Away from generalized gradient approximation: Orbital-dependent exchange-

correlation functionals
E. J. Baerends and O. V. Gritsenko

Citation: The Journal of Chemical Physics 123, 062202 (2005); doi: 10.1063/1.1904566
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 THE JOURNAL OF CHEMICAL PHYSICS 123, 062202 共2005兲

Away from generalized gradient approximation: Orbital-dependent

exchange-correlation functionals
E. J. Baerends and O. V. Gritsenko
Section Theoretical Chemistry, Vrije Universiteit, De Boelelaan 1083, 1081 HV Amsterdam,
The Netherlands
共Received 19 August 2004; accepted 17 March 2005; published online 17 August 2005兲

The local-density approximation of density functional theory 共DFT兲 is remarkably accurate, for
instance, for geometries and frequencies, and the generalized gradient approximations have also
made bond energies quite reliable. Sometimes, however, one meets with failure in individual cases.
One of the possible routes towards better functionals would be the incorporation of orbital
dependence 共which is an implicit density dependency兲 in the functionals. We discuss this approach
both for energies and for response properties. One possibility is the use of the Hartree–Fock-type
exchange energy expression as orbital-dependent functional. We will argue that in spite of the
increasing popularity of this approach, it does not offer any advantage over Hartree–Fock for
energies. We will advocate not to apply the separation of exchange and correlation, which is so
ingrained in quantum chemistry, but to model both simultaneously. For response properties the
energies and shapes of the virtual orbitals are crucial. We will discuss the benefits that Kohn–Sham
potentials can offer which are derived from either an orbital-dependent energy functional, including
the exact-exchange functional, or which can be obtained directly as orbital-dependent functional.
We highlight the similarity of the Hartree–Fock and Kohn–Sham occupied orbitals and orbital
energies, and the essentially different meanings the virtual orbitals and orbital energies have in these
two models. We will show that these differences are beneficial for DFT in the case of localized
excitations 共in a small molecule or in a fragment兲, but are detrimental for charge-transfer excitations.
Again, orbital dependency, in this case in the exchange-correlation kernel, offers a solution. © 2005
American Institute of Physics. 关DOI: 10.1063/1.1904566兴

I. INTRODUCTION crude and simplistic modeling of the exchange-correlation

The success of density functional theory1–4 共DFT兲 in the
description of molecules has been a source of surprise for the
quantum chemical community. The theory in its earliest
manifestation in molecular quantum theory, the exchange-
only local-density approximation, or X␣ model, looked like
a poor cousin of Hartree–Fock. So when it proved to do
better than Hartree–Fock in many cases, this did not sway
public opinion: one cannot 共and should not兲 prove by ex-
ample. We will in this paper try to remove the aura of mys-
tery: it is not a miracle that DFT, even with rather crude
approximations such as the local-density approximation
共LDA兲 or generalized gradient approximations 共GGAs兲, is so
often better than Hartree–Fock. The simple truth is not that
LDA/GGA is particularly good, but that Hartree–Fock is
rather poor. The Hartree–Fock mean-field theory is actually
remarkably good for atoms, where the central potential is a
dominant feature that determines crucial properties such as
the shell structure, and it is a meaningful approximation for
extended systems such as an electron gas. However, Hartree–
Fock simply is such a bad model to describe the electron-pair
bond, which is the crucial thing to do right for a quantum
chemical theory, that it is not a good starting point for the
theoretical description of molecules, and it is not so difficult
to do better. We will discuss the criticism against the
Hartree–Fock model for electron-pair bonds in Sec. III.
Density functional theory has provided a seemingly
term in the total energy, using the electron gas as starting
point 共in the LDA兲 or using refinements employing gradients
of the density 共GGA兲. As we will see, one can understand
that these simple modelings, irrespective from the way they
have been constructed, have been successful: they avoided
the essential error that the Hartree–Fock model is making.
This error is clear when one considers the statistical two-
electron distribution, which is usually cast in terms of the
exchange-correlation hole: the decrease in probability to find
other electrons in the neigborhood of a reference electron,
compared to the 共unconditional兲 one-electron probability dis-
tribution. The essential error of Hartree–Fock arises from the
fact that in the Hartree–Fock 共HF兲 model the exchange-
correlation hole in a two-electron bond is not centered
around the reference electron, but is too delocalized, having
considerable amplitude on both atoms involved in the bond.
This is a consequence of the fact that the hole is not gener-
ated by the physics of the Coulomb interaction, but by the
self-interaction correction and the antisymmetry require-
ment. The LDA and GGA models incorporate, simply by
using an electron-centered hole, an important part of the ef-
fect of the interelectron Coulomb repulsion.
It has proved very difficult to improve on the LDA and
GGA models. Recently the refinement of introducing orbital
dependence, not just density and gradient dependence, into
the functionals has received much attention. This is indeed a

0021-9606/2005/123共6兲/062202/17/$22.50 123, 062202-1 © 2005 American Institute of Physics

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 062202-2 E. J. Baerends and O. V. Gritsenko J. Chem. Phys. 123, 062202 共2005兲

possible way forward in the endeavour to improve function- H

als and put them on a more transparent physical basis. We ␳共r1兲 = 2 兺 兩␾i共r1兲兩2 . 共2.2兲
will in Sec. II briefly mention the approaches that have been i

taken to solve the Kohn–Sham equations when orbital de-
pendence is introduced in the functionals. Then, in Sec. III,
we discuss the most generally used orbital-dependent func-
tional, the exact-exchange 共EXX兲 functional. This functional
uses a Hartree–Fock-type energy expression for the ex-
change energy. The only difference is that Kohn–Sham orbit-
als instead of HF orbitals are used. Although this orbital-
dependent functional is receiving much attention, in
particular, since it automatically incorporates the self-
interaction correction, the lack of which is believed to cause
problems for the LDA and GGA functionals, we will argue
that this functional cannot be expected to be better than the
Hartree–Fock model itself, and therefore to be actually
poorer than the LDA and GGA functionals. In Sec. IV we
will discuss possible ways to incorporate both exchange and
correlation in orbital-dependent functionals. We will demon-
We use closed-shell systems throughout, with H = N / 2 dou-
bly occupied orbitals. Both the total density and the indi-
vidual orbitals are used in DFT as the arguments in approxi-
mations to the unknown exact functional of the xc energy
Exc关␳兴. While in the early LDA Exc was modeled as a func-
tion of only the local density ␳共r1兲, Exc
LDA
关␳兴 = Exc
LDA
关␳共r1兲兴,6
the GGA employs, in addition, a “semilocal” characteristic
of the density, its gradient ⵱␳共r1兲, Exc GGA
关␳兴
= Exc 关␳共r1兲 , ⵱␳共r1兲兴,
GGA 7–11
and next-generation functionals
include explicit dependence on individual KS orbitals ␾i.
Recently, the orbital-dependent exact-exchange 共EXX兲
group of methods has received much attention in the litera-
ture. One may approximate the xc functional by just the
exchange-only form that appears in the well-known Hartree–
Fock 共HF兲 energy expression

冕
H H
strate that it is possible in this way to actually avoid the main ␾*i 共r1兲␾ j共r1兲␾i共r2兲␾*j 共r2兲
deficiency of the Hartree–Fock and EXX models, and obtain Ex关兵␾i其兴 = − 兺 兺 dr1dr2 .
i j r12
a proper description of electron correlation even in weak
electron-pair bonds. In Sec. V and VI we will discuss the 共2.3兲
rather more subtle role that orbital-dependent functionals
Since the Kohn–Sham potential is a local multiplicative po-
play in the calculation of response properties. In that case
tential vs共r兲, the optimization problem to obtain the orbitals
already the EXX functional offers important advantages, be-
that minimize the total energy with the exchange part 共2.3兲 is
cause its functional derivative, the effective potential, is con-
slightly different from Hartree–Fock. The additional con-
siderably improved over the LDA/GGA ones. It yields im-
straint of locality of the potential will result in orbitals that
proved orbital energies and orbital shapes for the virtual
may be slightly different from the HF ones, and therefore the
orbitals, hence improved excitation energies, and it is able,
EXX energy 共the expectation value of the determinant with
through the orbital-dependent response part of its potential,
EXX orbitals兲 will be slightly higher than the HF energy 共see
to generate the counteracting electric field that is required to
Sec. III for examples兲. The KS potential, with its exchange
obtain realistic 共hyper兲polarizabilities compared to the huge
part vx can be obtained in this case with the self-consistent
overestimation by LDA and GGA. Finally 共Sec. VI兲, the dra-
solution of the integro-differential equations of the so-called
matic failure of the LDA and GGA approximations for
optimized effective potential 共OEP兲 method.12 Talman and
charge-transfer excitations can be solved by the introduction
Shadwick12 derived these equations by considering explicitly
of an orbital-dependent exchange-correlation kernel.
the optimization problem of finding the local potential that
gives the orbitals yielding minimum total energy of the
single determinantal wave function, but they may also be
straightforwardly derived by applying the chain rule 共taking
II. ORBITAL-DEPENDENT EXCHANGE-CORRELATION the general case of an orbital-dependent xc functional兲
FUNCTIONALS IN DFT ␦Exc关兵␸i关␳兴其兴
vxc共r兲 =
␦␳共r兲
With the advent of the orbital-dependent exchange-
correlation 共xc兲 functionals modern DFT comes to explore
the full potentiality of the Kohn–Sham 共KS兲 theory.5 How- =兺
i
冕 ␦Exc ␦␸i共r1兲␦vs共r2兲
dr dr + c.c.
␦␸i共r1兲 ␦vs共r2兲␦␳共r兲 1 2
ever, orbital-dependent xc functionals are technically much
harder to treat than the density and gradient dependent func- ␦Exc
=−兺 G 共r ,r 兲␸ 共r 兲␹−1共r ,r兲dr1dr2
tionals. The KS orbitals ␾i are obtained from the one- i ␦␸i共r1兲 i 1 2 i 2 s 2
electron equations 共throughout the paper we consider closed-
shell systems兲 + c.c., 共2.4兲

