The population relaxation of the OD stretching vibration of HOD diluted in H2O is studied by time-resolved infrared pump-probe spectroscopy for temperatures between 278 and 663 K in the density range 0.28ρ1.01g/cm3. Transient spectra recorded after exciting the v=01 OD stretching transition at low temperatures show a delay between excited state decay and formation of the thermalized spectrum pointing to an intermediately populated state. Above 400 K, the rates of excited state decay and ground state recovery become equivalent and the intermediate state is not detectable anymore. Over the entire thermodynamic range, the derived OD stretch relaxation rate constant kr depends linearly on the static dielectric constant ε of water, indicating a correlation of kr with the average hydrogen bond connectivity of HOD within the H2O network. However, in contrast to the OH stretch relaxation rate constant of the complementary system of HOD in D2O, the low density data of kr(ε) extrapolate to a nonzero intercept for ε1. Our analysis suggests that at ambient conditions the OD excited state is mainly depopulated by a direct v=10 transition, avoiding the excited v=1 HOD bending state. Therefore, at room temperature the detected intermediate is assigned to a nonthermalized state with respect to nuclear degrees of freedom of the solvent molecules, and subsequent formation of the final product spectrum is related to a rearrangement of the hydrogen bond network. Passing over to the gas phase the excited OD stretch state shifts into close resonance with the HOD bend overtone, thereby opening up an additional relaxation channel.

1.
Water: A Comprehensive Treatise
, edited by
F.
Franks
(
Plenum
,
New York
,
1972
), Vol. 1.
2.
R.
Rey
,
K. B.
Moller
, and
J. T.
Hynes
,
J. Phys. Chem. A
106
,
11993
(
2002
).
3.
C. P.
Lawrence
and
J. L.
Skinner
,
J. Chem. Phys.
118
,
264
(
2003
).
4.
Ultrafast Hydrogen Bonding Dynamics and Proton Transfer Processes in the Condensed Phase
, edited by
T.
Elsaesser
and
H. J.
Bakker
(
Kluwer
,
Dordrecht
,
2002
).
5.
E. T. J.
Nibbering
and
T.
Elsaesser
,
Chem. Rev. (Washington, D.C.)
104
,
1887
(
2004
).
6.
A.
Novak
,
Struct. Bonding (Berlin)
18
,
177
(
1974
).
8.
A.
Kandratsenka
,
D.
Schwarzer
, and
P.
Vöhringer
,
J. Chem. Phys.
128
,
244510
(
2008
).
9.
R.
Laenen
,
C.
Rauscher
, and
A.
Laubereau
,
Phys. Rev. Lett.
80
,
2622
(
1998
).
10.
S.
Woutersen
,
U.
Emmerichs
,
H. -K.
Nienhuys
, and
H. J.
Bakker
,
Phys. Rev. Lett.
81
,
1106
(
1998
).
11.
G. M.
Gale
,
G.
Gallot
, and
N.
Lascoux
,
Chem. Phys. Lett.
311
,
123
(
1999
).
12.
A. J.
Lock
and
H. J.
Bakker
,
J. Chem. Phys.
117
,
1708
(
2002
).
13.
P.
Bodis
,
O. F. A.
Larsen
, and
S.
Woutersen
,
J. Phys. Chem. A
109
,
5303
(
2005
).
14.
S.
Ashihara
,
N.
Huse
,
A.
Espagne
,
E. T. J.
Nibbering
, and
T.
Elsaesser
,
J. Phys. Chem. A
111
,
743
(
2007
).
15.
J.
Lindner
,
D.
Cringus
,
M. S.
Pshenichnikov
, and
P.
Vöhringer
,
Chem. Phys.
341
,
326
(
2007
).
16.
M. L.
Cowan
,
B. D.
Bruner
,
N.
Huse
,
J. R.
Dwyer
,
B.
Chugh
,
E. T. J.
Nibbering
,
T.
Elsaesser
, and
R. J. D.
Miller
,
Nature (London)
434
,
199
(
2005
).
17.
S.
Woutersen
,
U.
Emmerichs
, and
H. J.
Bakker
,
Science
278
,
658
(
1997
).
