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JC Cuevas DFT
JC Cuevas DFT
0.- Motivation I.
Walter Kohn was awarded with the Nobel Prize in Chemistry in 1998 for his development of the density functional theory.
Number of Publications
3000
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0
1980
1984
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Year
1996
2000
The density functional theory (DFT) is presently the most successfull (and also the most
promising) approach to compute the electronic structure of matter.
Its applicability ranges from atoms, molecules and solids to nuclei and quantum and
classical fluids.
In its original formulation, the density functional theory provides the ground state properties of a system, and the electron density plays a key role.
An example: chemistry. DFT predicts a great variety of molecular properties: molecular
structures, vibrational frequencies, atomization energies, ionization energies, electric and
magnetic properties, reaction paths, etc.
The original density functional theoy has been generalized to deal with many different
situations: spin polarized systems, multicomponent systems such as nuclei and electron
hole droplets, free energy at finite temperatures, superconductors with electronic pairing
mechanisms, relativistic electrons, time-dependent phenomena and excited states, bosons,
molecular dynamics, etc.
2e2 X
G=
Ti
h i
(b)
(e)
Density of states
(a)
b d
(c)
(d)
2
03
Landauer formula
0
1
E (eV)
REVIEW: Cuevas, Heurich, Pauly, Wenzel and Schon, Nanotechnology 14, 29 (2003).
0.- Literature.
The goal of this lecture is to give an elementary introduction to density functional theory. For
those who want to get deeper into the subtleties and performance of this theory, the following
entry points in the literature are strongly adviced:
Original papers
Inhomogeneous Electron Gas, P. Hohenberg and W. Kohn, Phys. Rev. 136, B864 (1964).
Self Consistent Equations Including Exchange and Correlation Effects, W. Kohn and L.J. Sham,
Phys. Rev. 140, A1133 (1965).
Review Articles
Nobel Lecture: Electronic structure of matterwave functions and density functionals,
W. Kohn, Rev. Mod. Phys. 71, 1253 (1998).
The density functional formalism, its applications and prospects, R.O. Jones and O. Gunnarsson, Rev. Mod. Phys. 61, 689 (1989).
Books
Density-Functional Theory of Atoms and Molecules, R.G Parr and W. Yang, Oxford University Press, New York (1989).
A Chemists Guide to Density Functional Theory, W. Koch and M.C. Holthausen, WILEYVCH (2001).
The ultimate goal of most appproaches in solid state physics and quantum chemistry is the
solution of the time-independent, non-relativistic Schr odinger equation
~ 1, R
~ 2, ..., R
~ M ) = Ei i(~
~ 1, R
~ 2 , ..., R
~M)
i(~
x1 , ~
x2 , ..., ~
xN , R
x1 , ~
x2, ..., ~
xN , R
H
(1)
M
M
N
N
M
N
N X
M X
X
X
1
ZA ZB
1 X 2 1 X 1 2 X X ZA
=
i
A
+
+
H
2 i=1
2
MA
riA
r
RAB
i=1
i=1 j>i ij
A=1
A=1
(2)
A=1 B>A
Here, A and B run over the M nuclei while i and j denote the N electrons in the system.
The first two terms describe the kinetic energy of the electrons and nuclei. The other three
terms represent the attractive electrostatic interaction between the nuclei and the electrons and
repulsive potential due to the electron-electron and nucleus-nucleus interactions.
Note: throughout this talk atomic units are used.
Born-Oppenheimer approximation: due to their masses the nuclei move much slower than
the electrons = we can consider the electrons as moving in the field of fixed nuclei = the
nuclear kinetic energy is zero and their potential energy is merely a constant. Thus, the electronic
Hamiltonian reduces to
elec
H
M
N
N
N
N X
X
1 X 2 X X ZA
1
N e + V
ee
=
i
+
= T + V
2 i=1
riA
r
i=1
i=1 j>i ij
(3)
A=1
where Enuc
(4)
M
M X
X
ZA ZB
=
RAB
A=1 B>A
(5)
When a system is in the state , the expectation value of the energy is given by
h|H|i
where h|H|i
=
E[] =
h|i
Hd~
x
(6)
The variational principle states that the energy computed from a guessed is an upper
bound to the true ground-state energy E0 . Full minimization of the functional E[] with
respect to all allowed N -electrons wave functions will give the true ground state 0 and energy
E[0] = E0 ; that is
N e + V
ee |i
E0 = minN E[] = minN h|T + V
(7)
For a system of N electrons and given nuclear potential V ext , the variational principle defines a
procedure to determine the ground-state wave function 0, the ground-state energy E0 [N, Vext ],
and other properties of interest. In other words, the ground state energy is a functional of
the number of electrons N and the nuclear potential Vext :
E0 = E[N, Vext ]
(8)
(10)
N
X
N
1 X
HF i =
= hHF |H|
Hi +
(Jij Kij )
2 i,j=1
i=1
Z
1
i(~
x) 2 Vext (~
x) i(~
x) d~
x
Hi
2
defines the contribution due to the kinetic energy and the electron-nucleus attraction and
(11)
(12)
Jij =
Z Z
i(~
x1 )i(~
x1 )
1
j (~
x2 )j (~
x2 )d~
x1 d~
x2
r12
(13)
Kij =
Z Z
i(~
x1 )j (~
x1 )
1
i(~
x2)j(~
x2 )d~
x1 d~
x2
r12
(14)
The integrals are all real, and Jij Kij 0. The Jij are called Coulomb integrals, the Kij
are called exchange integrals. We have the property Jii = Kii .