再 冎
where we have used the orbital Green’s function Gi共r1 , r2兲
1 = 兺 j⫽i␸ j共r1兲␸ j共r2兲* / 共␧ j − ␧i兲 which describes the response of
− ⵜ2 + vs共r1兲 ␾i共r1兲 = ␧i␾i共r1兲, 共2.1兲
2 an orbital to a change of potential ␦vs: ␦␸i共r1兲
= −兰Gi共r1 , r2兲␸i共r2兲␦vs共r2兲dr2. Gi共r1 , r2兲 follows directly
with the local, state-independent potential vs, and the subset from first-order perturbation theory. The constraint that the
of occupied orbitals 兵␾ j其 determines the electron density ␳ of KS orbitals be solutions in a local KS potential vs共r兲 is ex-
the system plicitly applied in the optimized potential method, but is here
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 062202-3 Orbital-dependent exchange-correlation functionals
introduced by the use of the chain rule in the functional
derivation in Eq. 共2.4兲. Multiplying by the density response
function ␹s共r , r3兲 = ␦␳共r兲 / ␦vs共r3兲 = −兺i=1
N/2
f i␸i共r兲*Gi共r , r3兲
⫻␸i共r3兲 + c.c. and integrating over r we obtain an integral
equation for vxc:
冕 vCEDA 共r1兲 = vhole
vxc共r兲␹s共r,r3兲dr
冕
=兺 vi共r1兲␸*i 共r1兲Gi共r1,r3兲␸i共r3兲dr1 + c.c., 共2.5兲
i CEDA
with vi共r1兲 = 关1 / ␸i共r1兲*兴␦Exc / ␦␸i共r1兲. Several methods of so-
lution of Eq. 共2.5兲 have been explored. Talman and Shadwick
used inversion of ␹s on a numerical grid in one-dimensional
共atomic兲 calculations. In principle, these equations can be
solved by using basis set expansions, as pointed out by
Görling.13–15 Validation and application of this approach has
been done by Bartlett and co-workers.16,17 The function ␹s
can be inverted on a subspace of its eigenfunctions, such that
the eigenfunctions with zero 共or near zero for practical pur-
poses兲 eigenvalues are excluded. To obtain vx of high quality,
a large basis is required, in particular, the KS basis should
include all occupied and a large number of unoccupied or-
bitals ␾i. The numerical stability of this inversion becomes a
problem, especially for molecular applications, see Ref. 17
for a detailed discussion. Recently, in Refs. 18 and 19, vx has
been constructed by using the Fermi–Amaldi potential,
which is a simple functional of ␳共r1兲 with the correct long-
range asymptotics, vx → −1 / 兩r1兩, 兩r1兩 → ⬁, as a constant part
of the potential 共using, e.g., the LDA ␳兲, and expanding the
unknown remainder in a finite basis set for which the coef-
ficients are to be determined. Since the Fermi–Amaldi part
already takes care of the asymptotic part of the potential, the
remainder can be expanded in Gaussian basis functions with
finite extent. The expansion coefficients are obtained in an
iterative optimization procedure. The EXX method of
Görling,20 which also uses basis set expansion, does not re-
quire the inversion of ␹s. Instead, vx is obtained as the po-
tential of the exchange charge density ␳x,
vx共r1兲 = 冕 ␳x共r2兲
r12
dr2 , 共2.6兲
from the solution of the corresponding Poisson’s equation
with a basis set expansion of ␳x.
Good-quality approximations to EXX have been ob-
tained with the Green’s function Gi being broken up in a
local 共␦-function兲 part and a remainder that is approximated.
An example is the admittedly crude Sharp and Horton ap-
proximation for Gi,21 which does not preserve the proper
orbital structure of the response function ␹s. Surprisingly,
this approximation yields the good-quality exchange poten-
tial vKLI
x of the Krieger, Li, and Iafrate 共KLI兲 method,22,23
which is expressed in terms of only the occupied KS orbitals.
Recently, a more physically reasonable common energy de-
nominator approximation 共CEDA兲 has been applied to the
Green’s function Gi.24 According to CEDA, the orbital en-
ergy differences for the occupied-unoccupied pairs in Gi are
approximated with the mean energy ⌬␧ ˜ , ␧c − ␧i ⬇ ⌬␧
˜ , while
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J. Chem. Phys. 123, 062202 共2005兲
the true differences 共␧ j − ␧i兲 for the occupied-occupied pairs
are retained. The exchange potential vCEDA x obtained with
this approximation is also expressed in terms of only the
occupied KS orbitals.24,25 It is partitioned naturally into
physically meaningful components
x 共r1兲 + vresp 共r1兲, 共2.7兲
CEDA
x
the Slater potential vhole
x of the Fermi 共exchange兲 hole 共see
CEDA
below兲 and the response potential vresp ,
H H
␾*i 共r1兲␾ j共r1兲
vresp 共r1兲 = 兺 兺 sCEDA , 共2.8兲
i
ij
j ␳共r1兲
which contains the characteristic orbital-shell “step” struc-
ture with “diagonal” contributions from the orbital densities
兩␾i兩2 共a similar structure is also present in the KLI potential兲
as well as with additional “off-diagonal” contributions from
the occupied-occupied orbital products ␾i␾*j . The orbital step
structure follows from the fact that in the region, where a
particular orbital density 兩␾i兩2 brings a dominant contribution
to the total density ␳, the potential 共2.8兲 is close to the cor-
responding constant 共“step height”兲 sCEDA ii . Note, that the
same potential vCEDA
x has been obtained by Della Sala and
Görling26 within the so-called localized Hartree–Fock 共LHF兲
approximation, in which the assumption is made that the
occupied KS orbitals are only unitary transforms of the oc-
cupied HF orbitals, i.e., the HF and KS determinants are
identical. For closed-shell systems, the derivation based on
this LHF assumption leads to exactly the vCEDA x of Eq. 共2.7兲.
For open-shell systems the LHF assumption cannot be used,
and in that case a variant of the CEDA approximation has
been proposed in Ref. 27. Krieger et al. have already derived
a method28 to improve on the KLI approximation and de-
velop the full EXX solution. A numerical procedure for this
further refinement of the KLI/CEDA potential has been de-
veloped by Kümmel and Perdew,29 which also employs only
occupied KS orbitals. It updates vKLI/CEDA
x with a correction
built from the products of the occupied orbitals ␾i and the
first-order perturbation theory corrections to ␾i for the per-
turbing potential 共vix − vx兲, where vix is the HF exchange po-
tential for ␾i.
We conclude that several methods are available to obtain
solutions of the optimized potential method for orbital-
dependent functionals. We will not go into further technical
details.
III. A CRITIQUE OF THE EXCHANGE-ONLY
APPROACH „EXX… IN DFT
Although it would be technically possible to deal with
all kinds of orbital-dependent functionals, one may observe
in the literature primarily application of the exact-exchange
functional of Eq. 共2.3兲. 共Notable exceptions are the work by
Bartlett and co-workers,30,31 who use many-body perturba-
tion theory and coupled-cluster methods to obtain more ad-
vanced functionals, and our own work,32 to be discussed in
the following section, which uses functionals inspired by
density matrix functional theory.兲 Two advantages of the
EXX functional are often mentioned: 共a兲 the self-interaction
correction is incorporated in this functional: 共b兲 it is natural
 062202-4 E. J. Baerends and O. V. Gritsenko
FIG. 1. Fermi hole, Coulomb hole, and total hole in the hydrogen molecule
at R = 1.4 共equilibrium distance兲 and 5.0 bohrs. The reference electron is
always placed at 0.3 bohr to the left of the right H atom.
to break up the total problem of electron-electron interaction
in the large 共due to self-interaction correction兲 exchange part
and the small correlation part. The hope is of course that it
will be simpler to find accurate density functionals for the
small correlation energy. We wish to argue that, on the con-
trary, starting with EXX is actually making life much more
difficult. It undermines the very basis of the success of DFT,
which has been the breaking away from the quantum chem-
istry paradigm of dividing up the full electron-electron inter-
action problem into two steps: first Hartree–Fock 共or
exchange-only兲 and next the remaining correlation problem.
That this is indeed the case is masked by the DFT terminol-
ogy which still uses the names “exchange” 共e.g., Becke ex-
change, Perdew exchange兲 and “correlation” 关e.g., Perdew–
Wang correlation, Lee–Yang–Parr 共LYP兲 correlation兴. Let us,
however, consider the simple electron-pair bond. One should
be aware that, while correlation is indeed much smaller than
exchange in for instance 共heavy兲 atoms, this is not true in the
electron-pair bond. This can be illustrated with the very
simple picture given in Fig. 1. Figure 1共a兲 displays the
Fermi, Coulomb, and the total xc holes for the prototype
electron-pair bond, the H2 molecule, at the equilibrium H–H
distance R共H–H兲 = 1.4 bohrs,33,34 while in Fig. 1共b兲 the holes
are plotted for the stretched H2 at R共H–H兲 = 5.0 bohrs. In the
H2 case HF and EXX-KS are identical, since the HF operator
in this case is just the local potential that is obtained by
correcting the full Hartree potential of the total density
␳共r2兲 = 2兩␴g共r2兲兩2, VH共r1兲 = 兰␳共r2兲 / r12dr2, with the self-
interaction correction from the potential at r1 due to the
Fermi hole, containing −1 electron, ␳hole x 共r2兩r1兲 = −兩␴g共r2兲兩 .
2 ence electron is located. This will provide the right potential,
In this case the Fermi hole is completely independent of the
position r1 of the reference electron, and is delocalized over
the two centers between which the bond exists. As becomes
particularly apparent at long bond distance, the resulting po-
tential in which the HF/EXX electron moves is very defi-
cient. When the reference position is chosen, as indicated in
Fig. 1, close to the nucleus at the right, the other electron is
most likely not close to the same nucleus, but will with great
probability be somewhere around the left nucleus. In other
words, the hole should remove density integrating to −1 elec-
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TABLE I. Correlation contributions 共in eV兲 to the various energy compo-
nents of the H2 molecule at equilibrium distance 共2.4 bohrs兲 and at elon-
gated distances.
corr corr corr
Etotal Tcorr Vel-nuc Wel-el
H2共R = Re兲 −1.1 eV +1.3 −0.5 −1.9
H2共R = 5.0 bohrs兲 −3.9 +8.9 −8.5 −4.3
H2共R = 10.0 bohrs兲 −6.3 +7.9 −8.6 −5.6
tron from around the right nucleus and nothing around the
left nucleus. The reference electron should see the right
nucleus unscreened by density of the other electron, which
will reside around the left nucleus. It can then build a den-
sity, which is like a H atom density, with correct behavior
around the nucleus and with the correct exponential decay.
This is of course in agreement with reality, where dissocia-
tion will be into two H atoms. The total hole has indeed
precisely this required shape. The Fermi hole, however, re-
moves half of an electron from around the left and from
around the right nucleus each, so it leaves half of an electron
around the right nucleus, which will partly screen that
nucleus. The wave function for the HF/EXX electron will
therefore become too diffuse. This is very clearly illustrated
with the breakdown of the correlation contribution to the
total energy in contributions to the kinetic energy, the
electron-nuclear attraction energy, and the electron-electron
interaction energy in Table I. A too diffuse orbital, with too
low gradients, will lead to a too low kinetic energy, and
indeed the correlation correction to the kinetic energy, Tcorr
= T − TEXX, is strongly positive. Also, the correlation correc-
tion to the density will make it more compact around the
nucleus, hence will make the electron-nuclear energy more
negative. We note that the correlation corrections in the one-
electron energies T and Ven are at long distance individually
corr
larger than the two-electron correlation correction Wel-el .
They are large compared to the total bond energy 共
−4.7 eV兲 already at Re, and become very large compared to
the much smaller bond energies at longer bond distance. This
substantiates the well-known fact that the Hartree–Fock
共EXX兲 model is a poor zero-order approximation for the
electron-pair bond. It is also extremely size inconsistent, in
the sense that when we introduce a second H atom in the
universe, remote from a given H atom, the HF/EXX model
totally fails to deliver the sum of the energies of two H
atoms. It is interesting to note that when we add the Cou-
lomb hole 共or correlation hole兲 to the Fermi hole, we obtain
a total hole that is localized at the nucleus where the refer-
and therefore the right density and kinetic energy. The local-
ized hole does not require any knowledge of where the other
H atom is located, it is the unphysical breaking up of this
total hole into a delocalized exchange part and an equally
delocalized Coulomb part that complicates the electron-
electron interaction treatment and requires knowledge of the
position of the second nucleus in order to build accurate
holes. Actually, this example illustrates that the division in
exchange and correlation holes creates one of the largest
problems of DFT.35 The problem basically is that the total
 062202-5 Orbital-dependent exchange-correlation functionals J. Chem. Phys. 123, 062202 共2005兲

