The optimized effective potential and the self-interaction correction in density

functional theory: Application to molecules

Jorge Garza, Jeffrey A. Nichols, and David A. Dixon

Citation: The Journal of Chemical Physics 112, 7880 (2000); doi: 10.1063/1.481421
View online: http://dx.doi.org/10.1063/1.481421
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/112/18?ver=pdfcov
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 JOURNAL OF CHEMICAL PHYSICS VOLUME 112, NUMBER 18 8 MAY 2000

The optimized effective potential and the self-interaction correction

in density functional theory: Application to molecules
Jorge Garza
Departamento de Quı́mica, División de Ciencias Básicas e Ingenierı́a, Universidad Autonóma
Metropolitana-Iztapalapa. A.P. 55-534, México Distrito Federal 09340, México
Jeffrey A. Nichols and David A. Dixona)
Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, P.O. Box 999,
Richland, Washington 99352
共Received 24 September 1999; accepted 13 January 2000兲
The Krieger, Li, and Iafrate approximation to the optimized effective potential including the
self-interaction correction for density functional theory has been implemented in a molecular code,
NWChem, that uses Gaussian functions to represent the Kohn and Sham spin–orbitals. The
differences between the implementation of the self-interaction correction in codes where
planewaves are used with an optimized effective potential are discussed. The importance of the
localization of the spin–orbitals to maximize the exchange-correlation of the self-interaction
correction is discussed. We carried out exchange-only calculations to compare the results obtained
with these approximations, and those obtained with the local spin density approximation, the
generalized gradient approximation and Hartree–Fock theory. Interesting results for the energy
difference 共GAP兲 between the highest occupied molecular orbital, HOMO, and the lowest
unoccupied molecular orbital, LUMO, 共spin–orbital energies of closed shell atoms and molecules兲
using the optimized effective potential and the self-interaction correction have been obtained. The
effect of the diffuse character of the basis set on the HOMO and LUMO eigenvalues at the various
levels is discussed. Total energies obtained with the optimized effective potential and the
self-interaction correction show that the exchange energy with these approximations is
overestimated and this will be an important topic for future work. © 2000 American Institute of
Physics. 关S0021-9606共00兲30114-3兴

I. INTRODUCTION
Density functional theory 共DFT兲1,2 has become an im-
portant tool for use by chemists and physicists in understand-
ing the chemical bond in molecules, solids, and surfaces.
From a computational point of view, the most important ver-
sion of this theory is that originally developed by Kohn and
Sham.3 With current computers, this theory can be used to
study the electronic structure of very large molecules. The
results obtained with this theory can be compared with re-
sults obtained from many-body perturbation theory 共MP2兲,
but with much reduced computational cost.4–6 In a number of
cases, especially for molecules containing transition metals
DFT is significantly better than most molecular orbital meth-
ods based on a single configuration. However, DFT fails in
predicting long-range interactions,7 does not describe weak
bonds very well,8 and, for a variety of chemical reactions,
barrier heights are predicted incorrectly.9 In many cases, the
principal reason for these errors is due to the wrong
asymptotic behavior exhibited by the exchange-correlation
potential.10 In addition, self-interaction is not cancelled ap-
propriately by many functionals that are an approximation to
the exact exchange-correlation functional, E xc . 10–13 The
self-interaction is defined to be the interaction of an electron
a兲
Electronic mail: david.dixon@pnl.gov
with itself and in Hartree–Fock 共HF兲 theory this term is ex-
actly cancelled from the Coulomb expression via the ex-
change contribution.
Perdew and Zunger have suggested a way to include
self-interaction in approximations to E xc . 11 Atoms are the
principal systems where the self-interaction correction 共SIC兲
has been applied11,14–20 and several efforts to include this
correction in molecular codes have been reported.21,22 Unfor-
tunately, the equations that emerge from this model depend
on each spin-orbital occupied in the system and the solution
of the Kohn–Sham equations is complicated.15,23,24 Even
with this handicap, techniques borrowed from the solid state
physics community can be used to find a solution to this
problem.25–29 For example, the Kohn–Sham equations can
be represented in reciprocal space and the spin–orbitals writ-
ten in terms of plane waves; we will refer to these as PW
methods. On the other hand, some effort21,22 has been de-
voted to incorporating the SIC approximation in molecular
codes where Gaussian functions are used; we will refer to
these as GF methods. The principal problem with the GF
methods is the dependence of each spin–orbital on the effec-
tive potential that is present in the differential equations and
the noncanonical equations that appear when the orthogonal-
ity restriction is applied.
Recent results in the literature have shown that the opti-
mized effective potential 共OEP兲30,31 with the approximation