18.
S.
Bratos
,
G. M.
Gale
,
G.
Gallot
,
F.
Hache
,
N.
Lascoux
, and
J. -C.
Leicknam
,
Phys. Rev. E
61
,
5211
(
2000
).
19.
G. M.
Gale
,
G.
Gallot
,
F.
Hache
,
N.
Lascoux
,
S.
Bratos
, and
J. -C.
Leicknam
,
Phys. Rev. Lett.
82
,
1068
(
1999
).
20.
H. -K.
Nienhuys
,
S.
Woutersen
,
R. A.
van Santen
, and
H. J.
Bakker
,
J. Chem. Phys.
111
,
1494
(
1999
).
21.
R.
Laenen
,
C.
Rauscher
, and
A.
Laubereau
,
J. Phys. Chem. B
102
,
9304
(
1998
).
22.
Z.
Wang
,
A.
Pakoulev
,
Y.
Pang
, and
D. D.
Dlott
,
J. Phys. Chem. A
108
,
9054
(
2004
).
23.
Z.
Wang
,
Y.
Pang
, and
D. D.
Dlott
,
Chem. Phys. Lett.
397
,
40
(
2004
).
24.
D.
Schwarzer
,
J.
Lindner
, and
P.
Vöhringer
,
J. Chem. Phys.
123
,
161105
(
2005
).
25.
D.
Schwarzer
,
J.
Lindner
, and
P.
Vöhringer
,
J. Phys. Chem. A
110
,
2858
(
2006
).
26.
R.
Rey
and
J. T.
Hynes
,
J. Chem. Phys.
104
,
2356
(
1996
).
27.
C. P.
Lawrence
and
J. L.
Skinner
,
J. Chem. Phys.
119
,
1623
(
2003
).
28.
C. P.
Lawrence
and
J. L.
Skinner
,
J. Chem. Phys.
119
,
3840
(
2003
).
29.
R.
Rey
,
K. B.
Moller
, and
J. T.
Hynes
,
Chem. Rev. (Washington, D.C.)
104
,
1915
(
2004
).
30.
A.
Kandratsenka
,
J.
Schroeder
,
D.
Schwarzer
, and
V. S.
Vikhrenko
,
J. Chem. Phys.
130
,
174507
(
2009
).
31.
T.
Steinel
,
J. B.
Ashbury
,
J.
Zheng
, and
M. D.
Fayer
,
J. Phys. Chem. A
108
,
10957
(
2004
).
32.
Y. L. A.
Rezus
and
H. J.
Bakker
,
J. Chem. Phys.
123
,
114502
(
2005
).
33.
H. J.
Bakker
,
Y. L. A.
Rezus
, and
R. L. A.
Timmer
,
J. Phys. Chem. A
112
,
11523
(
2008
).
34.
K. J.
Tielrooij
,
C.
Petersen
,
Y. L. A.
Rezus
, and
H. J.
Bakker
,
Chem. Phys. Lett.
471
,
71
(
2009
).
35.
R. A.
Kaindl
,
M.
Wurm
,
K.
Reimann
,
P.
Hamm
,
A. M.
Weiner
, and
M.
Woerner
,
J. Opt. Soc. Am. B
17
,
2086
(
2000
).
36.
P.
Hamm
,
R. A.
Kaindl
, and
J.
Stenger
,
Opt. Lett.
25
,
1798
(
2000
).
37.
PROPATHGroup
, PROPATH, a program package for thermophysical properties, Version 12.1,
2001
, Web site http://gibbs.mech.kyushu-u.ac.jp.
38.
E. U.
Franck
and
K.
Roth
,
Faraday Discuss. Chem. Soc.
43
,
108
(
1967
).
40.
N.
Yoshii
,
S.
Miura
, and
S.
Okazaki
,
Chem. Phys. Lett.
345
,
195
(
2001
).
41.
W. S.
Benedict
,
H.
Gailar
, and
E. K.
Plyler
,
J. Chem. Phys.
24
,
1139
(
1956
).
42.
M.
Falk
and
T. A.
Ford
,
Can. J. Chem.
44
,
1699
(
1966
).
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