TABLE II. Components of the LDA, BLYP, CEDA, HF, KS, and CI energies 共in atomic units兲 for CO at the
equilibrium bond distance R共C–O兲 = 2.13 bohrs. The difference of the exact 共CI兲 quantity with respect to the
model quantity is also given. For the exchange energy WX the KS value is the benchmark. The LDA and BLYP
WX values have been calculated from the corresponding exchange functionals. Eel is the sum T + Ven + WH
+ WX; the difference of the exact 共CI兲 energy with respect to Eel is by definition the correlation energy. The Ec
entries in the last row under LDA and BLYP are calculated with the corresponding DFT functionals and can be
compared with the required Ec numbers in the row above.

Energy LDA BLYP EXX 共CEDA兲 HF KS CI

T / Ts 111.951 113.181 112.395 112.641 112.881 113.185

⌬CI +1.234 +0.004 +0.790 +0.544 +0.304

Ven −310.170 −311.520 −310.651 −310.879 −311.256 −311.256

⌬CI −1.086 +0.264 −0.605 −0.377 0.00

WH 76.204 76.391 76.251 76.262 76.399 76.399

⌬CI +0.195 +0.008 +0.148 +0.137 0.00

WX −12.064 −13.475 −13.296 −13.331 −13.319 共−14.089兲

⌬KS −1.255 +0.156 −0.023 +0.012 共WXC兲

Eel = T + Ven + WH + WX −134.079 −135.423 −135.301 −135.307 −135.295

⌬CI = Ec = Etotal
CI
− Eel −1.682 −0.338 −0.460 −0.454 −0.466

Ec 共DFT兲 −0.950 −0.486

Etotal 135.029 −135.909 −135.761
⌬CI −0.732 +0.148

density ␳ around each H nucleus is identical at large H–H
distances to that in a free H atom. However, the exchange
and correlation energies in the stretched H2 are very different
from those in two isolated H atoms. In particular, the corre-
lation energy is zero in individual H atoms, in contrast with
the strong left-right nondynamical correlation in the dissoci-
ating H2 molecule. It is virtually impossible to devise func-
tionals that use only local information 共local density and de-
rivatives of the density兲 and still recognize the position of the
other H atom and build correctly the individual exchange and
correlation holes, the shape of which is determined by the
positions of the nuclei.
The LDA and GGA total holes are localized around the
reference electron, which is a definite advantage. Figure 1 in
Ref. 36 shows plots of the LDA and GGA exchange holes in
H2 around reference positions some 0.18 Å to the left and to
the right of the left nucleus. These pictures illustrate the per-
fect spherical symmetry of the LDA hole around the refer-
ence position, and for the somewhat more realistic GGA hole
the displacement of the maximum depth of the hole in the
direction opposite the density gradient, i.e., towards the
nearby nucleus. In the dissociating H2 molecule, this prop-
erty of LDA and GGA to localize the exchange hole around
the reference electron makes that the hole more closely ap-
proximates the total hole rather than the exchange hole.
However, the LDA and GGA exchange holes appear to be
too shallow in the dissociating H2 molecule to describe with
good numerical accuracy the strong left-right correlation.32
LDA produces a very large error 共ca. 70 kcal/ mol!兲 at large
R共H–H兲, although not as large as the HF method. GGA re-
duces the error in the dissociation limit compared to LDA,
but still yields a large error in this case 共ca. 45 kcal/ mol, see
also Refs. 32 and 35 and the following section兲.
In bonds between many-electron atoms the HF and EXX
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treatments will start to be somewhat different. There may be
several pairs of nonbonding electrons in core shells and lone
pairs, which account for almost all of the energies of various
kinds, such as kinetic energy, electron-nuclear potential en-
ergy, etc. The exchange-only approximation is not so poor
for these orbitals, so this approximation may appear better
justified. However, for the electron-pair bonds the exchange-
only approximation is as bad as in the prototype case of the
H2 molecule, and therefore the errors are large compared to
the bond energy. We illustrate these statements, and make a
comparison between HF and KS-EXX for the CO molecule
共Tables II and III兲. These tables compare various components
of the HF and EXX energies of the prototype molecule CO,
calculated at the equilibrium bond length R共C–O兲
= 2.13 bohrs 共Table II兲 and at elongated bond length R
= 2.8 bohrs 共Table III兲, with the energy components of an
accurate KS solution for CO. In the following we just use the
acronym “EXX” to denote the Kohn–Sham exchange-only
results, which have been obtained with the CEDA approxi-
mation, since they are very close approximations to the full
EXX data. The accurate KS solution has been obtained from
the correlated density ␳ of the multireference configuration
interaction 共MRCI兲 method with the iterative local updating
procedure of van Leeuwen and Baerends 共LB兲.37 This
method is based directly on the Hohenberg–Kohn 共HK兲 theo-
rem. The HK theorem compares the Hamiltonians Ĥ and Ĥ⬘,
which are characterized by different external potentials v and
v⬘, and have different ground-state wave functions ⌿ and
⌿⬘. If one adds the two inequalities, following from the
variation theorem,
 062202-6 E. J. Baerends and O. V. Gritsenko J. Chem. Phys. 123, 062202 共2005兲

TABLE III. Components of the LDA, BLYP, CEDA, HF, KS, and CI energies 共in atomic units兲 for CO at the
stretched bond distance R共C–O兲 = 2.8 bohrs. The difference of the exact 共CI兲 quantity with respect to the model
quantity is also given. For the exchange energy WX the KS value is the benchmark. The LDA and BLYP WX
values have been calculated from the corresponding exchange functionals. Eel is the sum T + Ven + WH + WX; the
difference of the exact 共CI兲 energy with respect to Eel is by definition the correlation energy. The Ec entries in
the last row under LDA and BLYP are calculated with the corresponding DFT functionals and can be compared
with the required Ec numbers in the row above.

Energy LDA BLYP EXX 共CEDA兲 HF KS CI

T / Ts 111.023 112.257 111.437 111.662 111.977 112.270

⌬CI +1.247 +0.013 +0.833 +0.608 +0.293

Ven −298.862 −300.239 −299.216 −299.430 −299.777 −299.777

⌬CI −0.915 +0.462 −0.561 −0.347 0.00

WH 71.038 71.241 71.071 71.045 71.073 71.073

⌬CI +0.035 −0.168 +0.002 +0.028 0.00

WX −11.752 −13.168 −12.973 −13.027 −12.980 共−13.822兲

⌬KS −1.228 +0.188 −0.007 +0.047 共WXC兲

Eel = T + Ven + WH + WX −128.553 −129.909 −129.738 −129.750 −129.707

⌬CI = Ec = Etotal
CI
− Eel −1.703 −0.347 −0.518 −0.506 −0.549

Ec 共DFT兲 −0.935 −0.472

Etotal −129.489 −130.381 −130.256

⌬CI −0.767 +0.125

具⌿兩Ĥ⬘兩⌿典 ⬎ 具⌿⬘兩Ĥ⬘兩⌿⬘典 series of atoms and molecules.37–43 Since the KS orbitals are
obtained in the iterative process, the KS kinetic energy Ts
⇒T+W+ 冕⬘v ␳dr ⬎ T⬘ + W⬘ + 冕 ⬘⬘v ␳ dr
and the KS exchange energy Ex become available. The tables
also contain the corresponding energy contributions for the
LDA and GGA-BLYP 共Refs. 7 and 10兲 energies. All calcu-
and lations have been performed in the correlation-consistent po-
具⌿⬘兩Ĥ兩⌿⬘典 ⬎ 具⌿兩Ĥ兩⌿典 larized core-valence quadruple zeta added 共cc-pCVQZ兲 basis
set44 using the ATMOL package45 and its DFT extension.46
⇒ T⬘ + W⬘ + 冕 v␳⬘dr ⬎ T + W + 冕 v␳dr,
Of course, since the KS density is identical to the CI
one, the electron-nuclear attraction energy Ven and the Har-
tree energy of the electrostatic electron repulsion WH are
one obtains “exact” in the KS case. It is enlightening to see how much

冕⬘ 冕 冕 ⬘⬘ 冕
HF
the electron-nuclear HF energy Ven differs from the exact
v ␳dr + v␳⬘dr ⬎ v ␳ dr + v␳dr one. Although in this case the total HF number is percentage-
wise not so bad, due to the large contributions of nonbonding
or 共particularly core兲 electrons, the absolute error of −0.377 at