0021-9606/2000/112(18)/7880/11/$17.00 7880 © 2000 American Institute of Physics

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 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000
of Krieger, Li, and Iafrate 共KLI兲32–34 is a good alternative to
obtain a local potential for functionals that depend explicitly
on the spin–orbitals,35–38 such as the SIC approximation.
This method offers the advantage of using a local potential
and canonical equations. In this way, we can use the OEP-
KLI method with the SIC approximation in a molecular GF
code such as NWChem.39 The aim of this paper is to show
the reliability of these techniques applied for the first time to
molecular systems. In Sec. II we present our working equa-
tions and briefly describe the implementation of these in
NWChem. The results are reported and contrasted with other
methodologies in Sec. III. Finally, in Sec. IV, conclusions
and discussion of future work are presented.
II. THE LOCAL EFFECTIVE POTENTIAL IN KOHN AND
SHAM THEORY
The exact total energy within the Kohn–Sham 共KS兲
theory3 can be written as
E KS关 ␳ ␣ , ␳ ␤ 兴 ⫽T s 关 兵 ␸ i ␴ 其 兴 ⫹J 关 ␳ 兴 ⫹E xc 关 ␳ ␣ , ␳ ␤ 兴
冕
⫹ dr␳ 共 r兲 ␷ 共 r兲 .
The first term in Eq. 共1兲 is the kinetic energy of a system of
noninteracting particles
N␴
T s⫽ 兺 兺 具 ␸ i␴兩 ⫺
␴ ⫽ ␣ , ␤ i⫽1
1
2 ⵜ 2兩 ␸ i␴典 ,
and the second term, J 关 ␳ 兴 , is the coulombic interaction en-
ergy of these particles
J⫽
1
2
冕冕 drdr⬘
␳ 共 r兲 ␳ 共 r⬘兲
兩 r⫺r⬘兩
. 共3兲
The interaction energy between the electron density, ␳ (r),
and the external potential due to the electron–nuclear attrac-
tion, ␷ (r), is given by the last term
冕
V ne ⫽ dr␳ 共 r兲 ␷ 共 r兲 .
These terms are all known exactly. The exchange-correlation
functional, E xc , contains the remaining contributions to both
the kinetic energy and the electron–electron interaction. This
functional is not well known. The partitioning of the total
energy in this way is an important characteristic of this
theory since the first three terms are well-known and we can
focus our attention on correctly determining E xc . Two addi-
tional important features of the theory are how the electron
density is built
N␴
␳ 共 r兲 ⫽ 兺 兺 ␸ i*␴共 r兲 ␸ i ␴共 r兲
␴ ⫽ ␣ , ␤ i⫽1
N␴
⫽ 兺 兺 ␳ i ␴共 r兲 ⫽ ␴ ⫽兺␣ , ␤ ␳ ␴共 r兲 ,
␴ ⫽ ␣ , ␤ i⫽1
and how the spin–orbitals, ␸ i ␴ , that minimize the total en-
ergy satisfy the differential equations
␴
共 ⫺ 21 ⵜ 2 ⫹ ␷ eff共 r兲兲 ␸ i ␴ 共 r兲 ⫽␧ i ␴ ␸ i ␴ 共 r兲 ,
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Optimized effective potential 7881
␴
where the local effective potential, ␷ eff (r), has three contri-
butions
冕
␳ 共 r⬘兲 ␦ E xc
␴
␷ eff共 r兲 ⫽ dr⬘ ⫹ ␷ 共 r兲 ⫹ ␴ . 共7兲
兩 r⫺r⬘兩 ␦ ␳ 共 r兲
Equation 共5兲 is a consequence of the anti-symmetric wave
function that corresponds to the system of noninteracting
particles. Equation 共6兲 is especially important because, by
construction, with a local potential we can know the state of
all particles of the system and consequently the exact elec-
tron density. Because the asymptotic behavior of the electron
density is determined by the first ionization potential 共IP兲,
the highest occupied molecular orbital 共HOMO兲 energy is
identified directly with this property, ␧ HOMO⫽⫺IP. 13,37,40–42
Up to now, many HOMO energies obtained from approxi-
mate exchange-correlation functionals do not satisfy this
requirement.37
The most frequently used approximations for E xc can be
classified into three categories;
共1兲 the local spin density approximation 共LSDA兲 which is
based on the electron gas approach and is explicitly de-
共1兲 pendent upon the electron density,1
共2兲 the generalized gradient approximation 共GGA兲 which is
explicitly dependent on both the electron density and its
derivative,1 and
共3兲 the hybrid approximations where some amount of exact-
共2兲 exchange is mixed with exchange-correlation functionals
from LSDA and GGA.
The hybrid approaches, for example the B3 or so-called
Becke ‘‘half and half,’’ have provided significantly im-
proved DFT results43,44 for some classes of chemical prob-
lems. Without doubt, these types of exchange-correlation
functionals can be used to reliably study many types of
chemical problems, but the simplest molecular one-electron
problem, the dissociation of the H⫹ 2 molecule, cannot be well
described with any of the above approximations because
self-interaction still remains an important issue.1,45
共4兲 A. The SIC approximation and its nonlocal exchange-
correlation potential
The SIC approximation of Perdew and Zunger11 can be
written in terms of the Columb and exchange-correlation en-
ergies of each spin–orbital in the following way:
SIC
E xc 关 兵 ␳ i␴其 兴
N␴
approx ␣ ␤
⫽E xc 关␳ ,␳ 兴⫺ 兺 兺 共 E xcapprox关 ␳ i ␴ ,0兴 ⫹J 关 ␳ i ␴ 兴 兲 .
␴ ⫽ ␣ , ␤ i⫽1
共8兲
From this equation, it is evident that the exchange-
correlation functional is dependent on each spin–orbital.
Furthermore, if a transformation is applied to the spin–
共5兲 orbitals, the resultant functional will differ from the former,
implying that the exchange-correlation-SIC functional is
noninvariant under any transformation 共including unitary
transformations兲.
When the SIC approximation was first introduced, the
共6兲 total energy was minimized with the restriction of normal-
 7882 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000
ization of the spin–orbitals in order to get canonical differ-
ential equations and post orthogonalization was then em-
ployed using the Schmidt method. Alternatively,
orthogonality could be included directly with the resulting
differential equations23–25
␴
共 ⫺ 21 ⵜ 2 ⫹ ␷ eff ␴ ,i
共 r兲 ⫹V sic 共 r兲兲 ␸ i ␴ 共 r兲 ⫽ 兺j ␧ j ␴ ␸ j ␴共 r兲 ,
where,
␦ E xc 关 ␳ i ␴ ,0兴
冕 ␳ i ␴ 共 r⬘ 兲
approx
␴ ,i
V sic 共 r兲 ⫽⫺ ⫺ dr⬘
␦ ␳ i␴ 兩 r⫺r⬘ 兩
The orthogonality restriction gives rise to the inclusion of the
off-diagonal terms in the sum found in Eq. 共9兲. At first
glance Eq. 共9兲 appears formidable because we have a nonlo-
cal potential together with a set of coupled differential equa-
tions. The usual approach to solving Eq. 共9兲 is to use PW46,47
methods where one obtains just one orbital at a time. This
leads to an algebraic problem 关Eq. 共9兲兴 which can be solved
with fewer restrictions than those used in GF methods.48 In
the GF methods, all orbitals, occupied and virtual, are ob-
tained at the same time. The incorporation of this approach
into current GF codes for the treatment of the electronic
structure of molecules is, thus, more difficult.
There has been recent work where Eq. 共9兲 was solved
with plane waves and with the additional restriction of maxi-
mizing the exchange-correlation-SIC energy.28,29 A conse-
quence of this restriction is localization of the
spin–orbitals.15,23,24,25 The results obtained are encouraging.
The SIC approximation appears to be a good alternative to
incorporate the correct asymptotic behavior of the exchange-
correlation potential. Up to now, the efforts to implement
SIC into GF codes has been limited to perturbative
schemes.21,22 In this approach the exchange-correlation-SIC
energy from Eq. 共8兲 is evaluated with the localized spin–
orbitals from an LDA or GGA calculation after the self-
consistent process is completed. In addition, the SIC ap-
proximation with maximization of the exchange-correlation-
SIC energy restriction has been implemented for diatomic
molecules. Unfortunately, this technique has not been ap-
plied to other systems.23,24
Independent of the method used to solve Eq. 共9兲, it is
important to point out a particular problem associated with
its solution. In many cases, the HOMO–LUMO 共lowest un-
occupied molecular orbital兲 gap is used in the characteriza-
tion of the reactivity of a chemical system.1,49 The HOMO
orbital can be obtained by solving Eq. 共9兲 with the Hamil-
tonian
␴ ␴ ␴ ,HOMO
h HOMO ⫽⫺ 21 ⵜ 2 ⫹ ␷ eff共 r兲 ⫹V sic 共 r兲 ,
but, it is unclear which Hamiltonian corresponds to the cor-
rect LUMO orbital.
B. The optimized effective potential and the Krieger,
Li, and Iafrate approximation
The HF potential has been broadly applied to atomic and
molecular systems and is the foundation of molecular orbital
theory.48 This potential, although very useful, is a nonlocal
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Garza, Nichols, and Dixon
potential and it is, therefore, useful to try to find a suitable
local potential. This is the essence of Slater’s approximation
to the Hartree–Fock potential which involves solving
integro-differential equations with a local potential50 in order
to approximate the HF potential directly. A more general
approach as described by Sharp and Horton30 is to ‘‘Find that
共9兲 potential, the same for all electrons, such that when it, and
consequently the wave functions, are given a small variation,
the energy of the system remains stationary.’’ With this same
idea in mind, Talman and Shadwick31 found the OEP for the
HF energy of many-electron atoms. Although the approach is
. 共10兲
clear, the resultant equations are hard to solve for molecules.
For this reason, these equations have not yet been applied to
large systems. Krieger, Li, and Iafrate 共KLI兲32,34 have ob-
tained a good approximation to the OEP which has been
successfully applied to atoms. The OEP-KLI offers the ad-
vantage of obtaining a local potential for systems where the
total energy depends explicitly on spin–orbitals. While it is
important to know the theory behind the approximations
made, we will mention only those topics most importantly
related to this work.
Suppose that we have the exchange-correlation func-
tional depending explicitly on spin–orbitals and we concern
ourselves with the HF, B3, or SIC approximations. The
OEP30,31 will be found if the total energy is minimized such
that
␦ E 关 兵 ␸ i␴其 兴
␦V␴ 冏 OEP
V␴
⫽0. 共12兲
In addition, V ␴OEP must be a local potential such that the
spin–orbitals can be obtained from
共 ⫺ 21 ⵜ 2 ⫹V ␴OEP共 r兲兲 ␸ i ␴ 共 r兲 ⫽␧ i ␴ ␸ i ␴ 共 r兲 . 共13兲
The last two equations are the principal components of the
OEP theory. To find V ␴OEP and the spin–orbitals we must
simultaneously solve these two equations. In principle, the
total energy from Eq. 共12兲 could be any energy represented
with spin–orbitals, for example, the HF or the Kohn–Sham
energies. In the HF context, the V ␴OEP will be different than
the effective potential that emerged from this theory. But in
the context of Kohn–Sham theory, if we are using the exact
exchange-correlation functional, the V ␴OEP will correspond to
the Kohn–Sham local effective potential.3 Because we are
using Kohn–Sham theory, E⫽E KS . If the chain rule and
arguments from perturbation theory are used, then Eq. 共12兲
共11兲 can be transformed in the following manner:
冕
⬁
␦ E KS ␸ k*␴ 共 r兲 ␸ k ␴ 共 r⬘ 兲
兺i dr⬘
␦ ␸ i␴
兺
共 r⬘ 兲 k⫽1 ␧ i ␴ ⫺␧ k ␴
␸ i ␴ 共 r兲
k⫽i
⫹complex conjugate⫽0. 共14兲
From Eq. 共1兲 the derivative ␦ E KS / ␦ ␸ i ␴ (r) can be evaluated
to get
 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000 Optimized effective potential 7883

