In this paper we report the calculation of molecular electric response properties with the help of explicitly time-dependent configuration interaction (TD-CI) methods. These methods have the advantage of being applicable (within the limitations of the time-dependent Schrödinger equation) to time-dependent perturbations of arbitrary shape and strength. Three variants are used to solve the time-dependent electronic Schrödinger equation, namely, the TD-CIS (inclusion of single excitations only), TD-CISD (inclusion of single and double excitations), and TD-CIS(D) (single excitations and perturbative treatment of double excitations) methods and applied for illustration to small molecules, H2 and H2O. In the calculation, slowly varying off-resonant electric fields are applied to the molecules and linear (polarizabilities) and nonlinear (hyperpolarizabilities, harmonic generation) response properties are determined from the time-dependent dipole moments.

1.
M.
Hentschel
,
R.
Kienberger
,
C.
Spielmann
,
G. A.
Reider
,
N.
Milosevic
,
T.
Brabec
,
P.
Corkum
,
U.
Heinzmann
,
M.
Drescher
, and
F.
Krausz
,
Nature (London)
414
,
509
(
2001
).
2.
R.
Kienberger
,
M.
Hentschel
,
M.
Uiberacker
 et al,
Science
297
,
1144
(
2002
).
3.
P.
Bucksbaum
,
Nature (London)
421
,
593
(
2003
).
4.
A.
Föhlisch
,
P.
Feulner
,
F.
Hennies
,
A.
Fink
,
D.
Menzel
,
D.
Sanchez-Portal
,
P.
Echenique
, and
W.
Wurth
,
Nature (London)
436
,
7049
(
2005
).
5.
M.
Drescher
,
M.
Hentschel
,
R.
Kienberger
,
M.
Uiberacker
,
V.
Yakovlev
,
A.
Scrinzi
,
T.
Westerwalbesloh
,
U.
Kleineberg
,
U.
Heinzmann
, and
F.
Krausz
,
Nature (London)
419
,
803
(
2002
).
6.
G. G.
Paulus
,
F.
Lindner
,
H.
Walther
,
A.
Baltuška
,
E.
Goulielmakis
,
M.
Lezius
, and
F.
Krausz
,
Phys. Rev. Lett.
91
,
253004
(
2003
).
7.
K.
Kulander
,
Phys. Rev. A
36
,
2762
(
1987
).
8.
R.
Grobe
and
J. H.
Eberly
,
Phys. Rev. A
48
,
4664
(
1993
).
9.
M.
Pindzola
,
P.
Gavras
, and
T.
Gorczyca
,
Phys. Rev. A
51
,
3999
(
1995
).
10.
H.
Yu
and
A.
Bandrauk
,
Phys. Rev. A
56
,
658
(
1997
).
11.
F.
Remacle
and
R.
Levine
,
J. Chem. Phys.
110
,
5089
(
1999
).
12.
F.
Calvayrac
,
P.-G.
Reinhard
,
E.
Suraud
, and
C.
Ullrich
,
Phys. Rep.
337
,
493
(
2000
).
13.
K.
Harumiya
,
I.
Kawata
,
H.
Kono
, and
Y.
Fujimura
,
J. Chem. Phys.
113
,
8953
(
2000
).
14.
H.
Harumiya
,
H.
Kono
, and
Y.
Fujimura
,
Phys. Rev. A
66
,
043403
(
2002
).
15.
J.
Breidbach
and
L.
Cederbaum
,
J. Chem. Phys.
118
,
3983
(
2003
).
16.
T.
Klamroth
,
Phys. Rev. B
68
,
245421
(
2003
).
17.
M.
Suzuki
and
S.
Mukamel
,
J. Chem. Phys.
119
,
4722
(
2003
).
18.
S.
Laulan
and
H.
Bachau
,
Phys. Rev. A
68
,
013409
(
2003
).
19.
F.
Zanghellini
,
M.
Kitzler
,
C.
Fabian
,
T.
Brabec
, and
A.
Scrinzi
,
Laser Phys.
13
,
1064
(
2003
).
20.
T.
Kato
and
H.
Kono
,
Chem. Phys. Lett.
392
,
533
(
2004
).
21.
X.
Chu
and
S. I.
Chu
,
Phys. Rev. A
70
,
61402
(
2004
).
22.
G.
Paramonov
,
Chem. Phys. Lett.
411
,
305
(
2005
).
23.
T.
Burnus
,
M.
Marques
, and
E.
Gross
,
Phys. Rev. A
71
,
010501
(
2005
).
24.
X. S.
Li
,
S. M.
Smith
,
A. N.
Markevitch
,
D. A.
Romanov
,
R. J.
Levis
, and
H. B.
Schlegel
,
Phys. Chem. Chem. Phys.
7
,
233
(
2005
).
25.
I.
Barth
and
J.
Manz
,
Angew. Chem., Int. Ed.
45
,
2962
(
2006
).
26.
I.
Barth
,
J.
Manz
,
Y.
Shigeta
, and
K.
Yagi
,
J. Am. Chem. Soc.
128
,
7043
(
2006
).
27.
A.
Castro
,
M.
Marques
,
H.
Appel
,
M.
Oliveira
,
C.
Rozzi
,
X.
Andrade
,
F.
Lorenzen
,
E.
Gross
, and
A.
Rubio
,
Phys. Status Solidi B
243
,
2465
(
2006
).
28.
P.
Saalfrank
,
T.
Klamroth
,
C.
Huber
, and
P.
Krause
,
Isr. J. Chem.
