a remar,a&le theorem due to )ohen&er% and Lohn *19B4+ that shows that
the %round state waefunction and ener%" of a pol"electronic s"stem is uni'uel" determined &"
a functional of the electron densit". 3n mathematical terms,
E
0
|(r)]
)ere, the &rac,ets indicate the presence of a functional. = functional is a mathematical opera#
tion that depends on the entire &ehaior of a function, not -ust its alue at a specific point. .or
e!ample, the functional/
|y] = _ y(x)Jx
1
0

depends on the complete &ehaior of the function y &etween x = u to 1. .unctionals differ
from functions in that a function ta,es a sin%le alue as an ar%ument, whereas a functional
ta,es a function itself.
3n K.(, the %round state ener%" functional is written as *Lohn and Sham, 19B@+/
E|(r)] = _I(r)(r)Jr + E
L
|(r)] +E
H
|(r)] + E
XC
|(r)]
(he first tem on the ;)S %ies the interaction of the electrons with e!ternal potentials2 here,
this is their interactions with the nuclei/
_I(r)(r)Jr = _
(r)
r R
k

M
k=1
Jr
(he second term %ies the ,inetic ener%". 3t is assumed to &e identical to that which would &e
attained for an e'uialent s"stem of noninteracting electrons/
E
L
|(r)] = _

(r) _

2
2
_

(r) Jr
N
=1

(he third term, the )artree term, is %ien &" the electron#electron repulsie interactions/
E
H
|(r)] =
1
2
__
(r
1
)(r
2
)
r
1
r
2

Jr
1
Jr
2

(he e!chan%e#correlation functional is not ,nown e!actl", &ut it is a universal function, inde#
pendent of the specific s"stem at hand. 3t includes e!chan%e and correlation effects, as well as
the difference &etween the true ,inetic ener%" and the noninteractin% ,inetic ener%" assump#

M. S. Shell 2009 1D/19 last modified 4/10/2012
tion defined a&oe. = num&er of appro!imations e!ist for E
XC
. (he simplest is the so#called
local density approimation *8K=+, %ien &"/
E
XC
|(r)] = _(r)e
XC
( (r))Jr
(he 8K= simpl" states that the onl" the local electron densit" affects the e!chan%e#correlational
ener%", and that it can &e appro!imated &" the use of a simple function of . )ere, e
XC
() is
t"picall" ta,en from simulations of homo%eneous electron %as. (hese are sometimes fitted to
simple forms. =s one e!ample, Cunnarsson and 8und'ist proposed *19DB+/
e
XC
() =
u.4S8
r
s

u.u666
2
(1 + x) log(1 + x
-1
) x
2
+
x
2

1
S
[
r
s
11.4
;
4n
S
r
s
3
=
-1

)inimi*ing the electron density functional
(o sole for (r) usin% the functional ener%" a&oe, one uses the ariational principle to
minimi1e E. (his is actuall" a functional minimi1ation since we are findin% an entire function,
rather than a sin%le num&er or set of num&ers, that minimi1es the e!pression of interest/
o
o(r)
E|(r)] p _(r)Jr = u
)ere, p is a 8a%ran%e multiplier that ensures that/
_(r)Jr
is constant, and e'ual to N, the total num&er of electrons.
(o sole this functional minimi1ation, we introduce an e!pression for the electron densit" in
terms of N or&ital e'uations/
(r) =

(r)
2
N
=1

Aaluatin% the functional minimi1ation with this e!pression for the densit" leads to the Lohn#
Sham e'uation/
_

1
2
2

Z
k
r
1
R
k

M
k=1
_ + _
(r
2
)
r
1
r
2

Jr
2
+
oE
XC
|(r
1
)]
o(r
1
)
_

(r
1
) = e

(r
1
)
(his e'uation must &e soled self#consistentl"/

M. S. Shell 2009 1F/19 last modified 4/10/2012
1. =n initial appro!imation for (r) is %uessed.
2. (he Lohn#Sham e'uation is used to derie a set of or&itals

and or&ital ener%ies e

.
(his approach is er" similar to the )artree#.oc, method, where the or&itals are e!#
pressed as a linear sum of &asis functions with coefficients that are determined aria#
tionall".
<. (he deried or&itals are used to update the electron densit" ia the e'uation a&oe.
4. (he process is iterated at step 2 until the densit" coner%es.
%ar-Parinello a# initio molecular dynamics
So far, we hae onl" seen electronic structure calculations for fi!ed positions of atomic nuclei.
Gltimatel", we would li,e to &e a&le to e!amine the time#eolution of the nuclei as well, in
order to e!amine molecular processes. (he immediate challen%e with this approach is compu#
tational e!pense/ eer" time we moe the positions of the nuclei, we re'uire a completel" new
electronic structure calculation.
6ar and 5arinello *19F@+ deeloped an ele%ant solution to couplin% the time#propa%ation of
moin% nuclei with the electronic structure determination. (his is often called a" initio mo-
lecular dynamics. (heir approach sets up "e'uations of motion" for the solutions of the coeffi#
cients that appro!imatel" follow the ariational#minimum or&ital coefficients one would find
from a K.( solution of the electronic structure at each step. (hese coefficients are eoled in
time as the nuclear positions are eoled. ?" correctl" pic,in% fictitious coefficient "masses"
this approach is a&le to 'uite accuratel" reproduce the time eolution of the electronic struc#
ture alon%side the time#eolution of the nuclear positions.
"imitations and computational expense
=& initio calculations are computational er" e!pensie. ("picall", the" can onl" handle 10
2

atoms and, if 6ar#5arinello d"namics is used, time scales on the order of 10ps. Hne pro&lem
with these methods is that the computational e!pense scales rou%hl" as N
4
where N is the
num&er of &asis functions *which must at least &e the electrons+. (his arises due to the four#
dimensional inte%rals that must &e performed &etween &asis functions. (his can ma,e a& initio
studies prohi&itie for een small molecular s"stems.
!emi-empirical methods
= num&er of appro!imate methods hae &een deeloped that achiee &etter performance and
scalin% than the )artree#.oc, and K.( approaches. (hese so#called semi-empirical methods

M. S. Shell 2009 19/19 last modified 4/10/2012
onl" treat the alence electrons e!plicitl" and incorporate parameters fitted to e!perimental
data to ma,e up for this lac, of e!plicit detail in all of the electrons. (hese methods can treat
~ 1u
3
atoms and time scales up to 10 ns. (he trade#off, howeer, is that lar%e parameter sets
are re'uired from e!perimental input.