Lecture 8:

Introduction to Density
Functional Theory
Marie Curie Tutorial Series: Modeling Biomolecules
December 6-11, 2004
Mark Tuckerman
Dept. of Chemistry
and Courant Institute of Mathematical Science
100 Washington Square East
New York University, New York, NY 10003
Background
1920s: Introduction of the Thomas-Fermi model.
1964: Hohenberg-Kohn paper proving existence of exact DF.
1965: Kohn-Sham scheme introduced.
1970s and early 80s: LDA. DFT becomes useful.
1985: Incorporation of DFT into molecular dynamics (Car-Parrinello)
(Now one of PRLs top 10 cited papers).
1988: Becke and LYP functionals. DFT useful for some chemistry.
1998: Nobel prize awarded to Walter Kohn in chemistry for
development of DFT.
1 1
( , ,..., , )
N N
s s r r
e e ee eN
H T V V = + +
External Potential:
Total Molecular Hamiltonian:
e N NN
H H T V = + +
2
1
,
1
2
| |
N
N I
I
I
N
I J
NN
I J I
I J
T
M
Z Z
V
=
>
=
=

R R
Born-Oppenheimer Approximation:

[ ]
1 0 1
0
(x ,..., x ; ) ( ) (x ,..., x ; )
[ ] ( , ) ( , )
e e
e ee eN N N
N NN
T V V E
T V E t i t
t

+ + =

+ + =

R R R
R R
x ,
i i i
s = r
Hohenberg-Kohn Theorem
Two systems with the same number N
e
of electrons have the same
T
e
+ V
ee
. Hence, they are distinguished only by V
en
.
Knowledge of |
0
> determines V
en
.
Let V be the set of external potentials such solution of
yields a non=degenerate ground state |
0
>.
Collect all such ground state wavefunctions into a set . Each
element of this set is associated with a Hamiltonian determined by the external
potential.
There exists a 1:1 mapping C such that
C : V
[ ]
0 e e ee eN
H T V V E = + + =
0 0
=
( )
0 0 0
(2)
e ee eN
T V V E

+ + =
( )
0 0 0 e ee eN
T V V E

+ + =
Hohenberg-Kohn Theorem (part II)
Given an antisymmetric ground state wavefunction from the set , the
ground-state density is given by
1
2
2 1 2 2
( ) ( , , , ,..., , )
e e e
N
e
e N N N
s s
n N d d s s s =

r r r r r r
Knowledge of n(r) is sufficient to determine |>
Let N be the set of ground state densities obtained from N
e
-electron ground
state wavefunctions in . Then, there exists a 1:1 mapping
D
-1
: N
D : N
The formula for n(r) shows that D exists, however, showing that D
-1
exists
Is less trivial.
Proof that D
-1
exists
0 0 0 0 0 e e ee eN
E H T V V

= = + +
[ ]
0 0 0
( ) ( ) ( ) (2)
ext ext
E E d n V V

<

r r r r
(CD)
-1
: N V
0 0 0 0 0

[ ] [ ] [ ] n O n O n =
The theorems are generalizable to degenerate
ground states!
The energy functional
The energy expectation value is of particular importance
0 0 0 0 0
[ ] [ ] [ ]
e
n H n E n =
From the variational principle, for |> in :
0 0 e e
H H
Thus,
0
[ ] [ ] [ ] [ ]
e
n H n E n E n =
Therefore, E[n
0
] can be determined by a minimization procedure:
0
( )
[ ] min [ ]
n
E n E n

=
r N
0 0
0 0
0 0
0 0
0 0 0
0 0
( ) ( ) ( )
n e ee eN n e ee eN
n e ee n ext e ee
n e ee n e ee
T V V T V V
T V d n V T V d n
T V T V
+ + + +
+ + + +
+ +

r r r r
0
( )
ext
V r r
( )
min [ ] ( ) ( )
ext
n
F n d n V

= +

r
r r r
*
2 1 2 2 1 2 2
{ }
( , , , ,..., , ) ( , , , ,
e e e
e N N N
s
N d d s s s s s =

r r r r r r r ( , ) ..., , )
e e
N N
s

r r r
The Kohn-Sham Formulation
Central assertion of KS formulation: Consider a system of N
e
Non-interacting electrons subject to an external potential V
KS
. It
Is possible to choose this potential such that the ground state density
Of the non-interacting system is the same as that of an interacting
System subject to a particular external potential V
ext
.
A non-interacting system is separable and, therefore, described by a set
of single-particle orbitals
i
(r,s), i=1,,N
e
, such that the wave function is
given by a Slater determinant:
1 1 1
1
(x ,..., x ) det[ (x ) (x )]
!
e e e
N N N
e
N
=
The density is given by
2
1
( ) (x)
e
N
i i j ij
i s
n
=
= =

r
The kinetic energy is given by
* 2
1
1
(x) (x)
2
e
N
s i i
i s
T d
=
=

r
KS
( )
( )
( )
xc
ext
E n
V V d
n

= + +

r
r r
r r r
/ 2
2
1
1
( ) ( )
2
e
N
s i i
i
T
=
=

r r
Some simple results from DFT
E
barrier
(DFT) = 3.6 kcal/mol
E
barrier
(MP4) = 4.1 kcal/mol
Geometry of the protonated methanol dimer
2.39
MP2 6-311G (2d,2p) 2.38
Results methanol
Dimer dissociation curve of a neutral dimer
Expt.: -3.2 kcal/mol
Lecture Summary
Density functional theory is an exact reformulation of many-body
quantum mechanics in terms of the probability density rather than
the wave function
The ground-state energy can be obtained by minimization of the
energy functional E[n]. All we know about the functional is that
it exists, however, its form is unknown.
Kohn-Sham reformulation in terms of single-particle orbitals helps
in the development of approximations and is the form used in
current density functional calculations today.