The variational freedom in the expression of the energy [Eq. (11)] is in the choice
R of the orbitals.
x)j (~
x)d~
x=
The minimization of the energy functional with the normalization conditions i (~
ij leads to the Hartree-Fock differential equations:
f i = i i , i = 1, 2, ..., N
(15)
These N equations have the appearance of eigenvalue equations, where the Lagrangian multipliers
i are the eigenvalues of the operator f. The Fock operator f is an effective one-electron operator
defined as
M
1 2 X ZA
+ VHF (i)
f = i
2
riA
A
(16)
N
X
j
x1 ) =
Jj (~
j (~
Jj (~
x1 ) K
x1 )
|j (~
x2 )|2
1
d~
x2
r12
(17)
(18)
(~
r) is an observable and can be measured experimentally, e.g. by X-ray diffraction.
(22)
(23)
0i = h0|H
0|0i+h0|H
H
0|0i = E00 +
E0 < h |H|
(~
r) Vext (~
r)
0
Vext
(~
r)
d~
r,
(26)
and H
0, respectively. Similarly, taking
where E0 and E00 are the ground-state energies for H
0 problem,
as a trial function for the H
Z
0
0|i = h|H|i
0 H|i
+ h|H
= E0 + (~
r) Vext (~
r) Vext
(~
r) d~
r,
E00 < h|H
(27)
Adding Eq. (26) and Eq. (27), we would obtain E0 + E00 < E00 + E0 , a contradiction, and so
r) that give the same (~
r) for their ground state.
there cannot be two different Vext (~
(~
r)VN e(~
r)d~
r + FHK [],
FHK [] = T [] + Eee .
(28)
(29)
This functional FHK [] is the holy grail of density functional theory. If it were known we would
have solved the Schrodinger equation exactly! And, since it is an universal functional completely
independent of the system at hand, it applies equally well to the hydrogen atom as to gigantic
molecules such as, say, DNA! FHK [] contains the functional for the kinetic energy T [] and
that for the electron-electron interaction, Eee []. The explicit form of both these functional lies
completely in the dark. However, from the latter we can extract at least the classical part J[],
1
Eee [] =
2
Z Z
(~
r1)(~
r2 )
d~
r1 d~
r2 + Encl = J[] + Encl [].
r12
(30)
Encl is the non-classical contribution to the electron-electron interaction: self-interaction correction, exchange and Coulomb correlation.
The explicit form of the functionals T [] and Encl [] is the major challange of DFT.
(31)
0|H|
0i.
(~
r)Vext d~
r = E[
] E0 [] = h
(32)
Z
r)VN ed~
r
E0 = minN F [] + (~
(34)
where the universal functional F [] contains the contributions of the kinetic energy, the classical
Coulomb interaction and the non-classical portion:
F [] = T [] + J[] + Encl []
(35)
Of these, only J[] is known. The main problem is to find the expressions for T [] and E ncl [].
The Thomas-Fermi model of section 2.2 provides an example of density functional theory. However, its performance is really bad due to the poor approximation of the kinetic energy. To solve
this problem Kohn and Sham proposed in 1965 the approach described below.
They suggested to calculate the exact kinetic energy of a non-interacting reference system with
the same density as the real, interacting one
N
1X
hi|2|ii
TS =
2 i
S (~
r) =
N X
X
i
|i(~
r, s)|2 = (~
r)
(36)
where the i are the orbitals of the non-interacting system. Of course, T S is not equal to the true
kinetic energy of the system. Kohn and Sham accounted for that by introducing the following
separation of the functional F []
F [] = TS [] + J[] + EXC [],
(37)
where EXC , the so-called exchange-correlation energy is defined through Eq. (37) as
EXC [] (T [] TS []) + (Eee [] J[]) .
