A new, computationally efficient approximation to calculating matrix elements between vibrational-electronic states that does not assume stationary nuclei is introduced. The approach emphasizes the importance of the conservation of nuclear momenta. The calculated quantities can be used wherever equivalent quantities from standard Franck-Condon treatments can be used. The new method is illustrated by a time-dependent perturbation theory description of the photodissociation of the Li2+ molecular cation in an intense laser field (I=0.9×1012Wcm2), which was previously identified in a detailed study of the electronic structure [Khait et al, J. Chem. Phys.122, 094111 (2005)] as likely to have unusual sensitivity to the initial vibrational state in dynamics. The current study confirms this speculation and shows this to be a specific instance of a situation in which nuclear dynamics during an electronic optical transition cannot be ignored.

1.
D.
Harris
and
M. D.
Bertolucci
,
Symmetry and Spectroscopy
(
Dover
,
Mineola, NY
,
1978
).
2.
A.
Hazra
,
H. H.
Chang
, and
M.
Nooijen
,
J. Chem. Phys.
121
,
2125
(
2004
).
3.
A.
Hazra
and
M.
Nooijen
,
J. Chem. Phys.
122
,
204327
(
2005
).
4.
R. M.
Rao
,
E. D.
Poliakoff
,
K.
Wang
, and
V.
McKoy
,
Phys. Rev. Lett.
76
,
2666
(
1996
).
5.
D. R.
Yarkony
,
Rev. Mod. Phys.
68
,
985
(
1996
).
6.
J.
Coe
and
T. J.
Martinez
,
J. Am. Chem. Soc.
127
,
4560
(
2005
).
7.
Y. G.
Khait
,
A.
Azenkeng
,
H.
Wang
,
T. J.
Dudley
, and
M. R.
Hoffmann
,
J. Chem. Phys.
122
,
094111
(
2005
).
8.
O.
Geßner
,
A. M. D.
Lee
,
J. P.
Shaffer
,
H.
Reisler
,
S. V.
Levchencko
,
A. I.
Krylov
,
J. G.
Underwood
,
H.
Shi
,
A. L. L.
East
,
D. M.
Wardlaw
,
E. t. H.
Chrysostom
,
C. C.
Hayden
, and
A.
Stolow
,
Science
311
,
219
(
2006
).
9.
P. W.
Dooley
,
I. V.
Litvinyuk
,
K. F.
Lee
,
D. M.
Rayner
,
D. M.
Vileneuve
, and
P. B.
Corkum
,
Phys. Rev. A
68
,
023406
(
2003
).
10.
T.
Kanai
,
S.
Minemoto
, and
H.
Sakai
,
Nature (London)
435
,
470
(
2005
).
11.
W.
Vanroose
,
F.
Martin
,
T. N.
Rescigno
, and
C. W.
McCurdy
,
Science
310
,
1787
(
2005
).
12.
H.
Nagai
,
H.
Ohmura
,
F.
Ito
,
T.
Nakanaga
, and
M.
Tachiya
,
J. Chem. Phys.
124
,
034304
(
2006
).
13.
M. E.
Sukharev
,
E.
Charron
,
A.
Suzor-Weiner
, and
M. V.
Federov
,
Int. J. Quantum Chem.
99
,
452
(
2004
).
14.
S.
Guérin
and
H. R.
Jauslin
,
Adv. Chem. Phys.
125
,
147
(
2003
).
15.
K.
Codling
and
L. J.
Frasinski
,
J. Phys. B
26
,
783
(
1993
).
16.
J. J.
Tanner
and
M.
Maricq
,
Phys. Rev. A
40
,
4054
(
1989
).
17.
G. V.
Steeg
,
K.
Bartschat
, and
I.
Bray
,
J. Phys. B
36
,
3325
(
2003
).
18.
M.
Isao
,
T.
Sako
, and
K.
Yamanouchi
,
J. Phys. B
37
,
3919
(
2004
).
19.
S.
Magnier
,
M.
Persico
, and
N.
Rahman
,
J. Phys. Chem. A
103
,
10691
(
1999
).
20.
G. M.
Sando
,
K. G.
Spears
,
J. T.
Hupp
, and
P. T.
Ruhoff
,
J. Phys. Chem. A
105
,
5317
(
2001
).
21.
M.
Dierksen
and
S.
Grimme
,
J. Chem. Phys.
122
,
244101
(
2005
).
22.
G.
Jolicard
and
J. P.
Killingbeck
,
J. Chem. Phys.
100
,
325
(
1994
).
23.
H.
Friedrich
,
Theoretical Atomic Physics
(
Springer-Verlag
,
New York
,
1991
).
24.
M. D.
Halls
,
H. B.
Schlegel
,
M. J.
DeWitt
, and
G. W. F.
Drake
,
Chem. Phys. Lett.
339
,
427
(
2001
).
25.
S.
Magnier
,
S.
Rousseau
,
A. R.
Allouche
,
G.
Hadinger
, and
M.
Aubert-Frécon
,
Chem. Phys.
246
,
57
(
1999
).
26.
R. A.
Bernheim
,
L. P.
Gold
, and
T.
Tipton
,
J. Chem. Phys.
78
,
3635
(
1983
).
27.
A. D.
Bandrauk
and
H.
Shen
,
J. Chem. Phys.
99
,
1185
(
1993
).
28.
S. R.
Barone
,
M. A.
Narcowich
, and
F. J.
Narcowich
,
Phys. Rev. A
15
,
1109
(
1977
).
29.
K. F.
Milfeld
and
R. E.
Wyatt
,
Phys. Rev. A
27
,
72
(
1983
).
30.
S.-I.
Chu
and
D. A.
Telnov
,
Phys. Rep.
390
,
1
(
2004
).
31.
C. A.
Mead
,
Rev. Mod. Phys.
64
,
51
(
1992
).
32.
C. M.
Tesch
and
R.
de Vivie-Riedle
,
Phys. Rev. Lett.
89
,
157901
(
2002
).
You do not currently have access to this content.