The predissociation dynamics of lithium iodide (LiI) in the first excited A-state is investigated for molecules in the gas phase and embedded in helium nanodroplets, using femtosecond pump-probe photoionization spectroscopy. In the gas phase, the transient Li+ and LiI+ ion signals feature damped oscillations due to the excitation and decay of a vibrational wave packet. Based on high-level ab initio calculations of the electronic structure of LiI and simulations of the wave packet dynamics, the exponential signal decay is found to result from predissociation predominantly at the lowest avoided X-A potential curve crossing, for which we infer a coupling constant VXA = 650(20) cm−1. The lack of a pump-probe delay dependence for the case of LiI embedded in helium nanodroplets indicates fast droplet-induced relaxation of the vibrational excitation.

1.
D.
Tannor
and
S.
Rice
,
J. Chem. Phys.
83
,
5013
(
1985
).
2.
D. J.
Tannor
,
R.
Kosloff
, and
S. A.
Rice
,
J. Chem. Phys.
85
,
5805
(
1986
).
3.
P.
Brumer
and
M.
Shapiro
,
Chem. Phys. Lett.
126
,
541
(
1986
).
5.
A.
Zewail
,
Femtochemistry
(
World Scientific
,
Singapore
,
1994
).
6.
Femtosecond Chemistry
, edited by
J.
Manz
and
L.
Wöste
(
VCH
,
Weinheim
,
1995
).
7.
Femtochemistry
, edited by
M.
Chergui
(
World Scientific
,
Singapore
,
1995
).
8.
T. S.
Rose
,
M. J.
Rosker
, and
A. H.
Zewail
,
J. Chem. Phys.
88
,
6672
(
1988
).
9.
T. S.
Rose
,
M. J.
Rosker
, and
A. H.
Zewail
,
J. Chem. Phys.
91
,
7415
(
1989
).
10.
P.
Cong
,
J. L.
Herek
, and
A. H.
Zewail
,
Nature
348
,
225
(
1990
).
11.
T. R.
Su
and
S. J.
Riley
,
J. Chem. Phys.
71
,
3194
(
1979
).
12.
K. B.
Møller
,
N. E.
Henriksen
, and
A. H.
Zewail
,
J. Chem. Phys.
113
,
10477
(
2000
).
13.
P.
Claas
,
G.
Droppelmann
,
C. P.
Schulz
,
M.
Mudrich
, and
F.
Stienkemeier
,
J. Phys. B
39
,
S1151
(
2006
).
14.
P.
Claas
,
G.
Droppelmann
,
C. P.
Schulz
,
M.
Mudrich
, and
F.
Stienkemeier
,
J. Phys. Chem. A
111
,
7537
(
2007
).
15.
M.
Schlesinger
,
M.
Mudrich
,
F.
Stienkemeier
, and
W. T.
Strunz
,
Chem. Phys. Lett.
490
,
245
(
2010
).
16.
M.
Mudrich
,
P.
Heister
,
T.
Hippler
,
C.
Giese
,
O.
Dulieu
, and
F.
Stienkemeier
,
Phys. Rev. A
80
,
042512
(
2009
).
17.
B.
Grüner
,
M.
Schlesinger
,
P.
Heister
,
W. T.
Strunz
,
F.
Stienkemeier
, and
M.
Mudrich
,
Phys. Chem. Chem. Phys.
13
,
6816
(
2011
).
18.
S.
Grebenev
,
J. P.
Toennies
, and
A. F.
Vilesov
,
Science
279
,
2083
(
1998
).
19.
N. B.
Brauer
,
S.
Smolarek
,
E.
Loginov
,
D.
Mateo
,
A.
Hernando
,
M.
Pi
,
M.
Barranco
,
W. J.
Buma
, and
M.
Drabbels
,
Phys. Rev. Lett.
111
,
153002
(
2013
).
20.
L. F.
Gomez
,
K. R.
Ferguson
,
J. P.
Cryan
,
C.
Bacellar
,
R. M. P.
Tanyag
,
C.
Jones
,
S.
Schorb
,
D.
Anielski
,
A.
Belkacem
,
C.
Bernando
 et al,
Science
345
,
906
(
2014
).
21.
D.
Pentlehner
,
J. H.
Nielsen
,
A.
Slenczka
,
K.
Mølmer
, and
H.
Stapelfeldt
,
Phys. Rev. Lett.
110
,
093002
(
2013
).
22.
P.
Cong
,
G.
Roberts
,
J. L.
Herek
,
A.