(38)
The exchange and correlation energy EXC is the functional that contains everything that is
unknown.
Now the question is: how can we uniquely determine the orbitals in our non-interacting reference
system? In other words, how can we define a potential V S such that it provides us with a Slater
determinant which is characterized by the same density as our real system? To solve this problem,
we write down the expression for the energy of the interacting system in terms of the separation
described in Eq. (37)
E[] = TS [] + J[] + EXC [] + EN e []
(39)
2 i
2 i j
r1 2
N Z X
M
X
ZA
|i(~
r1)|2d~
r1 .
(40)
r
1A
i
A
The only term for which no explicit form can be given is E XC . We now apply the variational
principle and ask: what condition must the orbitals { i} fulfill in order to minimize this energy
expression under the usual constraint hi|j i = ij ? The resulting equations are the KohnSham equations:
1
2 +
2
"Z
M
X
(~
r2 )
ZA
+ VXC (~
r1 )
r12
r1A
A
r1 ) =
VS (~
#!
1 2
i = + VS (~
r1) i = i i
2
(41)
M
X ZA
(~
r2 )
d~
r2 + VXC (~
r1 )
r12
r1A
A
(42)
Some comments:
Once we know the various contributions in Eqs. (41-42) we have a grip on the potential V S
which we need to insert into the one-particle equations, which in turn determine the orbitals
and hence the ground state density and the ground state energy employing Eq. (40). Notice
that VS depends on the density, and therefore the Kohn-Sham equations have to be solved
iteratively.
The exchange-correlation potential, VXC is defined as the functional derivative of EXC
with respect to , i.e. VXC = EXC /.
It is very important to realize that if the exact forms of E XC and VXC were known, the
Kohn-Sham strategy would lead to the exact energy!!
Do the Kohn-Sham orbitals mean anything? Strictly speaking, these orbitals have no physical significance, except the highest occupied orbital, max, which equals the negative of the
exact ionization energy.
The local density approximation (LDA) is the basis of all approximate exchange-correlation functionals. At the center of this model is the idea of an uniform electron gas. This is a system in
which electrons move on a positive background charge distribution such that the total ensemble
is neutral.
The central idea of LDA is the assumption that we can write E XC in the following form
Z
LDA
r)) d~
r
[] =
(~
r)XC ((~
EXC
(43)
(44)
The exchange part, X , which represents the exchange energy of an electron in a uniform electron
gas of a particular density, was originally derived by Bloch and Dirac in the late 1920s
X
3
=
4
3(~
r)
1/3
(45)
No such explicit expression is known for the correlation part, C . However, highly accurate numerical quantum Monte-Carlo simulations of the homogeneous electron gas are available (CeperlyAlder, 1980).
Some comments:
The accuracy of the LDA for the exchange energy is typically within 10%, while the
normally much smaller correlation energy is generally overstimated by up to a factor 2. The
two errors typically cancle partially.
Experience has shown that the LDA gives ionization energies of atoms, dissociation energies
of molecules and cohesive energies with a fair accuracy of typically 10-20%. However, the
LDA gives bond lengths of molecules and solids typically with an astonishing accuracy of
2%.
This moderate accuracy that LDA delivers is certainly insufficient for most applications in
chemistry.
LDA can also fail in systems, like heavy fermions, so dominated by electron-electron interaction effects.
The first logical step to go beyond LDA is the use of not only the information about the density
(~
r) at a particular point ~
r, but to supplement the density with information about the gradient
of the charge density, (~
r) in order to account for the non-homogeneity of the true electron
density. Thus, we write the exchang-correlation energy in the following form termed generalized
gradient approximation (GGA),
GEA
[, ] =
EXC
f ( , , , ) d~
r
(46)
Thanks to much thoughtful work, important progress has been made in deriving successful GGAs.
Their construction has made use of sum rules, general scaling properites, etc.
In another approach A. Becke introduced a successful hybrid functional:
hyb
KS
GGA
= EX
+ (1 )EXC
,
EXC
(47)
KS is the exchange calculated with the exact KS wave function, E GGA is an appropiate
where EX
XC
GGA, and is a fitting parameter.
Some comments:
GGAs and hybrid approximations has reduced the LDA errors of atomization energies of
standard set of small molecules by a factor 3-5. This improved accuracy has made DFT a
significant component of quantum chemistry.