冕
⌬v⌬␳dr ⬍ 0,
where ⌬␳ = ␳⬘ − ␳ is the difference between the densities be-
longing to the potentials v and v⬘ = v + ⌬v. The HK theorem
concludes that if ⌬v is nonzero, also ⌬␳ must be nonzero,
i.e., a change in the potential v must induce a change in the
density ␳. The relation 兰⌬v⌬␳dr ⬍ 0, however, not only tells
us that there is a unique mapping between density and po-
tential, but also that, if a target density ␳⬘ differs in a small
region from a trial density ␳ obtained with a trial potential v,
one may approach the target density more closely using an
update ⌬v on the potential v which is negative if ⌬␳ is
positive and vice versa. So using a ⌬v proportional to −⌬␳
will help to approximate v⬘. This affords an iterative proce-
dure to determine the potential that approaches the target
density ␳⬘ arbitrarily closely, which has been applied to a
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Re 共−0.347 hartree at R = 2.8 bohrs兲 is of the same order as
the total bond energy of ca. 0.40 hartree. The errors are also
given in the table, always as the difference of the benchmark
CI value with the value for a particular case; in the Hartree–
Fock case: ⌬CI共Ven兲 = Ven CI HF
− Ven HF
. The fact that the HF Ven is
not negative enough shows that the HF orbitals and density
are too diffuse. This is also reflected in the HF kinetic energy
term, which is less positive by 0.544 hartree 共0.608 hartree at
R = 2.8 bohrs兲 compared to the CI kinetic energy. 共In the re-
mainder of this parargaph numbers in parentheses will refer
to the elongated bond distance, Table III.兲 The electron-
electron repulsion energy WH is, as expected for a diffuse
HF
density, too low. Especially in the case of Ven and THF, the
correlation errors are not much smaller than the overall cor-
relation energy of −0.454 hartree 共−0.506 hartree兲. One
would expect these errors to persist in the EXX determinan-
tal wave function. As a matter of fact, they are still consid-
 062202-7 Orbital-dependent exchange-correlation functionals
erably larger in the EXX case: −0.605 hartree
共−0.561 hartree兲 for EXX
Ven and +0.790 hartree
共+0.833 hartree兲 for T . So the added constraint that the
EXX
potential be local makes the orbitals and density even more
diffuse than they already are at the HF level. It is interesting
to observe that these large effects in the individual energy
terms are not reflected in the variationally determined total
energy: the energy of the EXX determinant is only 0.006
hartree 共0.012 hartree兲 higher than the HF energy. This is to
be compared to the large total electronic energies 共sum T
+ Ven + WH + WX兲 EEXX = −135.301 hartree 共−129.738 hartree兲
and EHF = −135.307 hartree 共−129.750 hartree兲, and the cor-
relation energies of EEXX c = −0.460 hartree 共−0.518 hartree兲
and EHFc = −0.454 hartree 共−0.506 hartree兲.
Comparing next to the determinant with the KS orbitals,
we note that these orbitals and hence also the density are
contracted by the correlation effects embodied in the KS
model, so the KS energies Ts , Ven, and WH are all substan-
tially larger 共in absolute magnitude兲 than the corresponding
HF and EXX energies. The terms Ven and WH are actually
exact, but Ts is not yet equal to the exact T, it is still a sizable
0.304 hartree 共0.293 hartree兲 too low, about half of the error
of the HF case. Note, that in DFT the energy EKS of the KS
determinant is taken as the reference for the correlation en-
CI
ergy, Ec = Etotal − EKS. Since the lowest energy of the single
determinant is the HF energy EHF, the absolute value of the
DFT correlation energy Ec must be larger than the conven-
tional correlation energy EHF CI HF
c = Etotal − E , though the actual
difference 共0.012 hartree for the equilibrium CO distance,
0.043 hartree for R = 2.8 bohrs兲 is much smaller than the dif-
ferences between HF and KS in the individual kinetic and
potential energy terms. This is, of course, related to the fact
that for the HF orbitals a variational minimum in the total
energy is obtained, so that distortion to KS orbitals will not
affect the total energy greatly.
We note that the numbers at the elongated bond length
give the same overall picture as those at Re, with maybe a
slight increase of the errors. The CO molecule is not excep-
tional, essentially the same conclusions have been drawn
from a similar comparison for other diatomics such as N2 , F2,
and Li2.41 In summary, the HF and EXX models significantly
distort, compared to the KS model, the density and orbitals,
and therefore the separate energy terms, but there is error
cancellation when adding these terms up. One might also
take the opposite view: the KS model changes the orbitals
and density considerably from the HF and EXX models to
bring the separate energy terms much closer to the exact
ones, without being punished very much in the total energy
of the KS determinantal wave function.
Tables II and III also contain the corresponding data for
the LDA and the BLYP GGA models. Apparently, these mod-
els do not provide one-electron potentials that lead to accu-
rate densities and orbitals. The total density and the orbitals
are much too diffuse for LDA 共too low TLDA and WH LDA
, not
negative enough Ven 兲, but it appears that the BLYP ap-
LDA
proximation overcorrects, already at Re but particularly for
the longer bond distance, towards too contracted orbitals and
density 共too large energy components兲. Note that TBLYP
should be equal to TKS, so the small 0.004 a.u. difference 共at
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J. Chem. Phys. 123, 062202 共2005兲
Re兲 of TCI with respect to TBLYP is not so relevant, the large
difference of −0.30 a.u. of TKS with TBLYP demonstrates the
too contracted nature of the BLYP orbitals, and is mirrored in
CI BLYP
the +0.264 difference Ven − Ven . The WX numbers illustrate
the well-known ca. 10% error of the LDA exchange energy
and the considerable correction towards the exact exchange
provided by the GGA model. We use the KS exchange en-
ergy as the exact-exchange energy; it is the same exchange
energy expression as the HF one, but it is evaluated with the
KS orbitals instead of the HF ones. There remains a sizable
error in the BLYP exchange energy 共0.156 at Re兲. The tables
also contain the total electronic energies calculated using the
LDA or GGA density functionals for the exchange energy,
i.e., Eel is in all cases the sum T + Ven + WH + WX. The differ-
ence of the CI energy with respect to this Eel energy is by
definition the correlation energy. The correlation energy Ec is
overestimated by the well-known ca. 100% by the LDA
functional, at least when compared to the standard correla-
tion energy of ca. −0.45 a.u. at Re. However, it is interesting
to note that the other energy terms in the LDA energy are so
poor that actually the correlation error of the LDA calcula-
tion is, with −1.682 a.u., much larger, and the LDA correla-
tion energy of −0.950 a.u. is too low! The BLYP correlation
energy is much better, although the agreement is by no
means perfect. The BLYP correlation energy of −0.486 a.u.
at Re is fairly close the standard correlation energy 共KS
model兲 of −0.466 a.u., but it is rather too strongly negative
compared to the remaining correlation error of EBLYP el of
−0.338 a.u. The implication is that the total energy of the
BLYP model 共−135.909 at Re, −130.381 at R = 2.8 bohrs兲 is
too negative compared to the CI energy. The 共empirical兲 ex-
act nonrelativistic total energy will be lower than the CI total
energy, but is not known in the case of CO. It is not clear
therefore how closely the BLYP total energy happens to be to
this empirical total energy.
We observe that the BLYP exchange energy is consis-
tently too negative compared to the KS exchange energy. It
has been observed that a more consistent interpretation of the
LDA and GGA models is obtained if we conclude from the
fact that the LDA and GGA exchange holes are localized
around the reference position so that these model holes in
fact do not represent exchange, but the sum of exchange and
nondynamical correlation. In a number of cases where rea-
sonable estimates of the nondynamical correlation energies
were available, it has been shown41 that the GGA exchange
energy indeed represents with good quantitative accuracy the
sum of the KS exchange energy and the nondynamical cor-
relation energy. In its turn, the GGA correlation energy ac-
ccurately approximates the dynamical correlation energy,
which can be obtained as the sum of the total correlation
energy minus the nondynamical correlation energy. The total
correlation energy to be used here is not the one obtained
from the CI calculations in Table II, since it deviates 共due to
basis set deficiency and the necessarily limited CI兲 too much
from the conventional correlation energy, defined as the dif-
ference of the exact total energy and the Hartree–Fock en-
ergy. The “empirical correlation energy” can be obtained
from the “empirical” total energy established for a number of
molecules.47–49 Unfortunately, the empirical total energy is
 062202-8 E. J. Baerends and O. V. Gritsenko J. Chem. Phys. 123, 062202 共2005兲

not available for CO, so we cannot check the finding of Ref.
41 for N2 , F2, and Li2 that the GGA correlation energy is
indeed close to the dynamical part of the total correlation
energy.
One can argue that here is the real origin of the success
of DFT in its density/gradient forms. In reality 共maybe not
intentionally by the originators of LDA and GGA兲 the DFT
approximations have not tried to solve the total electron-
electron interaction problem by doing first exchange and
then correcting with the correlation energy. Instead, DFT has
broken away from that partitioning of the electron-electron
interaction, and first treats exchange plus nondynamical cor-
relation in one step 共by what is, unfortunately, called the
“exchange functional”兲 and in the next step obtains the dy-
namical correlation 共called “correlation”兲 from expressions
based on the correlation energy of the electron gas. The no-
tion that even the exchange-only LDA model 共i.e., X␣兲 al-
ready contains left-right correlation has been widespread 共cf.
the terminology exchange-correlation potential by Slater50兲
and has, e.g., been elaborated on by Cook and Karplus.51 It
should be noted, though, that Becke has recently argued in
favor of restoring the traditional steps of first doing exchange
and next the correlation.52
mations from ab initio theory.31 Also, expressions based on
random-phase approximation or Green’s functions can be
used.53–57 However, we have argued that one should not take
Hartree–Fock as the starting point. Since modeling of the
total exchange-correlation hole appears to be easier than
modeling of the exchange and correlation holes separately, it
should be feasible to develop orbital-dependent expressions,
which represent exchange and correlation simultaneously.
We, therefore, highlight here a development, which does not
use perturbation theory, but obtains an expression for the
exchange-correlation hole that is valid for both dynamic cor-
relation 共where perturbation theory might work兲 and nondy-
namic or near-degeneracy correlation 共where perturbation
theory typically fails兲. This approach makes use of recent
developments in the theory of functionals of the one-electron
density matrix35,46,58 共see also Refs. 59–64兲. In the latter
theory the exchange-correlation hole surrounding a reference
electron at position r1 is written as the square of an xc hole
amplitude ␸xc hole
: ␳xc
hole
共r2兩r1兲 = −兩␸xc
hole
共r2兩r1兲兩2. The concept of
a hole amplitude has been introduced earlier by Luken for
the pure exchange hole.65,66 When we write the exchange
energy 共for a closed-shell system with all doubly occupied
orbitals, ␥ is the one-electron density matrix兲,