45
,
205
(
2005
).
29.
P.
Krause
,
T.
Klamroth
, and
P.
Saalfrank
,
J. Chem. Phys.
123
,
074105
(
2005
).
30.
M.
Nest
,
T.
Klamroth
, and
P.
Saalfrank
,
J. Chem. Phys.
122
,
124102
(
2005
).
31.
T.
Klamroth
,
J. Chem. Phys.
124
,
144310
(
2006
).
32.
P.
Craig
and
T.
Thirunamachandran
,
Molecular Quantum Electrodynamics
(
Academic
,
New York
,
1984
).
33.
B.
Gao
,
C.
Pan
,
C.-R.
Liu
, and
A. F.
Starace
,
J. Opt. Soc. Am. B
7
,
622
(
1990
).
34.
M.
Casida
,
C.
Jamorski
,
K.
Casida
, and
D.
Salahub
,
J. Chem. Phys.
108
,
4439
(
1998
).
35.
M. J.
Frisch
,
G. W.
Trucks
,
H. B.
Schlegel
 et al, GAUSSIAN 03, Revision C.02,
Gaussian, Inc.
, Wallingford, CT,
2004
.
36.
A.
Szabo
and
N. S.
Ostlund
,
Modern Quantum Chemistry
, 1st ed. (
McGraw-Hill
,
New York
,
1989
).
37.
M.
Head-Gordon
,
R. J.
Rico
,
M.
Oumi
, and
T. J.
Lee
,
Chem. Phys. Lett.
219
,
21
(
1994
).
38.
A. D.
Bandrauk
,
E.
Aubanel
, and
S.
Chelkowski
, in
Femtosecond Chemistry
, edited by
J.
Manz
and
L.
Wöste
(
Verlag Chemie
,
Weinheim.
,
1995
), Vol.
2
, Chap. 25, p.
731
.
39.
M. W.
Schmidt
,
K. K.
Baldridge
,
J. A.
Boatz
 et al,
J. Comput. Chem.
13
,
1347
(
1993
).
40.
G.
Herzberg
and
L. L.
Howe
,
Can. J. Phys.
37
,
636
(
1959
).
41.
T. H.
Dunning
,
J. Chem. Phys.
90
,
1007
(
1989
).
42.
A. K.
Wilson
,
T.
van Mourik
, and
T. H.
Dunning
,
J. Mol. Struct.
388
,
339
(
1996
).
43.
W.
Kołos
and
L.
Wolniewicz
,
J. Chem. Phys.
49
,
404
(
1968
).
44.
T. E.
Sharp
,
At. Data
2
,
119
(
1971
).
45.
W.
Kołos
and
L.
Wolniewicz
,
J. Chem. Phys.
48
,
3672
(
1968
).
46.
W.
Kołos
and
L.
Wolniewicz
,
J. Chem. Phys.
46
,
1426
(
1967
).
47.
R. L.
Wilkins
and
H. S.
Taylor
,
J. Chem. Phys.
48
,
4934
(
1968
).
48.
N. J.
Bridge
and
A. D.
Buckingham
,
Proc. R. Soc. London, Ser. A
295
,
334
(
1966
).
49.
Zahlenwerte und Funktionen
,
Landolt-Börnstein, New Series
, Vol.
1
, Pt. 3, 1st ed. (
Springer-Verlag
,
Berlin
,
1951
).
50.
G. A.
Victor
and
A.
Dalgarno
,
J. Chem. Phys.
50
,
2535
(
1969
).
51.
P. W.
Atkins
and
R. S.
Friedmann
,
Molecular Quantum Mechanics
, 4th ed. (
Oxford University Press
,
New York
,
2005
).
52.
G. A.
Victor
,
J. C.
Browne
, and
A.
Dalgarno
,
Proc. Phys. Soc. London
92
,
42
(
1967
).
53.
T.
Ando
and
A.
Saika
,
J. Chem. Phys.
55
,
4203
(
1971
).
54.
S. J. A.
van Gisbergen
,
J. G.
Snijders
, and
E. J.
Baerends
,
J. Chem. Phys.
103
,
9347
(
1995
).
55.
S. J. A.
van Gisbergen
,
V. P.
Osinga
,
O. V.
Gritsenko
,
R.
van Leeuwen
,
J. G.
Snijders
, and
E. J.
Baerends
,
J. Chem. Phys.
105
,
3142
(
1996
).
57.
J. B.
Hasted
, in
Water a Comprehensive Treatise
, edited by
F.
Franks
(
Plenum
,
New York
,
1972
), Vol.
1
, pp.
255
309
.
58.
V.
Engel
,
R.
Schinke
, and
V.
Staemmler
,
J. Chem. Phys.
88
,
129
(
1988
).
59.
S.
Hirata
and
M.
Head-Gordon
,
Chem. Phys. Lett.
314
,
291
(
1999
).
60.
W. F.
Murphy
,
J. Chem. Phys.
67
,
5877
(
1977
).
61.
O.
Christiansen
,
J.
Gauss
, and
J. F.
Stanton
,
Chem. Phys. Lett.
302
,
147
(
1999
).
62.
S. A. C.
McDowell
,
R. D.
Amos
, and
N. C.
Handy
,
Chem. Phys. Lett.
235
,
1
(
1995
).
63.
J. A.
Pople
,
M.
Head-Gordon
, and
K.
Raghavachari
,
J. Chem. Phys.
87
,
5968
(
1987
).
64.
W.
Klopper
(private communication).
You do not currently have access to this content.