兺冕 i
1
2 冋
dr⬘ ⫺ ⵜ 2 ⫹ 冕 dr⬙
␳ 共 r⬙ 兲
兩 r⬘ ⫺r⬙ 兩
⫹ ␷ 共 r⬘ 兲 OEP-KLI
V xc ␴ 共 r兲 ⫽
N␴

兺
i⫽1
␴
␳ 共 r兲
i␴
␳ i ␴ 共 r兲 u xc 共 r兲

册 i␴
N␴
1 ␦ E xc ␳ i ␴ 共 r兲关 V̄ xc
OEP -KLI,i
⫺ū xc 兴
⫹
␸ i*␴ 共 r⬘ 兲 ␦ ␸ i ␴ 共 r⬘ 兲
⫹ 兺
i⫽1
␴
␴
␳ 共 r兲
. 共21兲

冋 册
i⫽HOMO␴
⬁
␸ k*␴ 共 r兲 ␸ k ␴ 共 r⬘ 兲
⫻ 兺
k⫽1 ␧ i ␴ ⫺␧ k ␴
␸ i*␴ 共 r⬘ 兲 ␸ i ␴ 共 r兲 ⫽0. 共15兲
In this equation, the second sum is restricted to run over all
spin–orbitals except the HOMO spin-orbital which insures
k⫽i the correct asymptotic behavior of the potential. The constant
i␴
Using Eq. 共13兲, the last equation can be written in terms of ū xc is the average value

冕
the V ␴OEP as
i␴ i␴
⫽ dr␳ i ␴ 共 r兲 u xc 共 r兲 . 共22兲
冕 ⬘冋
ū xc
兺i dr V ␴OEP共 r⬘ 兲 ⫺ 冕 dr⬙
␳ 共 r⬙ 兲
兩 r⬘ ⫺r⬙ 兩
⫺ ␷ 共 r⬘ 兲 OEP-KLI,i
V̄ xc ␴ is obtained from the algebraic equation

⫺
1 ␦ E xc
␸ i*␴ 共 r⬘ 兲 ␦ ␸ i ␴ 共 r⬘ 兲 册 N ␴ ⫺HOMO␴

兺
i⫽1
共 ␦ i j ⫺M ␴i j 兲共 V̄ xc
OEP-KLI,i
␴
i␴
⫺ū xc j␴
兲 ⫽V̄ Sxc j ␴ ⫺ū xc ,

冋 册
⬁
␸ k*␴ 共 r兲 ␸ k ␴ 共 r⬘ 兲 j⫽1,2, . . . , 共 N ␴ ⫺HOMO␴ 兲 , 共23兲
⫻ 兺
k⫽1 ␧ k ␴ ⫺␧ i ␴
␸ i*␴ 共 r⬘ 兲 ␸ i ␴ 共 r兲 ⫽0. 共16兲
k⫽i where

冕
N␴ i␴
Defining the following quantities: ␳ i ␴ 共 r兲 u xc 共 r兲
V̄ Sxc j ␴ ⫽ dr␳ j ␴ 共 r兲 兺 ␴
␳ 共 r兲
,

冕
i⫽1
␳ 共 r⬘ 兲
OEP
␴ 共 r 兲 ⫽V ␴ 共 r 兲 ⫺
OEP
dr⬘ ⫺ ␷ 共 r兲 共17兲 共24兲
冕
V xc
兩 r⫺r⬘ 兩 ␳ j ␴ 共 r兲 ␳ i ␴ 共 r兲
M ␴ji ⫽ dr .
␳ ␴ 共 r兲
and
Using the KLI approximation, the procedure to find the
i␴
1 ␦ E xc OEP-KLI is the following. For a given set of spin–orbitals,
u xc 共 r兲 ⫽ . 共18兲
␸ i*␴ 共 r兲 ␦ ␸ i ␴ 共 r兲 evaluate the constants defined in Eqs. 共22兲 and 共24兲 to find
OEP-KLI,i
the average values V̄ xc ␴ from Eq. 共23兲. These V̄ xc
OEP-KLI,i
␴
Equations 共16兲 and 共13兲 have their final form values are used in Eq. 共21兲 to determine the OEP-KLI,
OEP-KLI

冕
V xc ␴ . With this potential, new spin–orbitals can be ob-
兺i dr⬘ 关 V xc
OEP i␴
␴ 共 r⬘ 兲 ⫺u xc 共 r⬘ 兲兴
tained from Eq. 共20兲 and the iterative procedure continued
until convergence is reached.

