Within the adiabatic approximation, time-dependent density functional theory yields only single excitations. Near states of double excitation character, the exact exchange–correlation kernel has a strong dependence on frequency. We derive the exact frequency-dependent kernel when a double excitation mixes with a single excitation, well separated from the other excitations, in the limit that the electron–electron interaction is weak. Building on this, we construct a nonempirical approximation for the general case, and illustrate our results on a simple model.
REFERENCES
1.
2.
3.
4.
J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, Phys. Rev. Lett.
77
, 3865
(1996
);J. P.
Perdew
, K.
Burke
, and M.
Ernzerhof
, Phys. Rev. Lett.
78
, 1396
(1997
(E)).5.
6.
J. P.
Perdew
, S.
Kurth
, A.
Zupan
, and P.
Blaha
, Phys. Rev. Lett.
82
, 2544
(1999
);J. P.
Perdew
, S.
Kurth
, A.
Zupan
, and P.
Blaha
, Phys. Rev. Lett.
82
, 5179
(1999
(E)).7.
J. L. F.
Da Silva
, C.
Stampfl
, and M.
Scheffler
, Phys. Rev. Lett.
90
, 066104
(2003
).8.
9.
M.
Petersilka
, U. J.
Gossmann
, and E. K. U.
Gross
, Phys. Rev. Lett.
76
, 1212
(1996
).10.
M. E. Casida, in Recent Developments and Applications in Density Functional Theory, edited by J. M. Seminario (Elsevier, Amsterdam, 1996).
11.
12.
13.
A.
Tsolakidis
, D.
Sánchez-Portal
, and R. M.
Martin
, Phys. Rev. B
66
, 235416
(2002
).14.
N. T. Maitra, K. Burke, H. Appel, E. K. U. Gross, and R. van Leeuwen, in Reviews in Modern Quantum Chemistry: A Celebration of the Contributions of R. G. Parr, edited by K. D. Sen (World-Scientific, Singapore, 2002).
15.
H.
Appel
, E. K. U.
Gross
, and K.
Burke
, Phys. Rev. Lett.
90
, 043005
(2003
).16.
M. E.
Casida
, C.
Jamorski
, K. C.
Casida
, and D. R.
Salahub
, J. Chem. Phys.
108
, 4439
(1998
).17.
18.
19.
20.
N. T.
Maitra
, K.
Burke
, and C.
Woodward
, Phys. Rev. Lett.
89
, 023002
(2002
).21.
22.
D. J.
Tozer
and N. C.
Handy
, Phys. Chem. Chem. Phys.
2
, 2117
(2000
).23.
D. J.
Tozer
, R. D.
Amos
, N. C.
Handy
, B. O.
Roos
, and L.
Serrano-Andres
, Mol. Phys.
97
, 859
(1999
).24.
C.
Hsu
, S.
Hirata
, and M.
Head-Gordon
, J. Phys. Chem. A
105
, 451
(2001
).25.
26.
E. K. U.
Gross
, J. F.
Dobson
, and M.
Petersilka
, Top. Curr. Chem.
181
, 81
(1996
).27.
See, e.g., R. H. Cave, in Modern Electronic Structure Theory and Applications in Organic Chemistry, edited by E. R. Davidson (World, Singapore, Singapore, 1997), p. 197.
28.
29.
J. D.
Watts
, S. R.
Gwaltney
, and R. J.
Bartlett
, J. Chem. Phys.
105
, 6979
(1996
).30.
L.
Serrano-Andres
, M.
Merchan
, I.
Nebot-Gil
, R.
Lindh
, and B. O.
Roos
, J. Chem. Phys.
98
, 3151
(1993
).31.
32.
R. J. Cave, F. Zhang, N. T. Maitra, and K. Burke, Chem. Phys. Lett. (to be published).
33.
34.
I. N. Levine, Quantum Chemistry, 4th ed. (Prentice–Hall, Englewood Cliffs, NJ, 1991).
35.
36.
37.
C.
Filippi
, C. J.
Umrigar
, and X.
Gonze
, J. Chem. Phys.
107
, 9994
(1997
).38.
F. Zhang and K. Burke, Phys. Rev. A (to be published).
This content is only available via PDF.
© 2004 American Institute of Physics.
2004
American Institute of Physics
You do not currently have access to this content.