All the present functionals are inadequate for situations where the density is not a slowly
varying function. Examples are (a) Wigner crystals; (b) Van der Waals energies between
nonoverlapping subsystems; (c) electronic tails evanescing into the vacuum near the surfaces
of bounded electronic systems. However, this does not preclude that DFT with appropiate
approximations can successfully deal with such problems.
Z
N
M
X |j (~r2 )|2
X ZA
1 2 +
i = i i.
d~
r2 + VXC (~
r1 )
(48)
2
r
r
12
1A
j
A
The term in square brackets defines the Kohn-Sham one-electron operator and Eq. (48) can be
written more compactly as
fKS i = i i.
(49)
Most of the applications in chemistry of the Kohn-Sham density functional theory make use of the
LCAO expansion of the Kohn-Sham orbitals. In this approach we introduce a set of L predefined
basis functions {} and linearly expand the K-S orbitals as
i =
L
X
ci.
(50)
=1
We now insert Eq. (44) into Eq. (43) and obtain in very close analogy to the Hartree-Fock case
r1 )
fKS (~
L
X
=1
ci (~
r1 ) = i
L
X
=1
ci (~
r1 ).
(51)
If we now multiply this equation from the left with an arbitrary basis function and integrate
over space we get L equations
L
X
=1
ci
(~
r1 )fKS (~
r1) (~
r1)d~
r1 = i
L
X
=1
ci
(~
r1) (~
r1 )d~
r1 for 1 i L
(52)
(53)
which are the elements of the Kohn-Sham matrix and the overlap matrix, respectively. Both
matrices are L L dimensional. Eqs.(52) can be rewritten compactly as a matrix equation
=S
C
.
FKS C
(54)
Hence, through the LCAO expansion we have translated the non-linear optimization problem into
a linear one, which can be expressed in the language of standard algebra.
By expanding fKS into its components, the individual elements of the KS matrix become
KS
F
=
!
Z
M
X
1
ZA
(~
r2 )
(~
r1 ) 2
+
d~
r2 + VXC (~
r1) (~
r1 )d~
r1
2
r1A
r12
A
(55)
The first two terms describe the kinetic energy and the electron-nuclear interaction, and they are
usually combined one-electron integrals
!
Z
M
1 2 X ZA
(~
r1 )
(~
r1)d~
r1
(56)
h =
2
r1A
A
For the third term we need the charge density which takes the following form in the LCAO
scheme
(~
r) =
L
X
i
|i(~
r)|2 =
L
L X
N X
X
cici (~
r) (~
r).
(57)
nu
The expansion coefficients are usually collected in the so-called density matrix P with elements
P =
N
X
cici.
(58)
J =
L
L X
X
Z Z
(~
r1) (~
r1 )
1
(~
r2) (~
r2)d~
r1 d~
r2 .
r12
(59)
Up to this point, exactly the same formulae also apply in the Hartree-Fock case. The difference
is only in the exchange-correlation part. In the Kohn-Sham scheme this is represented by the
integral
Z
XC
=
(~
r1)VXC (~
r1) (~
r1 )d~
r1 ,
(60)
V
whereas the Hartree-Fock exchange integral is given by
K =
L
L X
X
Z Z
(~
x1 )(~
x1 )
1
(~
x2 ) (~
x2 )d~
x1 d~
x2 .
r12
(61)
The calculation of the L2/2 one-electron integrals contained in h can be fairly easily computed.
The computational bottle-neck is the calcalution of the L 4 two-electron integrals in the
Coulomb term.
(62)
Here, n corresponds to the principal quantum number, the orbital exponent is termed and
Ylm are the usual spherical harmonics. Unfortunately, many-center integrals are very difficult
to compute with STO basis, and they do not play a major role in quantum chemistry.
Gaussian-type-orbitals (GTO): they are the usual choice in quantum chemistry. They
have the following general form
GT O = N xl y mz n exp [r] .
(63)
A
X
a
da aGT O .
(64)
Molecular structures: DFT gives the bond lengths of a large set of molecules with a precision
of 1-2%. The hybrid functionals have improved the LDA results.
Bond lengths for different bonding situations [
A]:
Bond
H-H
H3C-CH3
HCCH
RHH
RCC
RCH
RCC
RCH
LDA
0.765
1.510
1.101
1.203
1.073
BLYP
0.748
1.542
1.100
1.209
1.068
BP86
0.752
1.535
1.102
1.210
1.072
Experiment
0.741
1.526
1.088
1.203
1.061
Vibrational frequencies: DFT predicts the vibrational frequencies of a broad range of molecules
within 5-10% accuracy.