冋兺 册
⬁ The OEP-KLI theory discussed above is completely gen-
␸ k*␴ 共 r兲 ␸ k ␴ 共 r⬘ 兲 eral. It can be applied to any method which explicitly de-
⫻ ␸ i*␴ 共 r⬘ 兲 ␸ i ␴ 共 r兲 ⫽0 共19兲
k⫽1 ␧ k ␴ ⫺␧ i ␴ pends on the spin–orbitals, such as, HF, B3, or SIC approxi-
k⫽i
mations. If our interest is restricted to the SIC
and approximation, then from Eqs. 共18兲 and 共8兲 we have

冉 冕 冊
␦ E xc 关 ␳ i ␴ ,0兴
冕 ␳ i ␴ 共 r⬘ 兲
approx
1 ␳ 共 r⬘兲 i␴
u xc 共 r兲 ⫽⫺ ⫺ dr⬘ . 共25兲
⫺ ⵜ 2⫹ dr⬘ ⫹ ␷ 共 r兲 ⫹V xc
OEP
␴ 共 r兲 ␸ i ␴ 共 r兲 ␦ ␳ i␴ 兩 r⫺r⬘ 兩
2 兩 r⫺r⬘兩
⫽␧ i ␴ ␸ i ␴ 共 r兲 . 共20兲 Whereas this quantity is included directly in the potential of
Eq. 共9兲, in the OEP-KLI approximation it is included through
Now the problem is reduced to finding the exchange- Eq. 共21兲.
correlation optimized effective potential V xc OEP In the implementation of the OEP-KLI in NWChem’s
␴ rather than
whole OEP, V ␴ . Equations 共19兲 and 共20兲 suggest an itera-
OEP DFT module, the matrix elements 具 f ␮ 兩 V xc OEP-KLI
␴ 兩 f ␯ 典 are re-
tive procedure. Start with a set of spin–orbitals in order to quired to build the Fock matrix. In this case, f ␮ and f ␯
␴ from Eq. 共19兲. Substitute this potential in Eq.
OEP
obtain V xc represent Gaussian functions. The effort to evaluate the inte-
共20兲 to find a new set of spin–orbitals. Iterate this procedure grals that appear in the OEP-KLI theory, namely Eqs. 共22兲
until convergence has been reached. Unfortunately, the inte- and 共24兲, is in addition to the effort used to evaluate the Fock
gral equations of Eq. 共19兲 are hard to solve and have been matrix in usual DFT calculations.4 The most expensive inte-
applied only to systems with spherical symmetry. Kriger, Li, gral is related to the matrix element
and Iafrate developed an approximation which avoided N␴ i␴ N␴ i␴
␳ i ␴ 共 r兲 u xc 共 r兲 ␳ i ␴ 共 r兲 u xc 共 r兲
working with the infinite sum that appeared in Eq. 共19兲.32,34 具 f ␮兩 兺 兩 f ␯典 ⫽ 兺 具 f ␮兩 兩 f ␯典 . 共26兲
This approximation to V xcOEP
␴ is written as i⫽1 ␳ ␴ 共 r兲 i⫽1 ␳ ␴ 共 r兲
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 7884 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000 Garza, Nichols, and Dixon

TABLE I. Effect of the addition of diffuse basis functions to the cc-pVTZ basis set on LUMO and HOMO energies, and the GAP (␧ LUMO – ␧ HOMO), for Be,
LiH, and H2 O. See Table II for the definition of the diffuse functions. All quantities are in Hartrees.

HOMO LUMO GAP

LDA GGA SIC-OEP HF LDA GGA SIC-OEP HF LDA GGA SIC-OEP HF

Be
cc-pVTZ ⫺0.170 ⫺0.181 ⫺0.308 ⫺0.309 ⫺0.044 ⫺0.051 ⫺0.178 0.049 0.126 0.130 0.130 0.358
aug-cc-pVTZ ⫺0.170 ⫺0.181 ⫺0.308 ⫺0.309 ⫺0.045 ⫺0.052 ⫺0.178 0.015 0.125 0.129 0.130 0.324
aug-cc-pVTZ⫹1 ⫺0.170 ⫺0.181 ⫺0.308 ⫺0.309 ⫺0.045 ⫺0.053 ⫺0.179 0.002 0.125 0.129 0.130 0.312
aug-cc-pVTZ⫹2 ⫺0.170 ⫺0.181 ⫺0.308 ⫺0.309 ⫺0.046 ⫺0.053 ⫺0.179 0.000 0.124 0.129 0.130 0.310
aug-cc-pVTZ⫹3 ⫺0.170 ⫺0.181 ⫺0.308 ⫺0.309 ⫺0.046 ⫺0.053 ⫺0.179 0.000 0.124 0.129 0.130 0.309
LiH
cc-pVTZ ⫺0.128 ⫺0.139 ⫺0.301 ⫺0.301 ⫺0.040 ⫺0.048 ⫺0.150 ⫺0.001 0.088 0.091 0.151 0.300
aug-cc-pVTZ ⫺0.128 ⫺0.139 ⫺0.301 ⫺0.302 ⫺0.041 ⫺0.049 ⫺0.151 ⫺0.007 0.087 0.090 0.150 0.294
aug-cc-pVTZ⫹1 ⫺0.128 ⫺0.139 ⫺0.301 ⫺0.302 ⫺0.041 ⫺0.049 ⫺0.151 ⫺0.008 0.087 0.090 0.150 0.294
aug-cc-pVTZ⫹2 ⫺0.128 ⫺0.139 ⫺0.301 ⫺0.302 ⫺0.041 ⫺0.049 ⫺0.151 ⫺0.008 0.087 0.090 0.150 0.294
aug-cc-pVTZ⫹3 ⫺0.128 ⫺0.139 ⫺0.301 ⫺0.302 ⫺0.041 ⫺0.049 ⫺0.151 ⫺0.008 0.087 0.090 0.150 0.294
H2O
cc-pVTZ ⫺0.207 ⫺0.217 ⫺0.513 ⫺0.505 0.034 0.023 ⫺0.205 0.132 0.240 0.240 0.308 0.637
aug-cc-pVTZ ⫺0.225 ⫺0.235 ⫺0.503 ⫺0.510 ⫺0.014 ⫺0.024 ⫺0.201 0.029 0.211 0.211 0.302 0.540
aug-cc-pVTZ⫹1 ⫺0.225 ⫺0.235 ⫺0.518 ⫺0.510 ⫺0.016 ⫺0.026 ⫺0.216 0.008 0.209 0.209 0.302 0.509
aug-cc-pVTZ⫹2 ⫺0.225 ⫺0.235 ⫺0.518 ⫺0.510 ⫺0.016 ⫺0.026 ⫺0.216 0.002 0.209 0.209 0.302 0.513
aug-cc-pVTZ⫹3 ⫺0.225 ⫺0.235 ⫺0.518 ⫺0.510 ⫺0.016 ⫺0.026 ⫺0.216 0.001 0.209 0.209 0.302 0.511