冕
Though we have been critical about the exact-exchange
1
functional, since one cannot expect it to do any better than Ex = − ␥共r1,r2兲␥共r2,r1兲dr1dr2
the Hartree–Fock model, we should point out that in one 4
important respect the Kohn–Sham exact-exchange model
differs from Hartree–Fock. The Kohn–Sham potential is a
local potential, which is the same for the occupied and the
=
1
2
冕 冕 ␳共r1兲
␳hole
x 共r2兩r1兲
r12
dr2 共4.1兲

virtual orbitals. The Hartree–Fock model effectively uses a which defines the exchange hole as
different potential for the virtual orbitals. The virtual elec-
trons in the HF model see a potential due to all N electrons, 1 ␥共r1,r2兲␥共r2,r1兲
␳hole
x 共r2兩r1兲 = − , 共4.2兲
not that of N − 1 electrons, as the HF electrons in occupied 2 ␳共r1兲
orbitals do, and the Kohn–Sham electrons in both occupied
we find immediately from the fact that the one-electron den-
and virtual orbitals. The orbital energies of the virtual orbit-
sity matrix is, in the case of a closed-shell single determinant
als therefore are considerably different in the Kohn–Sham
wave function,
and the Hartree–Fock models. When the exact-exchange
functional is used in the Kohn–Sham model, the optimized H

potential remains a single local potential for all states, occu- ␥共r1,r2兲 = 兺 2␸i共r1兲␸*i 共r2兲, 共4.3兲
pied and virtual. The difference of the virtual orbital energies i=1

with respect to HF therefore remains. For excitation energy and that ␳hole can be written as the square of an amplitude,
x
calculations in the time-dependent DFT, where the orbital
energies and orbital shapes play an important role, the dif- 冑2␸*i 共r1兲
N/2 N/2
冑2␸ j共r1兲 *
␳hole =−兺 ␸i共r2兲 兺
ference between HF and Kohn–Sham EXX will be very im- x 共r2兩r1兲
i=1
冑␳共r1兲 j=1
冑␳共r1兲 ␸ j 共r2兲
portant. We will return to this point in Sec. V.
⬅ − 兩␸hole
x 共r2兩r1兲兩 .
2
共4.4兲
IV. A „VIRTUAL… ORBITAL-DEPENDENT XC
FUNCTIONAL The amplitude ␸hole
x ,
also called the Fermi amplitude, can in
general be expanded in a complete one-electron basis,
The KS EXX approximation cannot be regarded to be ␸hole
x 共r2兩r1兲 = 兺ci␸i共r2兲. The expansion coefficients will de-
the next improvement beyond GGA, which has now been pend on the reference position, and in the exchange case they
awaited for a long time but has not materialized yet. Still, have the simple form
such improvement can come from explicitly orbital-
dependent functionals. The requirement should be that such 冑2␸*i 共r1兲
ci共r1兲 = for occupied orbitals
orbital-dependent functionals incorporate correlation effects. 冑␳共r1兲
Such functionals can be based on perturbation theoretic ex-
共4.5兲
pressions, such as the second-order Görling–Levy perturba-
ci共r1兲 = 0 for virtual orbitals.
tion expression, which is the DFT equivalent of the well-
known Møller–Plesset one, cf. the OEP-MBPT共2兲 work of This expression helps to understand the properties of the
Bartlett and co-workers,30 or on still more advanced approxi- Fermi hole. When at a reference point a specific orbital ␸i
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 062202-9 Orbital-dependent exchange-correlation functionals J. Chem. Phys. 123, 062202 共2005兲

makes a predominant contribution to the density, the hole
will have the shape of 共the negative of兲 that orbital density.
This explains why the exchange hole has the shape of a core
orbital density when the reference point is inside that orbital,
or a lone pair shape when the hole is in that region. In the
case of H2 the summation reduces to just one orbital, the
occupied ␴g, and with ␳共r1兲 = 2兩␴g共r1兲兩2 we obtain
guments Arias and Csanyi63兲. Following these density matrix
functional theory arguments, a similar expression has been
proposed recently in Refs. 32 and 35 for the amplitude of the
coupling constant integrated xc hole in DFT, with all H oc-
cupied ␾ j and a finite number Nv of virtual KS orbitals ␾a
being used instead of the NOs 共M = H + Nv兲,

␸hole
冑2␴g共r1兲 ¯␸xc
hole
共r2兩r1兲 = 兺
M
冑 wi *
␾ 共r1兲␾i共r2兲,
␳共r1兲 i
共4.11兲
x 共r2兩r1兲 =
冑2兩␴g共r1兲兩2 ␴g共r2兲 = ␴g共r2兲, i

共4.6兲 M M
冑wiw j
␳hole
x 共r2兩r1兲 = − 兩␴g共r2兲兩 , =−兺兺
2
¯␳xc
hole
共r2兩r1兲 ␾*i 共r1兲␾i共r2兲␾ j共r1兲␾*j 共r2兲.
i j ␳共r1兲
which is in agreement with our earlier observation that this
hole is independent of the reference postion r1 and extends 共4.12兲
over the two nuclei whatever the distance between the two This yields the following orbital-dependent potential of the
nuclei. hole共BB兲
xc hole v̄xc 共BB—Buijse–Baerends兲
It is possible to extend this simple representation of the
hole to the full exchange-correlation case.58 The amplitude is
again expanded in a complete set, for instance, in the set of
hole共BB兲
v̄xc 共r1兲 = − 冕 ␳xc
hole
共r2兩r1兲
r12
dr2
natural orbitals 共NOs兲, M M
冑wiw j
␳xc
hole
共r2兩r1兲 =− 兩␸xc
hole
共r2兩r1兲兩2 , =−兺兺 ␾*i 共r1兲␾ j共r1兲
i j ␳共r1兲
共4.7兲
␸xc
hole
共r2兩r1兲 = 兺 ci共r1兲␹i共r2兲.

In this way one defines a trial two-electron density matrix,

⫻ 冕 dr2
␾i共r2兲␾*j 共r2兲
r12
共4.13兲

BB
and the xc energy functional Exc
⌫trial共r1,r2兲 = ␳共r1兲␳共r2兲 − ␳共r1兲␳xc
hole
共r2兩r1兲. 共4.8兲
BB
Exc 关兵␾ j其,兵␾a其兴
One can derive from symmetry properties and sum rules of
the two-electron density matrix 关such as permutation symme- M M

兺 兺 冑w i w j
1
try in r1 and r2; integration of ⌫ over r2 should yield 共N =−
2 i j
− 1兲␳共r1兲; integration of the hole density should yield −1兴
that the coefficients should be
冑ni␹*i 共r1兲
⫻ 冕 dr1dr2
␾*i 共r1兲␾i共r2兲␾ j共r1兲␾*j 共r2兲
r12
. 共4.14兲
ci共r1兲 = 共4.9兲
冑␳共r1兲 , Here wi关␳兴 is the xc orbital weight, which governs the in-
volvement of the occupied/virtual orbital ␾i in the xc func-
where ni are the NO occupation numbers. Evidently, not just
tional. The weights wi关␳兴 are the important novel density
the heavily occupied orbitals, which resemble the occupied
functionals. We note that the link with the EXX functional
Hartree–Fock orbitals, enter, but also the weakly occupied
can be made when we restrict the summations to just the H
ones. The latter are not similar to virtual Hartree–Fock orbit-
occupied orbitals, and take for the weights wi the occupation
als, but are much more compact. In the case of dissociating
H2, the wave function reduces to 共1 / 冑2兲兩␴g共r1兲¯␴g共r2兲兩
numbers 2.0.
− 共1 / 冑2兲兩␴u共r1兲¯␴u共r2兲兩, and the hole amplitude becomes
By giving weights to the virtual orbitals we can incorpo-
rate the effect of correlation, as is clear from the discussion
冑ng␴g共r1兲 冑nu␴u共r1兲 of the density matrix theory. The weights have to take into
␸xc ␴g共r2兲 +
共r2兩r1兲 =
冑␳共r1兲 ␴u共r2兲.
hole
冑␳共r1兲 account that the full coupling constant integrated hole in-
cludes both kinetic energy and electron-electron potential en-
共4.10兲 ergy effects of electron correlation and also they have to
compensate for the approximate form of the BB functional
One can easily verify that this representation of the total
共4.4兲. We use overbars in ¯␳xchole hole
and v̄xc to indicate that we
exchange-correlation hole obeys the required localization on
are dealing with the coupling constant integrated quantities.
the site where the reference position is located 共in the limit
In Ref. 32 the functional form of wi has been approximated
where ng = nu = 1.0兲: if r1 is close to nucleus A共r1 苸 ⍀A兲,
共r2兩r1 苸 ⍀A兲 = 共1 / 冑2兲关␴g共r2兲 + ␴u共r2兲兴 = 1sA共r2兲,
with the Fermi-type distribution
␸xc
hole
and
when r1 is close to nucleus B, ␸xc 共r2兩r1 苸 ⍀B兲 = 共1 / 冑2兲
hole
2
⫻关␴g共r2兲 − ␴u共r2兲兴 = 1sB共r2兲. wi = , 共4.15兲
1 + exp关f共␧i − ␧F兲兴
Effectively, a representation of the two-electron density
matrix in terms of the one-electron density matrix has been where ␧i are the KS orbital energies in Eq. 共1.1兲 and ␧F is the
obtained 共see for further generalization of the symmetry ar- Fermi level parameter.
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 062202-10 E. J. Baerends and O. V. Gritsenko J. Chem. Phys. 123, 062202 共2005兲

The various OEP approaches13,14,16–18,20,67,68 which have ployed; however, the contributions of the derivatives
until now been applied mostly to the EXX functional involv- ␦wi关␳兴 / ␦␳共r1兲 to the potential vxc
BB-CEDA
were neglected.
ing only occupied orbitals, can, in principle, be extended to These derivatives contribute only to the response potential
treat functionals, which depend on both occupied and virtual BB-CEDA
vresp , so that they do not affect the leading term of
orbitals. In Ref. 32 a generalized CEDA 共Ref. 24兲 has been BB-CEDA
vxc
hole共BB兲
, the xc hole potential v̄xc . On the other hand, a
employed to develop a variational, self-consistent KS functional dependence wi关␳兴 could, in principle, be devised
method with the BB functional 共4.14兲 and 共4.15兲. Within in such a way that its derivative would cancel the asymptotic
CEDA, all terms of the exact KS Green’s function 共2.5兲 with divergence in the potential 共4.20兲. This divergence is a seri-
M occupied and virtual orbitals included in Eqs. 共4.14兲 and ous problem of functionals of virtual orbitals. It is immedi-
共4.15兲 are treated rigorously, while in the remaining terms ately apparent from Eq. 共4.20兲 that asymptotically the den-
the common energy denominator ⌬␧ ˜ is used. The resultant sity ␳共r1兲 in the denominator, which decays as the highest
CEDA Green’s function has the following form occupied orbital density, will tend to zero faster than the
M ⬁ numerator if virtual orbitals appear in the numerator. The
␾ j共r1兲␾*j 共r2兲 1
GCEDA
i 共r1,r2兲 =兺
ji ␧ j − ␧i
+
⌬␧
兺 ␾a共r1兲␾*a共r2兲
˜ a⬎M
potential will therefore exhibit a divergence when r → ⬁. The
divergence of the potential has been highlighted in Refs. 70
␦共r1 − r2兲 1
M and 71 for the second-order Görling–Levy 共GL2兲 perturba-
=
⌬␧
˜
−
⌬␧
兺 dij␾ j共r1兲␾*j 共r2兲,
˜ j
tion theoretic Exc. There has been some debate about the
question whether the divergence is an inherent property of
共4.16兲 every functional that includes virtual orbitals. According to
Niquet et al. this is not the case. In, for instance, the GL2
˜ 共1 − ␦ij兲兴 / 共␧ j − ␧i兲. The function 共4.16兲
where dij = 关␧ j − ␧i − ⌬␧ expression for Exc, and indeed other perturbation theoretic
is to be inserted in the master OEP equation, which in this expressions based on the Green’s function, one can show that
general case has the following form
the optimized potential will exhibit proper −1 / r decay for

