A means of finding a compact orbital representation for the electronic transition density matrix is described. The technique utilizes the corresponding orbital transformation of Amos and Hall and allows a dramatic simplification in the qualitative description of an electronic transition.

1.
J.
Ridley
and
M. C.
Zerner
,
Theor. Chim. Acta
32
,
111
(
1973
);
W. P.
Anderson
,
W. D.
Edwards
, and
M. C.
Zerner
,
Inorg. Chem.
25
,
2728
(
1986
).
2.
S.
Tretiak
,
A.
Saxena
,
R. L.
Martin
, and
A. R.
Bishop
,
Chem. Phys. Lett.
331
,
561
(
2000
).
3.
G. R.
Hutchinson
,
M. A.
Ratner
, and
T. J.
Marks
,
J. Phys. Chem. A
106
,
10596
(
2002
).
4.
J.
Fabian
,
L. A.
Daiz
,
G.
Seifert
, and
T.
Niehaus
,
J. Mol. Struct.: THEOCHEM
594
,
41
(
2002
).
5.
E. K. U.
Gross
and
W.
Kohn
,
Adv. Quantum Chem.
21
,
255
(
1990
).
6.
M. E. Casida, in Recent Advances in Density Functional Methods, Vol. 1, edited by D. P. Chong (World Scientific, Singapore, 1995).
7.
M.
Petersilka
,
U. J.
Grossmann
, and
E. K. U.
Gross
,
Phys. Rev. Lett.
76
,
1212
(
1996
);
M.
Petersilka
and
E. K. U.
Gross
,
Int. J. Quantum Chem., Quantum
30
,
181
(
1996
).
8.
S. J. A.
van Gisbergen
,
J. G.
Snijders
, and
E. J.
Baerends
; ibid.
103
,
9347
(
1995
);
S. J. A.
van Gisbergen
,
C. Fonseca
Guerra
, and
E. J.
Baerends
,
J. Comput. Chem.
21
,
1511
(
2000
).
9.
R.
Bauernschmitt
and
R.
Ahlrichs
,
Chem. Phys. Lett.
256
,
454
(
1996
);
R.
Bauernschmitt
,
R.
Ahlrichs
,
F. H.
Hennrich
, and
M. M.
Kappes
,
J. Am. Chem. Soc.
120
,
5052
(
1998
).
10.
R. E.
Stratmann
,
G. E.
Scuseria
, and
M. J.
Frisch
,
J. Chem. Phys.
109
,
8218
(
1998
).
11.
S.
Hirata
and
M.
Head-Gordon
,
Chem. Phys. Lett.
314
,
2091
(
1999
);
C.-P.
Hsu
,
S.
Hirata
, and
M.
Head-Gordon
,
J. Phys. Chem. A
105
,
451
(
2001
).
12.
A. T. Amos and G. G. Hall, Proc. Roy. Soc. A263, 483 (1961).
13.
An example which uses this transformation in the same spirit in order to aid in the interpretation of ΔSCF calculations of ionization potentials is given in
R. L.
Martin
and
E. R.
Davidson
,
Phys. Rev. A
16
,
1341
(
1977
).
14.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, et al. GAUSSIAN 98, REVISION A.11, Gaussian, Inc., Pittsburgh PA. 1998.
15.
D. M.
Dattelbaum
,
K. M.
Omberg
,
J. R.
Schoonover
,
R. L.
Martin
, and
T. J.
Meyer
,
Inorg. Chem.
41
,
6071
(
2002
).
16.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
).
17.
W. R.
Wadt
and
P. J.
Hay
,
J. Chem. Phys.
82
,
284
(
1985
);
P. J.
Hay
and
W. R.
Wadt
,
J. Chem. Phys.
82
,
299
(
1985
).
This content is only available via PDF.
You do not currently have access to this content.