This is principally because the electrostatic potential gener-
ated by each spin-orbital density 关in Eq. 共25兲兴 must be cal-
culated numerically. Although we are using new techniques
to efficiently obtain the electrostatic potential,51 this is the
major problem to incorporating the OEP-KLI in standard GF
based DFT codes. In addition, it is well known that the SIC
energy is maximized when the spin–orbitals are localized,
and we use the Foster–Boys localization criteria with the
Edmiston–Ruedenburg method,52 in each step of the self-
OEP-KLI
consistent process to build V xc ␴ . the previous basis set 共see Table II for orbital exponents兲.
The OEP-KLI potential for open shell systems, as de-
scribed in Eq. 共21兲, is built separately for both alpha and beta
spin–orbital densities with a HOMO for each density. In the
case of symmetry degeneracies, all symmetry equivalent
HOMOs are excluded in the second term of Eq. 共21兲 to in-
sure proper asymptotic behavior. In addition, the required
localization is performed for each set of alpha and beta
spin–orbitals.53 The type of localization scheme used is not
important, since the objective here is to maximize the
exchange-correlation self-interaction energy. The SIC PW
methods as well as the numerical SIC methods applied to
atoms observed localization as a by-product of maximizing
the exchange-correlation self-interaction.15,23–25,28,29
III. RESULTS
We have applied the OEP-KLI and SIC approximations
to atomic and molecular systems. We limited our study to
exchange-only calculations using experimental geometries,
because we wanted to assess the applicability of these ap-
proximations in GF molecular codes. Furthermore, we
wanted to investigate the role of the localization of the orbit-
als and the energy differences between the perturbative
method, as described in Sec. II A, and the OEP-KLI self-
consistent method as described and implemented in Sec. II B.
Because we are interested in the energies of the occupied
and unoccupied orbitals, we show in Table I the convergence
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of the HOMO, LUMO, and their difference, GAP⫽␧ L
⫺␧ H , for Be, LiH, and H2 O obtained with the HF and SIC-
OEP methods as a function of adding diffuse functions to the
basis set. We started from the cc-pVTZ,54 and aug-cc-
pVTZ54 correlation-consistent basis sets and added addi-
tional diffuse functions 共diffuse S, P, D, and F shells where
appropriate, labeled as aug-cc-pVTZ⫹1, aug-ccpVTZ⫹2,
and aug-cc-pVTZ⫹3兲 to the aug-cc-pVTZ basis set with the
diffuse functions obtained by geometric extrapolation from
Table I illustrates the correct asymptotic convergence of the
LUMO obtained at the HF level to zero. Furthermore, it
shows that the LUMO obtained at the SIC-OEP level does
not converge to zero as does the HF value. The LUMOs at
the LDA and GGA levels for these three species also do not
converge to zero as does the HF value but rather converge to
a negative value with a smaller absolute value as compared
to the SIC-OEP results. In addition, the LUMO is apparently
converged to the asymptotic value 共in terms of additional
diffuse functions兲 with the aug-cc-pVTZ⫹1 basis set. Thus,
this basis set was used for all of the calculations discussed
below.
In Table III we show the total energies and components
of the electronic energy obtained with the Dirac55 共LSDA兲
and Becke56 共GGA兲 functionals for He, H2 , Be, LiH, H2 O,
and CH4 with the aug-cc-pVTZ⫹1 basis set. In addition,
Table III includes the results obtained with the SIC approxi-
mation in its variants: SIC perturbative 共SIC–Pert兲, SIC with
OEP without localized spin–orbitals 共SIC–Noloc兲, and SIC
with OEP and localized spin–orbitals 共SIC-OEP兲. The SIC
energy was evaluated using the Dirac5 functional and in all
calculations the exact Coulomb potential is used. Table III
also includes the HF results for comparison.
The well-known underestimation of the exchange energy
at the LSDA level can be seen in Table III. This behavior is
corrected when the SIC approximation is applied. The total
 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000 Optimized effective potential 7885

TABLE II. Exponents for additional diffuse functions added to the aug-cc-pVTZ basis set.a

Basis set Shell function Exponent Basis set Shell function Exponent

H Be
aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹ aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹
S 0.008 000 S 0.005 124
P 0.025 000 P 0.000 998
D 0.080 000 D 0.023 720
aug-cc-pVTZ⫹2 aug-cc-pVTZ⫹1⫹ F 0.072 310
S 0.002 530 aug-cc-pVTZ⫹2 aug-cc-PVTZ⫹1⫹
P 0.006 130 S 0.001 747
D 0.025 911 P 0.000 141
aug-cc-pVTZ⫹3 aug-cc-pVTZ⫹2⫹ D 0.008 604
S 0.000 622 F 0.034 108
P 0.001 611 aug-cc-pVTZ⫹3 aug-cc-pVTZ⫹2⫹
D 0.006 055 S 0.000 594
O P 0.000 020
aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹ D 0.003 121
S 0.023 050 F 0.016 088
P 0.016 677 Li
D 0.071 000 aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹
F 0.175 070 S 0.002 040
aug-cc-pVTZ⫹2 aug-cc-pVTZ⫹1⫹ P 0.004 040
S 0.007 130 D 0.017 184
P 0.004 656 F 0.036 405
D 0.023 560
F 0.061 299 aug-cc-pVTZ⫹2 aug-cc-pVTZ⫹1⫹
aug-cc-pVTZ⫹3 aug-cc-pVTZ⫹2⫹ S 0.000 548
S 0.002 206 P 0.001 794
P 0.001 300 D 0.007 959
D 0.007 817 F 0.016 242
F 0.021 463 aug-cc-pVTZ⫹3 aug-cc-pVTZ⫹2⫹
He S 0.000 147
aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹ P 0.000 797
S 0.012 637 D 0.003 686
P 0.052 402 F 0.007 246
D 0.107 310
C N
aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹ aug-cc-pVTZ⫹1 aug-cc-p-VTZ⫹
S 0.015 080 S 0.018 570
P 0.010 536 P 0.013 980
D 0.031 447 D 0.048 620
F 0.094 381 F 0.121 220
F
aug-cc-pVTZ⫹1 aug-cc-pVTZ⫹
S 0.027 579
P 0.020 279
D 0.099 724
F 0.273 436
a
Primary basis set is given on the line above the exponents and the diffuse functions are added to this basis set.
For example, for C, aug-cc-pVTZ⫹1⫽aug-cc-pVTZ basis set⫹diffuse s⫹diffuse p⫹diffuse d⫹diffuse f.