冕 r → ⬁ due to cancellation of divergent terms in the part of the

H
2 兺 ␾*i 共r1兲 vxc共r2兲Gi共r1,r2兲␾i共r2兲dr2 + c.c. potential containing derivatives with respect to the orbitals
i
against divergent terms from derivatives with respect to or-

冕
M bital energies. This is a quite subtle effect. In the investigated
= 兺 ␾*i 共r1兲 i
vxc 共r2兲Gi共r1,r2兲␾i共r2兲dr2 + c.c., 共4.17兲 functionals it does not arise from term-by-term cancellation
i
of expressions with finite summations over virtual orbitals,
i
where the nonlocal potentials vxc are defined as but builds up when complete summations are carried

冋 册
through. This may make it difficult to devise an orbital en-
1 ␦Exc关兵␾i其兴 ergy dependence of the functional 共in our case through the
i
vxc 共r2兲 = . 共4.18兲
␾i共r2兲 ␦␾*i 共r2兲 orbital dependency of wi兲 in such a way that the cancellation
is obtained when using a finite number of virtual orbitals.
BB
Inserting Exc of Eq. 共4.14兲 in Eq. 共4.18兲 and GCEDA
i in Eq.
Alternatively, since the exact potential is known to exhibit
共4.17兲, and then solving Eq. 共4.17兲 for the potential vxc, we
the −1 / r asymptotic behavior, one may constrain in the op-
obtain the BB-CEDA xc potential in the characteristic CEDA
timization the asymptotic behavior of the potential to this
form
form. This is effectively the strategy of Wu, Ayers, and Yang
BB-CEDA
vxc 共r1兲 = v̄xc
hole共BB兲
共r1兲 + vresp
BB-CEDA
共r1兲. 共4.19兲 in Ref. 72 to corect the wrong asymptotic behavior of the
LDA and GGA potentials. In the same vein, in Ref. 32 the
The main xc effect is represented with the first term of Eq.
density in the denominators of the potentials 共4.15兲 and
共4.19兲, the potential 共4.13兲 of the xc hole 共4.12兲. In particular,
hole共BB兲 共4.20兲 was replaced with the function ˜␳共r1兲 = 兺iM wi兩␾i共r1兲兩2,
having the component v̄xc , the BB-CEDA potential rep-
i.e., the xc weights wi were interpreted as effective occupa-
resents correctly the effect of strong left-right correlation in
tion numbers in an effective density ˜␳共r1兲. It is expected that
the important special case of stretched H2 considered above.
˜␳共r1兲 is actually a close approximation to ␳共r1兲, except for
The second term of Eq. 共4.19兲 is the response potential
the crucial difference in how these two densities tend asymp-
M M
␾*i 共r1兲␾ j共r1兲 totically to zero.
BB-CEDA
vresp 共r1兲 = 兺 兺 sBB-CEDA . 共4.20兲 The 共virtual兲 orbital-dependent xc energy functional Exc BB
i
ij
j ␳共r1兲
共4.14兲 and its xc potential ␯xc
BB-CEDA
共4.19兲 have been applied
The diagonal terms corresponding to occupied orbitals rep- in Ref. 32 in self-consistent KS calculations of the potential
resent the characteristic step structure of the response part of curve of the H2 molecule. Figure 2 compares the total energy
the KS potential,23,69 which is responsible for the well- curve obtained with this method with those calculated with
known “bumps” in the KS potential at atomic shell bound- HF and full configuration interaction 共FCI兲 methods as well
aries. The BB-CEDA potential has a similar orbital structure as with LDA and GGA-BP BP—Becke 88–Perdew 86 共Refs.
to that of the exchange-only CEDA potential 共2.7兲 and 共2.8兲, 7 and 9兲 functionals. The most dramatic is the HF failure due
which is now extended to virtual orbitals. to the neglect of the Coulomb correlation, which was dis-
In the implementation of Ref. 32 a particular param- cussed above. The HF curve goes higher than other curves at
etrized form of the xc weight functional 共4.15兲 was em- nearly all H–H distances and at R共H–H兲 = 10 bohrs the error
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 062202-11 Orbital-dependent exchange-correlation functionals
FIG. 2. Total energy of the hydrogen molecule as a function of internuclear
distance for the Hartree–Fock approximation 共HF兲, the local density ap-
proximation 共LDA兲, the Becke88–Perdew86 generalized gradient approxi-
mation 共BP兲, a full CI calculation, and the Buijse–Baerends 共BB兲 exchange-
correlation functional.
of the HF total energy is EHF − EFCI = 148 kcal/ mol and the
the error of the dissociation energy is DHF FCI
e − De
= 123 kcal/ mol.
Spin- and symmetry-restricted LDA and GGA-BP also
produce too high energy of the dissociating H2 共see Fig. 2兲,
although not as high as HF. In particular, near the equilib-
rium distance the LDA curve is close to the HF one, while at
larger R共H–H兲 it goes in between the HF and FCI curves. At
R共H–H兲 = 10 bohrs the LDA total energy error is ELDA
− EFCI = 69 kcal/ mol and the LDA dissociation energy error
is DLDA
e − DFCI
e = 46 kcal/ mol. The gradient correction lowers
the GGA-BP energy compared to the LDA one and the BP
curve goes below and almost in parallel to the LDA curve.
Near the equilibrium the BP curve is close to the FCI one,
however, the BP energy is still much too high at long dis-
tances. The BP total energy error at R共H–H兲 = 10 bohrs is
EBP − EFCI = 44 kcal/ mol and the BP dissociation energy error
is DLDA
e − DFCI
e = 47 kcal/ mol, even slightly larger than the
LDA one.
In contrast to the LDA and GGA curves, the potential
curve of the self-consistent 共virtual兲 orbital-dependent BB
method, taken with the two-parameter Fermi-distribution
functional 共4.15兲, excellently reproduces the FCI curve, both
curves practically coincide at all H–H distances 共see Fig. 2兲.
The average absolute error of BB is only 0.72 kcal/ mol and
the maximal error is 2.4 kcal/ mol at R共H–H兲 = 3 bohrs. The
important feature of the functional 共4.14兲 and 共4.19兲 is its
correct behavior for dissociating H2. Due to this, the BB
dissociation energy error is only 0.20 kcal/ mol. We conclude
that, in contrast to the EXX model, the BB functional is able
to treat the electron-electron correlation all the way from the
mostly dynamical correlation situation at Re to the purely
nondynamical correlation at R → ⬁. It is achieved by a mod-
eling of the xc functional that does not separate exchange
and correlation but treats them on equal footing, in the trad-
tional statistical physical manner by modeling directly the
conditional probability of finding an electron in the neigbor-
hood of a reference electron.
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J. Chem. Phys. 123, 062202 共2005兲
V. MOLECULAR RESPONSE PROPERTIES WITH
ORBITAL-DEPENDENT XC FUNCTIONALS:
POLARIZABILITIES
We have seen that orbital-dependent xc functionals can
improve greatly over LDA and GGA functionals for the en-
ergy. Another important field of application of orbital-
dependent functionals is in response properties, calculated
with time-dependent DFT, where sometimes the purely den-
sity dependent functionals exhibit fundamental weaknesses.
The orbital dependence 共which implies an implicit density
dependence兲 can introduce features in the density functionals
that would be very hard to obtain in an explicitly density
dependent form.
Until now, the EXX model and its close approximations
have been applied within time-dependent DFT 共TDDFT兲 to
the calculation of various molecular response properties,
such as 共hyper兲polarizabilities and electron excitation ener-
gies, see Refs. 19, 25, and 73–75. While the EXX model has
deficiences for total and bond energies, similar to Hartree–
Fock, for response properties this close resemblance between
KS-EXX and HF need not necessarily apply in view of the
difference between the shapes and energies of virtual orbitals
in the two models. In the present section we will discuss
共hyper兲polarizabilities, and find that KS-EXX is actually
close to Hartree–Fock. It is of course not necessary to use the
functional derivatives of improved energy functionals in or-
der to improve on the deficient orbital energy spectrum of
LDA/GGA. The KS orbital energy spectrum may also be
modeled directly by introducing functionals, possibly orbital
dependent, for the KS potential itself. Recently, a relatively
simple orbital-dependent potential with statistical averaging
of 共model兲 orbital potentials 共SAOP兲 共Ref. 76兲 has been ap-
plied to the response properties, including excitation ener-
gies, of small prototype molecules77,78 and to the calculation
of electron excitations of practically important porphyrin
systems and their complexes.79,80 Excitation energies will be
discussed in the following section.
A remarkable effect of the full KS response theory,
which requires orbital mechanisms for its explanation and
orbital-dependent functionals for its adequate description, is
the field-counteracting effect of the xc potential of molecular
chains24,25,81,82 and extended dielectric systems83–88 in an ex-
ternal electric field, compared to the LDA or GGA approxi-
mation. Specifically, a characteristic ultranonlocal term 关not
describable by a local-density 共or density-gradient兲 func-
tional兴 is induced in the xc potential by an applied uniform
electric field, which spans the entire system and counteracts
the field. The orbital-dependent EXX exchange potentials
共also in their KLI and CEDA approximations兲 possess this
field-counteracting behavior19,25 and Fig. 3 displays the KLI
and CEDA potentials together with their exchange hole
共Slater兲 and response components 共2.7兲 calculated for the
prototype hydrogen chain H18 with alternating H–H bonds of
2 and 3 bohrs in an electric field of 0.004 a.u. 共the dotted line
in Fig. 3 indicates the external potential generating this
field兲. The Slater 共exchange-hole兲 potential 共indistinguish-
able for KLI and CEDA in Fig. 3兲 exhibits only periodical
variation, representing the individual H2 units. The
exchange-hole potential does not exhibit any field counter-
 062202-12 E. J. Baerends and O. V. Gritsenko J. Chem. Phys. 123, 062202 共2005兲

FIG. 3. The CEDA 共drawn line兲 and

the KLI 共broken line兲 total exchange
potential 共bottom兲 and the response
共top兲 and Slater 共middle兲 components
are plotted along the main axis for the
chain H18 in an electric field of 0.004
a.u. 共the external field-induced poten-
tial is displayed with a dotted line in
the panel of the response components兲.