Mohktari
, and
A. H.
Zewail
,
J. Phys. Chem.
100
,
7832
(
1996
).
23.
C.
Jouvet
,
S.
Martrenchard
,
D.
Solgadi
,
C.
Dedonder-Lardeux
,
M.
Mons
,
G.
Grégoire
,
I.
Dimicoli
,
F.
Piuzzi
,
J. P.
Visticot
,
J. M.
Mestdagh
 et al,
J. Phys. Chem. A
101
,
2555
(
1997
).
24.
V.
Engel
and
H.
Metiu
,
J. Chem. Phys.
91
,
1596
(
1989
).
25.
M.
Braun
,
C.
Meier
, and
V.
Engel
,
J. Chem. Phys.
105
,
530
(
1996
).
26.
S.
Chapman
and
M. S.
Child
,
J. Phys. Chem.
95
,
578
(
1991
).
27.
Y.
Arasaki
,
K.
Takatsuka
,
K.
Wang
, and
V.
McKoy
,
J. Chem. Phys.
119
,
7913
(
2003
).
28.
S.
Schaefer
,
D.
Bender
, and
E.
Tiemann
,
Chem. Phys.
102
,
165
(
1986
).
29.
G. A. L.
Delvigne
and
J.
Los
,
Physica
67
,
166
(
1973
).
30.
G. A. L.
Delvigne
and
J.
Los
,
Mol. Phys.
27
,
159
(
1974
).
31.
H.
Stoll
,
B.
Metz
, and
M.
Dolg
,
J. Comput. Chem.
23
,
767
(
2002
).
32.
K. A.
Peterson
,
B. C.
Shepler
,
D.
Figgen
, and
H.
Stoll
,
J. Phys. Chem. A
110
,
13877
(
2006
).
33.
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
).
34.
H.-J.
Werner
,
P. J.
Knowles
 et al, molpro, version 2010.1, a package of ab initio programs, 2010, see http://www.molpro.net.
35.
H.-J.
Werner
and
P. J.
Knowles
,
J. Chem. Phys.
89
,
5803
(
1988
).
36.
S. R.
Langhoff
and
E. R.
Davidson
,
Int. J. Quantum Chem.
8
,
61
(
1974
).
37.
H.-J.
Werner
and
P. J.
Knowles
,
J. Chem. Phys.
82
,
5053
(
1985
).
38.
P. J.
Knowles
,
C.
Hampel
, and
H.-J.
Werner
,
J. Chem. Phys.
99
,
5219
(
1993
).
40.
F.
Stienkemeier
and
K. K.
Lehmann
,
J. Phys. B: At., Mol. Opt. Phys.
39
,
R127
(
2006
).
41.
M.
Mudrich
and
F.
Stienkemeier
,
Int. Rev. Phys. Chem.
33
,
301
(
2014
).
42.
L.
Fechner
,
B.
Grüner
,
A.
Sieg
,
C.
Callegari
,
F.
Ancilotto
,
F.
Stienkemeier
, and
M.
Mudrich
,
Phys. Chem. Chem. Phys.
14
,
3843
(
2012
).
43.
J.
von Vangerow
,
A.
Sieg
,
F.
Stienkemeier
,
M.
Mudrich
,
A.
Leal
,
D.
Mateo
,
A.
Hernando
,
M.
Barranco
, and
M.
Pi
,
J. Phys. Chem. A
118
,
6604
(
2014
).
44.
I. S.
Averbukh
and
N. F.
Perelman
,
Phys. Lett. A
139
,
449
(
1989
).
45.
S. I.
Vetchinkin
,
A. S.
Vetchinkin
,
V. V.
Eryomin
, and
I. M.
Umanskii
,
Chem. Phys. Lett.
215
,
11
(
1993
).
46.
J.
Tiggesbäumker
and
F.
Stienkemeier
,
Phys. Chem. Chem. Phys.
9
,
4748
(
2007
).
47.
C.
Giese
,
F.
Stienkemeier
,
M.
Mudrich
,
A. W.
Hauser
, and
W. E.
Ernst
,
Phys. Chem. Chem. Phys.
13
,
18769
(
2011
).
48.
U.
Riss
and
H.-D.
Meyer
,
J. Phys. B
26
,
4503
(
1993
).
49.
R.
Kosloff
,
Annu. Rev. Phys. Chem.
45
,
145
(
1994
).
50.
F.
Lackner
,
G.
Krois
,
T.
Buchsteiner
,
J. V.
Pototschnig
, and
W. E.
Ernst
,
Phys. Rev. Lett.
113
,
153001
(
2014
).
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