energy is improved using any of the SIC approaches de- SIC-OEP as an alternative in describing atomization energies
scribed in Sec. II above. The SIC–Pert total energies are or transition states.
greater than that obtained with the self-consistent OEP pro- The differences we found between the total energy of the
cess, except when the localization of the orbitals is relevant, SIC-OEP and the other methods are even more accentuated
for example water or methane. In this case, if we want to use when looking at the orbital energies. In Table IV we show
the OEP with the SIC approximation, the additional restric- the energies that correspond to the HOMO, LUMO, and
tion of localization of the spin–orbitals must be applied in GAP as defined above for the systems contained in Table III.
each step of the self-consistent process to assure a maximi- In addition, we have included results for the H⫺ and F⫺
zation of the exchange-SIC energy. Although we obtain a anions as issues have been raised in the literature as to the
better total energy with the SIC approximation, the exchange appropriate DFT treatment of such ions due to the presence
energy obtained with this approximation is greater than the of unbound HOMOs at the LDA and GGA DFT levels.57–59
Hartree-Fock value in almost all of the cases studied here. As shown in Table IV, we also find unbound LUMOs at the
More attention must be given to this issue in order to use the LDA and GGA levels with the aug-cc-pVTZ⫹1 basis set. In
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 7886 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000 Garza, Nichols, and Dixon

TABLE III. Total energy and components of the electronic energy in Hartrees. The core component is the
kinetic energy plus the electron–nuclei interaction.

Slater (V x ␴ ) Slater (V x ␴ ) Slater (V x ␴ )

System Slater (V x ␴ ) Becke (V x ␴ ) ⫹SIC–Pert ⫹SIC–Noloc ⫹SIC–OEP HF

He 共Total兲 ⫺2.723 197 ⫺2.862 856 ⫺2.857 412 ⫺2.861 228 ⫺2.861 225 ⫺2.861 225
Core ⫺3.844 288 ⫺3.871 284 ⫺3.844 288 ⫺3.886 696 ⫺3.886 692 ⫺3.886 683
Coulomb 1.973 751 2.024 315 1.973 751 2.050 942 2.050 934 2.050 916
Exchange ⫺0.852 660 ⫺1.015 887 ⫺0.986 875 ⫺1.025 474 ⫺1.025 467 ⫺1.025 458

H2 共Total兲 ⫺1.043 125 ⫺1.131 443 ⫺1.131 264 ⫺1.133 066 ⫺1.133 066 ⫺1.133 064
Core ⫺2.484 669 ⫺2.499 845 ⫺2.484 669 ⫺2.505 683 ⫺2.505 683 ⫺2.505 680
Coulomb 1.278 531 1.308 504 1.278 531 1.316 959 1.316 959 1.316 953
Exchange ⫺0.551 126 ⫺0.654 242 ⫺0.639 266 ⫺0.658 481 ⫺0.658 481 ⫺0.658 477

Be 共Total兲 ⫺14.222 935 ⫺14.565 850 ⫺14.574 566 ⫺14.578 265 ⫺14.578 265 ⫺14.572 881
Core ⫺19.002 548 ⫺19.063 009 ⫺19.002 548 ⫺19.046 123 ⫺19.046 123 ⫺19.061 952
Coulomb 7.058 227 7.149 524 7.058 227 7.125 233 7.125 233 7.155 953
Exchange ⫺2.278 614 ⫺2.652 365 ⫺2.630 245 ⫺2.657 375 ⫺2.657 375 ⫺2.666 882

LiH 共Total兲 ⫺7.703 725 ⫺7.983 855 ⫺7.983 703 ⫺7.991 106 ⫺7.991 106 ⫺7.986 976
Core ⫺12.383 961 ⫺12.433 448 ⫺12.383 963 ⫺12.469 409 ⫺12.469 409 ⫺12.470 525
Coulomb 5.487 338 5.577 515 5.487 342 5.627 292 5.627 292 5.634 917
Exchange ⫺1.802 420 ⫺2.123 240 ⫺2.082 399 ⫺2.144 307 ⫺2.144 307 ⫺2.146 686

H2O 共Total兲 ⫺75.246 235 ⫺76.110 666 ⫺76.269 010 ⫺76.115 362 ⫺76.281 562 ⫺76.061 105
Core ⫺122.714 318 ⫺122.861 208 ⫺122.714 323 ⫺123.005 205 ⫺123.176 771 ⫺123.020 316
Coulomb 46.333 444 46.525 750 46.333 450 46.673 694 46.880 878 46.723 556
Exchange ⫺8.044 541 ⫺8.954 387 ⫺9.067 316 ⫺8.963 029 ⫺9.164 848 ⫺8.943 524

CH4 共Total兲 ⫺39.527 008 ⫺40.207 213 ⫺40.352 396 ⫺40.142 637 ⫺40.362 383 ⫺40.213 847
Core ⫺79.785 146 ⫺79.846 199 ⫺79.785 146 ⫺79.903 336 ⫺80.003 470 ⫺79.826 598
Coulomb 32.612 800 32.729 153 32.612 800 32.751 725 32.895 191 32.725 860
Exchange ⫺5.839 549 ⫺6.575 054 ⫺6.664 937 ⫺6.475 913 ⫺6.738 992 ⫺6.597 996

addition, convergence problems were encountered at the
non-localized SIC-OEP level. However, the SIC-OEP
共which includes localization兲 properly corrects this defi-
ciency giving bound HOMOs and no difficulties in conver-
gence. The HOMOs for the anions are converged at the SIC-
OEP/aug-cc-pVTZ⫹1 level. The HOMO for F⫺ at the SIC-
OEP/aug-cc-pVTZ⫹1 level is similar to the HF value. The
HF electron affinity based on the HOMO eigenvalue is 4.93
eV and the SIC-OEP electron affinity calculated in the same
way is 5.14 eV, both of which can be compared to the ex-
perimental value of 3.40 eV.60 The HOMO eigenvalue at the
BLYP level with a very large basis set is much less, 1.69
eV.57 For H⫺ , the HF and SIC-OEP eigenvalues are the
same, 1.25 eV, as compared to the experimental value of
0.76 eV.61
A number of authors have noted that the Kohn–Sham
eigenvalues do have a physical meaning beyond the applica-
tion of a Koopmanns’ theorem type argument relating the
energy of the HOMO to the first ionization potential.62–66
We note that Görling explicitly states: ‘‘the KS orbital eigen-
values are not just auxiliary quantities without physical
meaning; their difference is a well-defined approximation to
excitation energies of zeroth order in the electron-electron
interaction.’’62 Thus the GAP should be an approximation to
an experimental excitation energy and, so, in Table IV, we
also include experimental excitation energies.67 As shown in
Table IV, when localization of the spin–orbitals is important
to the total energy, it is important to the energies 共eigenval-
ues兲 of the spin–orbitals as well. This means that the maxi-
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mization of the exchange-SIC energy is reflected by a deeper
OEP. In all systems that we studied, the occupied orbital
energies obtained with SIC and OEP are more negative
共larger absolute value兲 than those obtained from LDA and
GGA functionals and thus the HOMO eigenvalue is closer to
the HF values for which Koopmans’ theorem rigorously
holds.
Whereas the HOMO energies at the SIC-OEP level are
similar to the HF values, there are significant differences in
the LUMO values. The HF values, of course, go to zero as a
more complete basis set with diffuse functions is employed;
thus at the HF level, ⫺␧ HOMO⫽GAP. The SIC-OEP ap-
proach gives bound 共negative energy兲 LUMO eigenvalues
for all of the molecules studied in this work. The LDA and
GGA LUMOs are quite similar to each other and are always
much more positive than the SIC-OEP values. For He, H2 ,
and H2 O, the LDA and GGA values are near zero, being
slightly bound or unbound depending on the species. The
value of the GAP corresponds to the difference in the
HOMO and LUMO eigenvalues. Thus the GAP at the HF
level just corresponds to the IP. Because of the variation in
the HOMO and LUMO values, one cannot simply look at
one or the other to predict the behavior of the GAP. In the
systems that we studied, the GAP at the SIC-OEP level is
greater than the GAP obtained with LDA and GGA, except
for the beryllium atom where they are all approximately
equal as shown in Fig. 1.
As noted above, the GAP obtained from DFT using
exchange-correlation potentials with the correct asymptotic
 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000 Optimized effective potential 7887

