The optimized effective potential (OEP) equations are solved in a matrix representation using the orbital products of occupied and virtual orbitals for the representation of both the local potential and the response function. This results in a direct relationship between the matrix elements of local and nonlocal operators for the exchange-correlation potential. The effect of the truncation of the number of such products in the case of finite orbital basis sets on the OEP orbital and total energies and on the spectrum of eigenvalues of the response function is examined. Test calculations for Ar and Ne show that rather large AO basis sets are needed to obtain an accurate representation of the response function.

1.
W.
Kohn
and
L. J.
Sham
,
Phys. Rev.
140
,
A1133
(
1965
).
2.
S. H.
Vosko
,
L.
Wilk
, and
M.
Nusair
,
Can. J. Phys.
58
,
1200
(
1980
).
3.
A. D.
Becke
,
Phys. Rev. A
38
,
3098
(
1988
).
4.
P.
Hohenberg
and
W.
Kohn
,
Phys. Rev.
136
,
B864
(
1964
).
5.
R. T.
Sharp
and
G. K.
Horton
,
Phys. Rev.
90
,
317
(
1953
).
6.
J. D.
Talman
and
W. F.
Shadwick
,
Phys. Rev. A
14
,
36
(
1976
).
7.
E.
Engel
and
S. H.
Vosko
,
Phys. Rev. A
47
,
2800
(
1993
).
8.
A.
Görling
and
M.
Levy
,
Phys. Rev. A
50
,
196
(
1994
).
9.
A.
Görling
and
M.
Levy
,
Int. J. Quantum Chem., Quantum Chem. Symp.
29
,
93
(
1995
).
10.
A.
Görling
,
Phys. Rev. Lett.
83
,
5459
(
1999
).
11.
A.
Görling
,
A.
Hesselmann
,
M.
Jones
, and
M.
Levy
, arXiv:physics/0705.1717v1.
12.
A.
Hesselmann
,
A. W.
Götz
,
F.
Della Sala
, and
A.
Görling
,
J. Chem. Phys.
127
,
054102
(
2007
).
13.
S.
Ivanov
,
S.
Hirata
, and
R. J.
Bartlett
,
Phys. Rev. Lett.
83
,
5455
(
1999
).
14.
S.
Hirata
,
S.
Ivanov
,
I.
Grabowski
,
R. J.
Bartlett
,
K.
Burke
, and
J. D.
Talman
,
J. Chem. Phys.
115
,
1635
(
2001
).
15.
S.
Ivanov
,
S.
Hirata
, and
R. J.
Bartlett
,
J. Chem. Phys.
116
,
1269
(
2002
).
16.
O. V.
Gritsenko
and
E. J.
Baerends
,
Phys. Rev. A
64
,
042506
(
2001
).
17.
D.
Rohr
,
O. V.
Gritsenko
, and
E. J.
Baerends
,
J. Mol. Struct.: THEOCHEM
762
,
193
(
2006
).
18.
T.
Grabo
and
E. K. U.
Gross
,
Chem. Phys. Lett.
240
,
141
(
1995
).
19.
R.
Colle
and
R. K.
Nesbet
,
J. Phys. B
34
,
2475
(
2001
).
20.
W.
Yang
and
Q.
Wu
,
Phys. Rev. Lett.
89
,
143002
(
2002
).
21.
S.
Ivanov
and
M.
Levy
,
J. Chem. Phys.
119
,
7087
(
2003
).
22.
S.
Kümmel
and
J. P.
Perdew
,
Phys. Rev. B
68
,
035103
(
2003
).
23.
S.
Kümmel
and
J. P.
Perdew
,
Phys. Rev. Lett.
90
,
043004
(
2003
).
24.
V. N.
Staroverov
,
G. E.
Scuseria
, and
E. R.
Davidson
,
J. Chem. Phys.
124
,
141103
(
2006
).
25.
J. B.
Krieger
,
Y.
Li
, and
G. J.
Iafrate
,
Phys. Rev. A
45
,
101
(
1992
).
26.
J. B.
Krieger
,
Y.
Li
, and
G. J.
Iafrate
,
Phys. Rev. A
46
,
5453
(
1992
).
27.
F.
Della Sala
and
A.
Görling
,
J. Chem. Phys.
115
,
5718
(
2001
).
28.
V. N.
Staroverov
,
G. E.
Scuseria
, and
E. R.
Davidson
,
J. Chem. Phys.
125
,
081104
(
2006
).
29.
A.
Okńinski
,
J. Chem. Phys.
60
,
4098
(
1974
).
30.
A. F.
Izmaylov
,
V. N.
Staroverov
,
G. E.
Scuseria
,
E. R.
Davidson
,
G.
Stoltz
, and
E.
Cancés
,
J. Chem. Phys.
126
,
084107
(
2007
).
31.
P. O.
Löwdin
,
Adv. Quantum Chem.
5
,
185
(
1970
).
32.
J. E.
Harriman
,
Phys. Rev. A
27
,
632
(
1983
).
33.
J. E.
Harriman
,
Phys. Rev. A
34
,
29
(
1986
).
34.
D. E.
Hoch
and
J. E.
Harriman
,
J. Chem. Phys.
102
,
9590
(
1995
).
35.
J. E.
Harriman
and
D. E.
Hoch
,
Int. J. Quantum Chem.
63
,
111
(
1997
).
36.
H.-J.
Werner
,
P. J.
Knowles
,
R.
Lindh
 et al, MOLPRO, version 2006.1, a package of ab initio programs, 2006, see http://www.molpro.net
37.
K.
Aashamar
,
T. M.
Luke
, and
J. D.
Talman
,
At. Data Nucl. Data Tables
22
,
443
(
1978
).
38.
M. W.
Schmidt
and
K.
Ruedenberg
,
J. Chem. Phys.
71
,
3951
(
1979
).
39.
A. K.
Wilson
,
T. v.
Mourik
, and
T. H.
Dunning
, Jr.
,
J. Mol. Struct.: THEOCHEM
388
,
339
(
1996
).
40.
Y.
Li
,
J. B.
Krieger
,
J. A.
Chevary
, and
S. H.
Vosko
,
Phys. Rev. A
43
,
5121
(
1991
).
41.
M.
Levy
and
A.
Görling
,
Phys. Rev. A
53
,
3140
(
1996
).
You do not currently have access to this content.