CEDA
acting effect. In the sense that one could consider incorpora- region makes the potential vresp higher in this region. In
tion of the full exchange hole potential 共the hole integrates to other words, while the total density ␳ does not directly feel
−1 electron兲 equivalent to avoiding a self-interaction error, the polarizations of occupied orbitals in opposite directions
the absence of a counteracting field effect does not appear to in an electric field, the weighted density 兺H CEDA
i sii 兩␾i共r1兲兩2
arise from a self-interaction error. However, it has been ar- produces under this polarization a field-counteracting term
gued by Mori-Sanchez et al.19 that the wrong scaling of the 共5.1兲, which is responsible for the field-counteracting behav-
LDA exchange energy with effective occupation number ior of the total exchange potential. This basic “weighted-
when an electronic charge density is fractionally distributed density” mechanism is valid for both KLI and CEDA, which
over noninteracting or weakly interacting sites89,90 can be possess diagonal terms with 兩␾i兩2, and the additional CEDA
related to the wrong polarizability of the chain of weakly off-diagonal contributions increase further its field-
interacting H2 units. In contrast to LDA and GGA, the KLI counteracting term compared to KLI 共see Fig. 3兲.
and CEDA response potentials counteract the external field- Effective reduction of an external applied potential by
induced potential, i.e., they become more positive at the the induced field-counteracting terms in the KS xc potential
down-field end of H18. This determines the overall field- is required in order that DFT methods yield an adequate
counteracting effect of the KLI and CEDA exchange poten- description of the response properties of molecular chains.
tials. From the upper part of Fig. 3 one can clearly see that LDA and standard GGA potentials all lack the abovemen-
CEDA develops a larger field-counteracting response poten- tioned compensation structure and, in the absence of the
tial than KLI. As was established in Refs. 24, 25, 81, and 82 counteracting effect, they produce a dramatic overestimation
the field-counteracting behavior of the CEDA 共and KLI兲 re- of 共hyper兲polarizabilities of molecular chains.25,81,91 Table IV
sponse potential originates from its orbital step structure presents the static longitudinal polarizabilities ␣ of the hy-
共2.8兲 and from the characteristic pattern of the polarization of
the orbitals of the valence “band” of a molecular chain in an TABLE IV. Comparison of the LDA, GGA, KLI, CEDA, EXX, HF, MP2,
external electric field. The dominant term of the change MP4, and CCSDT static longitudinal polarizabilities ␣ 共in atomic units兲 of
␦vresp
CEDA
of the potential 共2.8兲 appears to be that containing linear hydrogen chains Hn.
changes ␦兩␾i兩2 of individual orbital densities
H
␣ H6 H12 H18
␦兩␾i共r1兲兩2
␦vresp
CEDA
共r1兲 ⬃ 兺 sCEDA . 共5.1兲 LDA 72.7 210.6 367.3
i
ii
␳共r1兲 BLYP 68.98 194.80 334.85
BP 69.18 196.68 339.10
But then, a fundamental feature of the orbital response to an
PW 68.96 195.84 337.47
external-field potential, which can easily be established with KLI 60.50 157.15 260.66
perturbation theory 共see Ref. 82兲, is that the densities of CEDA 59.28 149.35 244.24
lower occupied orbitals in Eq. 共5.1兲 are localized more in the EXXa 227.97
down-field region, while higher occupied orbitals are local- HF 56.38 137.64 222.31
ized more in the up-field region. These individual changes in MP2b 54.16 134.00 217.42
opposite directions hardly change the total density ␳, how- MP4b 51.59 126.90 205.39
ever, they produce a field-counteracting change ␦vresp CEDA
. The CCSDTb 50.54 123.63 199.65
explanation is that lower orbitals ␾i possess larger steps a
Reference 19.
sCEDA
ii in Eq. 共5.1兲, so that their localization in the down-field b
Reference 94.
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 062202-13 Orbital-dependent exchange-correlation functionals
drogen chains H6 , H12, and H18 calculated within the finite-
field approach with KLI, CEDA, and HF. They are compared
with those calculated with LDA and GGA Becke–Lee–Yang–
Parr 共BLYP兲,7,10 Becke–Perdew 共BP兲,7,9 and Perdew–Wang
共PW兲 共Refs. 92 and 93兲 methods. The ␣ values obtained in
Ref. 94 with the correlated Møller–Plesset 共MP2 and MP4兲
and with the coupled cluster 共CCSDT兲 methods serve as a
reference. Although the effects are much more dramatic for
the second hyperpolarizability ␥ 共more than a factor 10 over-
estimation by LDA, reduced to a factor 1.2 for EXX-CEDA兲,
we take the longitudinal polarizability ␣ as an example since
comparison can be made to the recently19 obtained accurate
EXX ␣ for H18. One can see from Table IV that the better the
quality of the method, the lower is the calculated ␣ value. In
particular, LDA greatly overestimates ␣, the LDA error in-
creases with the length of the chain. While for H6 the LDA ␣
value is 1.4 times higher than that of CCSDT, for H18 this
ratio grows to 1.84. ␣ values of different GGAs are close to
each other and GGAs improve only slightly upon LDA. Con-
trary to this, the orbital-dependent KLI and CEDA dramati-
cally decrease ␣ values upon LDA/GGAs, with CEDA pro-
ducing consistently lower ␣ than KLI. The CEDA
approximation to the EXX lowers the LDA overestimation of
184% to 122%, the accurate EXX ␣ lowers this to 114%.
Still, just as in the case of the ground-state total energy con-
sidered in the previous sections, one is not gaining anything
compared to Hartree–Fock. Indeed, the HF ␣ values are the
lowest among the exchange-only methods 共see Table IV兲.
Furthermore, ␣ values of the correlated MP2, MP4, and
CCSDT methods are consistently lower than the HF ones. So
we can conclude that an orbital-dependent functional is re-
quired to avoid the large errors of the LDA and GGA meth-
ods for 共hyper兲polarizabilities in this particular case, but
DFT within the EXX model does not offer any advantage
over straight Hartree–Fock. Here, again, further improve-
ment beyond the exchange-only approach is required. It
could come from orbital-dependent functionals, which com-
bine the effects of both exchange and correlation in their
orbital structure. Natural candidates for this role are func-
tionals, which depend explicitly on both occupied and virtual
KS orbitals, such as the BB functional presented in the pre-
ceding section, but the performance of such functionals for
共hyper兲polarizabilities has not yet been studied.
VI. MOLECULAR RESPONSE PROPERTIES WITH
ORBITAL-DEPENDENT XC FUNCTIONALS:
EXCITATION ENERGIES
The orbital energies, both of occupied and of virtual or-
bitals, are key quantities in the calculation of response prop-
erties. This is the case, in particular, for electron excitations
calculated with time- dependent DFT 共TDDFT兲. In TDDFT
the zero-order estimate of the excitation energy ␻k is just the
energy difference of the occupied ␾i and virtual ␾a ground-
state orbitals associated with the excitation95
␻0k = ␧a − ␧i .
Actually, the energies of occupied HF and KS orbitals have
the same physical meaning. By virtue of Koopmans’
theorem96 and its DFT analog established recently in Refs.
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J. Chem. Phys. 123, 062202 共2005兲
97–100, the energy ␧i of an occupied orbital can be inter-
preted approximately as 共minus兲 the vertical ionization po-
tential 共VIP兲 Ii of the corresponding primary ionization, −␧i
⬇ I共␸−1 i 兲. Remarkably, for accurate KS solutions 共see the dis-
cussion in Sec. III on how these can be obtained兲 it is found
for a series of prototype molecules that the quality of this
approximation appears, in the case of valence orbitals, to be
an order of magnitude better than for the HF orbitals97,99 共0.1
eV versus 1.0 eV兲, and for the KS highest occupied molecu-
lar orbital 共HOMO兲 it becomes an exact equality.101–104
To illustrate this point, Table V displays valence orbital
energies of the accurate KS solution obtained in Ref. 99 for
prototype molecules with the LB procedure37 from the cor-
related CI density as well as the HF orbital energies, the
EXX orbital energies 共from Ref. 67兲, and the GGA-BP or-
bital energies. They are compared with the experimental
VIPs.105–109 One can see from Table V that only inclusion of
both exchange and correlation in the KS potential ␯xc can
provide a high quality of the DFT analog of Koopmans’
theorem. Indeed, the orbital energies of the accurate KS xc
potential excellently reproduce the experimental VIPs with a
typical absolute average difference 共AAD兲 of only 0.1 eV.
The quality of Koopmans’ theorem for EXX is much worse,
it is similar to that of the HF Koopmans’ theorem. Just as HF,
EXX tends to overestimate VIPs with the Koopmans’ esti-
mate. Only for the FCN molecule the EXX AAD of 0.42 eV
is substantially smaller than the HF one of 1.85 eV. For CO,
N2, and H2O the EXX AAD values of 0.95, 1.30, and 1.02
eV, respectively, are similar to the corresponding HF differ-
ences, and for the HF molecule the EXX deviation of the
energies of the two highest occupied MOs appears to be
higher than the Hartree–Fock one.
While HF and EXX occupied orbital energies overesti-
mate VIPs, GGA-BP consistently underestimates them 共see
Table V兲. For a particular molecule, the upward shift of the
BP ␧i with respect to the vertical −Ii is remarkably uniform.
For each molecule we also present for the BP HOMO this
shift 共␧H BP
+ IH兲. For the other orbitals the energies shifted
downwards by 共␧H BP
+ IH兲 are given, as well as the corre-
sponding AADs. Note, that for CO, N2 , H2O, and FCN the
upward shift of the GGA-BP HOMO orbital energies varies
within the rather narrow margins of 4.83–5.30 eV, and only
for the HF molecule the BP shift is higher at 6.44 eV. One
can see from Table V that the 共␧H BP
+ IH兲-shifted BP orbital
energies reproduce the valence VIPs very well, with the
AAD values being close to those of the accurate KS solution.
Unlike the abovementioned similarity of the Koopmans’
type interpretation for occupied orbitals, there is an impor-
tant qualitative difference between virtual HF and KS orbit-
als. The energies of virtual HF orbitals represent approxi-
mately the energy of an added electron in the field of all
other N electrons, in particular, the HF lowest unoccupied
molecular orbital 共LUMO兲 energy represents, within the
Koopmans approximation, the molecular electron affinity. In
contrast to this, as observed earlier, it is a basic feature of the
共6.1兲
KS solution 共2.1兲 of an N-electron system that all occupied
and virtual orbitals are obtained with the same local, state-
independent KS potential vs, so that they all “feel” the effec-
tive field of N − 1 electrons. As a result, the energies of the
 062202-14 E. J. Baerends and O. V. Gritsenko J. Chem. Phys. 123, 062202 共2005兲

TABLE V. Comparison of the KS, HF, EXX, and GGA-BP orbital energies −␧i 共eV兲 with experimental VIPs 共the corresponding references are indicated in
the table兲. AAD are the average absolute differences between the KS orbital energies and VIPs. For BP the deviation of ␧HBP from −IH, i.e., the sum 共␧HBP
+ IH兲 for the HOMO, is given in parentheses; for all lower orbitals, next to the orbital energies, the energies shifted up by this amount are given. AADs for
the shifted orbital energies are also included in the table.