TABLE IV. HOMO (␧ H ) and LUMO (␧ L ) energies and their difference 共GAP兲 in Hartrees.

Slater (V x␴ ) Slater (V x␴ ) Exp. Excit.

System Slater (V x␴ ) Becke (V x␴ ) SIC–Noloc SIC–OEP HF a energyb

H⫺: ␧H 0.059 0.056 ⫺0.046 ⫺0.046 ⫺0.046

␧L 0.877 0.575 0.015 0.015 0.099
He: ␧H ⫺0.517 ⫺0.554 ⫺0.918 ⫺0.918 ⫺0.918
␧L 0.014 0.003 ⫺0.158 ⫺0.158 0.019
GAP 0.531 0.557 0.760 0.760 0.918 0.728(2 3 S)
0.758(2 1 S)
H2: ␧H ⫺0.331 ⫺0.356 ⫺0.594 ⫺0.594 ⫺0.594
␧L 0.008 ⫺0.001 ⫺0.161 ⫺0.161 0.012
GAP 0.339 0.355 0.434 0.434 0.594 0.42( 3 ⌺ ⫹
u )
0.46( 1 ⌸ u )
Be: ␧H ⫺0.170 ⫺0.181 ⫺0.308 ⫺0.308 ⫺0.309
␧L ⫺0.045 ⫺0.053 ⫺0.179 ⫺0.179 0.002
GAP 0.125 0.129 0.130 0.130 0.309 0.100(1 3 P)
0.194(1 1 P)
LiH: ␧H ⫺0.128 ⫺0.139 ⫺0.301 ⫺0.301 ⫺0.302
␧L ⫺0.041 ⫺0.049 ⫺0.151 ⫺0.151 ⫺0.008
GAP 0.087 0.090 0.150 0.150 0.302 0.12( 1 ⌺ ⫹ )
F⫺: ␧H 0.075 0.069 c ⫺0.189 ⫺0.181
␧L 0.152 0.145 c 0.040 0.174
H2O: ␧H ⫺0.225 ⫺0.235 ⫺0.466 ⫺0.518 ⫺0.510
␧L ⫺0.016 ⫺0.026 ⫺0.196 ⫺0.216 0.008
GAP 0.209 0.209 0.269 0.302 0.510 0.26( 3 B 1 )
0.28( 1 B 1 )
CH4 ␧H ⫺0.302 ⫺0.317 ⫺0.480 ⫺0.564 ⫺0.546
␧L ⫺0.002 ⫺0.011 ⫺0.146 ⫺0.174 0.008
GAP 0.299 0.306 0.334 0.390 0.546 0.40( 3 T 2 )
0.41( 1 T 2 )
a
The GAP value at the HF level is given for the basis set limit in terms of a complete set of diffuse functions
and is just the absolute value of ␧ H .
b
The lowest energy singlet and triplet transitions.
c
Convergence not achieved.

behavior can be used to approximate excited state
energies.62–68 As shown in Table IV, the values of the GAP
can be used to predict excited state energies 共vertical兲 just
based on information from the ground state. The agreement
is reasonable. We can compare our GAP values to those of
others. For example, Umrigar et al.65,66 calculate a value of
0.746 a.u. for He as compared to our value of 0.760 a.u. and
the experimental value65,66 of 0.758 a.u. for the excitation to
the 2 1 S state. For Be, the Umrigar et al. value65,66 is 0.133
a.u. as compared to our value of 0.130 共the LUMO is a p
FIG. 1. The HOMO–LUMO gap 共GAP兲 for the closed shell systems; He,
Be, H2 , LiH, H2 O, and CH4 . All energies are in electron-Volts.
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orbital兲 and the experimental value65,66 of 0.194 for the
2s→2p singlet transition. For H2 , Kim et al.64 obtain 0.47
a.u. as compared to our value of 0.434 a.u. and an experi-
mental value64 of 0.46 for the 1 ⌸ u transition. For H2 O, Kim
et al. find 0.34 a.u. as compared to our value of 0.302 and an
experimental value67 of 0.28 a.u. for the 1 B 1 excitation. For
CH4 , Kim et al. find 0.42 a.u. as compared to our value of
0.39 a.u. and an experimental value67 of 0.41 a.u. for the 1 T 2
excitation. More accurate estimates of excited state energies
will require the additional inclusion of electron correlation;
this topic is currently under investigation in our laboratory.
Next, we applied the SIC-OEP approach to describe the
dissociation of the H⫹ 2 molecule, a one-electron system for
which the SIC would be expected to be large. Figure 2 de-
picts energy versus bond length curves for the LDA, GGA,
and SIC-OEP approximations. The HF curve is not shown in
Fig. 2 because it is the same as the SIC-OEP curve. Clearly
the SIC-OEP improves upon the results obtained with either
LDA or GGA functionals. Table V displays the important
electronic structure properties obtained for this system. In
this table the SIC–Noloc results are not included because
they are the same as the SIC–OEP results. The results ob-
tained with LDA and GGA are truly different from those
obtained with either the SIC approximation or HF theory.
The equilibrium distance is significantly overestimated with
LDA and GGA, with LDA giving the poorer result of the
 7888 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000 Garza, Nichols, and Dixon

TABLE V. Binding energy, equilibrium distance, and energetics for the H⫹

2
molecule in Hartrees.

Equilibrium Electronic Binding

Method distance energy Total energy energy ␧H

LDA 2.217 ⫺1.0504 ⫺0.5623 ⫺0.1054 ⫺0.795

GGA 2.147 ⫺1.0654 ⫺0.6077 ⫺0.1100 ⫺0.841
SIC–Perta 1.995 ⫺1.1027 ⫺0.6016 ⫺0.1034
SIC-OEP 1.998 ⫺1.1027 ⫺0.6024 ⫺0.1026 ⫺1.1027
HF 1.998 ⫺1.1027 ⫺0.6024 ⫺0.1026 ⫺1.1027
Exactb 1.997 ⫺1.1033 ⫺0.6026 ⫺0.1026 ¯
a
In the SIC–Pert method, the orbital energies are not modified with respect
to the LDA method.
b
Reference 63.