Vibrational frequencies of a set of 122 molecules: method, rms deviations, proportion outside a
10% error range and listings of problematic cases (taken from Scott and Radom, 1996).
Method
BP86
B3LYP
RMS
41
34
10%
6
6
Atomization energies: the most common way of testing the performance of new functionals is
the comparison with the experimental atomization energies of well-studied sets of small molecules.
These comparisons have established the following hierarchy of functionals:
LDA < GGA < hybrid functionals
The hybrid functionals are progressively approaching the desired accuracy in the atomization
energies, and in many cases they deliver results comparable with highly sophisticated post-HF
methods.
Molecule
CH
CH3
CH4
C2 H 2
C2 H 4
LDA
7
31
44
50
86
BLYP
0
-2
-3
-6
-6
Molecule
F2
O2
N2
CO
CO2
LDA
47
57
32
37
82
BLYP
18
19
6
1
11
Deviations [kcal/mol] between computed atomization energies and experiment (taken from Johnson et al., 1993).
Ionization and affinity energies: the hybrid functionals can determined these energies with an
average error of around 0.2 eV for a large variety of molecules.
Experiment
2.57
1.65
1.70
Metal
Rb
Cs
Experiment
1.72
2.24
Example 2: DFT fails to describe strongly correlated system such as heavy fermions or high
temperature superconductors.
R + H
C + V
=H
L + H
H
C =
H
i i
di di
di molecular orbitals
=
V
ij
vij (di
cj + h.c.).
vij : hopping elements between the lead orbitals and the MOs of the central cluster (L owdin
transformation).
self-consistent determination of
the electrostatic profile
[F]
d[iG<()/2]
HF / DFT
HF / DFT
NEGF
(a)
F, N
(b)
F, 1 ,
2 , 1, 2
t
t [f ( eV /2) f ( + eV /2)]
d Tr
Transmission matrix:
1/2
L
rC (, V )
1/2
t(, V ) = 2
( eV /2) G
R ( + eV /2)
= self-energy)
(
L,R () =
vCL,R gL,R()
vL,RC
2e2 X
Ti
G=
h i=1
I CHANNEL > = Ca
+ Cb
+ ...
b
Ultimately, this information concerning the channels can eventually be measured using superconducting electrodes or other means.
polyimide
sacrificial layer
Aluminum film
pushing rod
flexible substrate
counter supports
Main observations
The H2 bridge has a nearly perfect conductance of one quantum unit, carried by a single
channel.
The presence of the molecule was identified by the analysis of its vibration modes.
The number of channels was estimated from the analysis of the conductance fluctuations.
T()
Simple model:
0.6
0.4
0.2
0
DOS()
= 1.0tH
bonding state at 0 + t:
anti-bonding state at 0 t:
Approximations:
flat DOS: () =
no charge transfer
= 0.4tH
1.5
= 0.2tH
= 0.05tH
1
0.5
0
-2
-1
Result:
( 0)/|tH|
0.8
T()
0.4
0.2
0
5d
6p
6s
0.8
0.6
DOS()
Pt Bulk DOS
0.6
t = 0.10tH
t = 0.15tH
0.1
0.05
0.4
0.2
0
-10 -5
5 10 15 20
(eV)
-10 -5
5 10 15 20
(eV)
Hollow position
0.06
0.04
0.02
0
1.2
Transmission
Transmission
LDOS (1/eV)
bonding
Ttotal
T1
T2
3
2
Ttotal
T1
T2
T3
T4
T5
T6
T7
0.8
0.6
0
3
0.4
(eV)
0.2
0
6 5 4 3 2 1
(eV)
Conclusions.
The density functional theory (DFT) is presently the most successfull (and also the most
promising) approach to compute the electronic structure of matter.
Its applicability ranges from atoms, molecules and solids to nuclei and quantum and
classical fluids.
In its original formulation, the density functional theory provides the ground state properties of a system, and the electron density plays a key role.
An example: chemistry. DFT predicts a great variety of molecular properties: molecular
structures, vibrational frequencies, atomization energies, ionization energies, electric and
magnetic properties, reaction paths, etc.
The original density functional theoy has been generalized to deal with many different
situations: spin polarized systems, multicomponent systems such as nuclei and electron
hole droplets, free energy at finite temperatures, superconductors with electronic pairing
mechanisms, relativistic electrons, time-dependent phenomena and excited states, bosons,
molecular dynamics, etc.