GGA-BP EXXa HF KS Expt.

Molecule MO −␧i −␧i −␧i −␧i

COb 5␴ 9.18; 共4.83兲 15.14 15.12 14.01 14.01
1␲ 11.95; 16.78 17.56 17.42 16.80 16.91
4␴ 14.27; 19.10 20.80 21.94 19.37 19.72
AAD 5.08; 0.25 0.95 1.28 0.15

N 2c 3␴g 10.39; 共5.19兲 17.24 17.27 15.57 15.58

1␲u 11.72; 16.91 17.68 16.72 16.68 16.93
2␴u 13.60; 18.79 20.24 21.21 18.77 18.75
AAD 5.21; 0.02 1.30 1.45 0.09

HFd 1␲ 9.75; 共6.44兲 17.70 17.69 16.18 16.19

3␴ 13.61; 20.04 21.14 20.92 19.90 19.9
AAD 6.51; 0.07 1.37 1.26 0.00

H 2O e 1b1 7.32; 共5.3兲 13.85 13.85 12.62 12.62

3a1 9.46; 14.76 15.82 15.89 14.73 14.74
1b2 13.19; 18.49 19.31 19.35 18.33 18.55
AAD 5.34; 0.04 1.02 1.06 0.08

FCNf 2␲ 8.83; 共4.82兲 13.64 13.68 13.65 13.65

7␴ 9.68; 14.50 14.91 16.38 14.72 14.56
1␲ 14.02; 18.84 20.26 22.16 19.74 19.3
6␴ 17.43; 22.25 22.98 25.31 22.83 22.6
AAD 5.02; 0.22 0.42 1.85 0.21
a
Reference 67.
b
Reference 105.
c
Reference 106.
d
Reference 107.
e
Reference 108.
f
Reference 109.

KS virtual orbitals represent an “excited” electron interacting
with N − 1 electrons, rather than an extra electron interacting
with N electrons. They have therefore much lower orbital
energies than the virtual HF orbitals, and are much more
contracted. In KS-EXX calculations this will remain true,
since there is, in contrast to HF, still a single local optimized
effective potential for both the occupied levels and the unoc-
cupied ones.
Due to this physical nature of the virtual orbital energies,
the KS virtual-occupied orbital energy differences are, in
principle, much better approximations to the real excitation
energies than in the case of HF. In order to reproduce this
feature of the exact KS orbitals in approximate calculations,
the shape of the potential has to approach the exact one suf-
ficiently closely. In this respect the LDA/GGA potentials are
very deficient. This is already apparent from the large upshift
of the occupied orbital energies noted before. Such an upshift
cannot occur for the Rydberg orbitals, which are typically at
high energy, already close to the energy zero. Excitations to
such orbitals will become much too low. Often this failure
for the Rydberg excitations in the LDA and GGA methods is
ascribed to the lack of proper −1 / r decay of the potential in
those cases. That is not the true origin: it is the wrong posi-
tion 共not negative enough兲 of the occupied levels with re-
spect to the energy zero which causes this problem. We note
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that this problem does not occur in the KS-EXX model. Even
though the wrong energies for excitations to Rydberg orbitals
are not caused by the lack of proper asymptotic decay of the
LDA/GGA potentials, this deficiency of the these potentials
does have some adverse effects. It causes the Rydberg orbit-
als to have the wrong shape. In Ref. 78 a detailed account
has been given for the case of the Rydberg excitations in N2,
where the oscillator strengths of these excitations are se-
verely underestimated 共by factors of more than 50兲 in LDA/
GGA calculations. This is simply caused by the too tight
nature of the Rydberg orbitals in these calculations, which is
caused by the too rapid, exponential decay to zero of the
potential. As a consequence, also the spectral analysis of, for
instance, the polarizability reveals a wrong distribution over
the various excitations. We are not aware of such an analysis
in the case of KS-EXX calculations, but since its KS poten-
tial possesses the correct Coulombic asymptotics vx共r兲
→ −1 / 兩r兩, 兩r兩 → ⬁, we expect also the oscilator strengths to
be meaningful. The abovementioned crucial features of the
potential—proper behavior in the bulk molecular region in
order to get correct orbital energies and proper −1 / r decay to
get correct orbital shapes—are incorporated in the refined
approximate xc potentials37,110–112 which have been intro-
duced. The SAOP potential76,77 is an orbital-dependent func-
tional for the KS potential, which exhibits reasonably accu-
 062202-15 Orbital-dependent exchange-correlation functionals
FIG. 4. Schematic illustration of the positions of the exact Kohn–Sham
orbital energies in relation to the ionization energies and electron affinities
of the neutral donor 共D兲 and acceptor 共A兲 systems and of the negative A−.
The magnitude of the gap ⌬ between LUMO energy and electron affinity −A
is indicated for D and A, as well as the equality of −AA and ␧−a .
rate occupied orbital energies97 due to shape corrections of
the potential in the bulk molecular region, and in addition
has −1 / r asymptotic behavior. Both excitation energies and
oscillator strengths, and hence the spectral structure of re-
sponse properties, are therefore realistic.78
It is interesting to note that for a particular type of exci-
tations the abovementioned advantageous characteristic fea-
ture of the KS orbital spectrum turns, actually, to a serious
problem of TDDFT. These are excitations associated with
molecular long-range charge transfer 共CT兲 between an elec-
tron donor D and electron acceptor A.113–115 With a weak
interfragment interaction at the large D-A separation R the
corresponding excitation energy ␻CT becomes the difference
between VIP ID of the donor and the electron affinity AA of
the acceptor corrected with the electron-hole interaction
−1 / R
␻CT ⬇ ID − AA − 1/R, 共6.2兲
and at large separations R the difference 共ID − AA兲 becomes
the dominant term of Eq. 共6.2兲. Figure 4 presents a schematic
picture of the relevant KS orbital energies of the donor D,
acceptor A, and anionic acceptor A− fragments. In this case,
as follows from the abovementioned rigorous KS theory, a
fair estimate of ␻CT would be produced with the energy dif-
ference 共␧−a − ␧d兲 of the orbital energies of the singly occupied
MO of A− and the HOMO of D. But then, the energy differ-
ence 共␧a − ␧d兲 of the LUMO of A and HOMO of D, which is
the zero-order approximation 共6.1兲 of the excitation in TD-
DFT, yields a poor estimate of ␻CT. It has been pointed out
by Dreuw et al.114 that in the asymptotic limit of negligible
overlap between the donor orbital 共HOMO of D兲 and accep-
tor orbital 共LUMO of A兲 the modifications due to the cou-
pling matrix disappears when the standard adiabatic LDA
ALDA
kernel f xc is used, and the TDDFT result reduces to the
zero-order value 共␧a − ␧d兲. This value is much too low com-
pared to 共␧−a − ␧d兲 because of the essentially positive and large
difference ⌬A = ␧−a − ␧a between the energies of the extra and
excited electrons on the orbital ␾a 共see Fig. 4兲. For small
prototype molecules the evaluation of the difference ⌬A from
the accurate KS solution99 obtained from the correlated ab
initio CI density with the LB procedure37 produces ⌬A values
in the range 7–10 eV, and this is, basically, the error of the
TDDFT with the zero-order 共␧a − ␧d兲. As mentioned earlier,
this zero-order result is obtained when the standard xc kernel
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146.189.194.69 On: Sat, 20 Dec 2014 15:07:34
J. Chem. Phys. 123, 062202 共2005兲
ALDA
f xc is used. The proper treatment in TDDFT of long-range
ALDA
charge-transfer excitations requires a correction to f xc . It
is possible to formulate an orbital-dependent f xc which incor-
porates the required divergence at large R.115
VII. SUMMARY
We have argued that both Hartree–Fock and the use of
the exact-exchange functional in Kohn–Sham DFT are very
deficient models for the description of chemical bonding.
They both use a two-particle probability distribution which is
wrong, as can be seen from the shape of the “hole” a refer-
ence electron creates around itself: the hole is not centered
around the reference electron, but is delocalized over the
atoms forming the bond. From this wrong hole shape one can
understand deficiencies of this model, such as too diffuse
orbitals and density, hence wrong kinetic energy and
electron-nuclear attraction energy. The true xc hole is sub-
stantially more localized around the reference electron. That
is why rough localized model holes, like those of GGA,
which approximate this total hole, are so successful. Maybe,
we should not say that GGA is very accurate, but rather that
HF 共and EXX兲 is so inaccurate that it proved not to be very
difficult to do considerably better even with a rough hole
modeling like the one used in the LDA and GGA models.
It is possible to devise orbital-dependent functionals that
do describe the shape of the exchange-correlation correctly,
both for the dynamical correlation at equilibrium bond length
and for the nondynamical correlation at elongated bond
lengths. We have discussed the functional introduced in Refs.
35 and 58, and discussed its application to dissociating H2.32
Any functional, including the EXX functional, that rem-
edies the major deficiencies of the self-consistent orbitals
and orbital energies of LDA and GGA, which are caused by
the too weak attractive nature in the bulk molecular region
and the wrong asymptotic behavior of the corresponding po-
tential, will improve response properties as calculated with
time-dependent DFT. We have discussed such improvement
for the polarizability, which involves the orbital dependency
of the EXX model rather directly. It is also possible to use
orbital-dependent functionals for the KS potential directly,
such as the SAOP potential,76,77 which are easy to use and
remedy the deficiencies of the LDA/GGA potentials. Excel-
lent response properties are obtained. We have finally indi-
cated that the long-standing problem of wrong charge-
transfer transition energies in TDDFT can also be remedied
by invoking orbital dependence, this time in the exchange-
correlation kernel.
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