FIG. 2. The binding energy of H⫹

2 . All energies are in kcal per mole.
two. In addition to the total energy, we also include the elec-
tronic energy in order to compare to the HOMO energy. If
the self-interaction is suitably removed, these quantities must
be the same for this one electron system 关only the first term
is used in Eq. 共21兲兴. As shown in Table V, the HOMO values
from LDA and GGA are above the HF and SIC-OEP values.
Furthermore, the comparison between the electronic energy
and the HOMO energy is not good for either LDA or GGA.
This example exhibits the lack of an appropriate canceling
of the self-interaction in the Kohn–Sham effective potential
of these functionals. The situation is different with the
SIC-OEP approach where the total and spin–orbital energies
match appropriately and all results are in good agreement
with the exact analytical solution.69
Although the SIC perturbative 共SIC–Pert兲 approach
gives improved results as compared to the LDA and GGA
results, the SIC-OEP results are even better. However, as we
have noted above, the SIC-OEP method is more expensive
than the SIC–Pert approach. Thus, the SIC–Pert approach
appears to be useful for total energies and associated prop-
erties. It is more easily implemented, requires less computa-
tional effort, and seems to give very reasonable results for
the systems we have tested. However, if orbital energies or
properties dependent upon orbital densities are desired, then
this method cannot be used.
Finally, we utilized the same concept of spin–orbital lo-
calization in order to maximize the exchange-SIC energy as
used in our closed-shell systems to treat open-shell systems.
The total energy and its components for the open-shell sys-
tems; H, C, and N are shown in Table VI. In this table we
include the results that correspond to the SIC-OEP. The
SIC–Noloc results are not included because their total ener-
gies were always greater than the corresponding SIC–Pert or
SIC-OEP methods. As shown in Table VI, the SIC-OEP
method gives exchange energies greater than the HF ex-
change and consequently results in larger absolute values of
the total energies, except for the hydrogen atom where there
is an appropriate cancellation of the Coulomb and exchange
energies.
IV. CONCLUSIONS
The incorporation of the optimized effective potential
with the self-interaction correction into the Gaussian
function-based DFT code NWChem has been presented. The
SIC-OEP model improves the asymptotic behavior of the
exchange potential and, thus, it is important to have this
method in widely available codes that are used for the study
of the electronic structure of atoms and molecules. The oc-
cupied spin–orbital eigenvalues with the SIC-OEP are
deeper than those obtained with functionals like LSDA or
GGA. In particular, for exchange-only calculations, the

TABLE VI. Total energy and components of the electronic energy of open-shell systems in Hartrees. The core
component is the kinetic energy plus the electron–nuclei interaction.

Slater (V x ␴ ) Slater (V x ␴ )
System Slater (V x ␴ ) Becke (V x ␴ ) SIC–Pert SIC–OEP HF

H 共Total兲 ⫺0.456 924 ⫺0.497 727 ⫺0.498 235 ⫺0.499 835 ⫺0.499 836
Core ⫺0.498 235 0.499 106 ⫺0.498 235 ⫺0.499 835 ⫺0.499 836
Coulomb 0.294 467 0.307 178 0.294 467 0.312 347 0.312 355
Exchange ⫺0.253 157 ⫺0.305 799 ⫺0.294 467 ⫺0.312 347 ⫺0.312 355

C 共Total兲 ⫺37.111 788 ⫺37.687 906 ⫺37.745 065 ⫺37.752 280 ⫺37.691 997
Core ⫺50.303 298 ⫺50.407 992 ⫺50.303 181 ⫺50.479 416 ⫺50.446 542
Colomb 17.621 460 17.763 157 17.621 318 17.850 273 17.830 356
Exchange ⫺4.429 949 ⫺5.043 071 ⫺5.063 202 ⫺5.123 137 ⫺5.075 810

N 共Total兲 ⫺53.706 188 ⫺54.397 086 ⫺54.488 278 ⫺54.496 323 ⫺54.401 558
Core ⫺73.738 816 ⫺73.858 453 ⫺73.738 839 ⫺73.974 525 ⫺73.948 461
Coulomb 25.868 300 26.025 038 25.868 329 26.166 688 26.152 307
Exchange ⫺5.835 672 ⫺5.563 670 ⫺6.617 768 ⫺6.688 486 ⫺6.605 404

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 J. Chem. Phys., Vol. 112, No. 18, 8 May 2000
HOMO eigenvalue is similar to the HF eigenvalue whereas
the LUMO eigenvalue is usually a quite negative number in
contrast to the HF result of a zero eigenvalue for an infinite
basis set. The LUMO energy does converge quickly to a
finite number with addition of diffuse functions at the SIC-
OEP level. The HOMO–LUMO gaps calculated with SIC-
OEP appear to give good estimates of first excitation ener-
gies in the molecules that we studied. In general, the LDA
and GGA GAPs are smaller than the SIC-OEP values. In
terms of total energies, the SIC-OEP gives absolute values
larger than HF values, which seems to imply that the ex-
change is overestimated with the SIC-OEP model. Thus, a
revision may be needed in order to use this method as an
option in the prediction of atomization energies or transition
states; we are exploring how well this approximation works
for such properties. The SIC-OEP model does promise im-
provement over the LSDA, GGA, and B3 functionals. Its
principal computational handicap is the evaluation of the
electrostatic potential of each spin-orbital density, but con-
tinued improvements in the numerical integral techniques
will make the SIC-OEP approach much less expensive. The
use of localized spin–orbitals to maximize the exchange self-
interaction is recommended for both closed and open-shell
systems. However, due to the fact that we are localizing the
spin–orbitals in each step of the self-consistent process, we
need, in general, more iterations to converge the SCF equa-
tions. We believe it is now necessary to carry out a system-
atic study of the SIC-OEP on many molecular systems to see
how it performs on geometries, atomization energies, ener-
gies of weak interactions such as hydrogen bonds, and tran-
sition states; as noted above, we are currently pursuing such
studies.
ACKNOWLEDGMENTS
Financial support for J. Garza was partially provided by
CONACYT, México. This work was funded by the Office of
Basic Energy Sciences and by the Office of Biological and
Environmental Research in the U.S. Department of Energy.
This research was performed in part using the Molecular
Science Computing Facility 共MSCF兲 in the William R.
Wiley Environmental Molecular Sciences Laboratory at the
Pacific Northwest National Laboratory. The MSCF is funded
by the Office of Biological and Environmental Research in
the U.S. Department of Energy. Pacific Northwest is oper-
ated by Battelle for the U.S. Department of Energy under
Contract DE-AC06-76RLO 1830.
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