We report simulated Raman and infrared spectra of liquid water and water clusters in the frequency range 0–1000 cm−1. The librational peak in the Raman spectrum of the liquid, which has a strong dependence on the anisotropy of the assumed gas‐phase polarizability tensor, allows us to choose between various models for that tensor. Most of the spectroscopically probed dynamics of the liquid are present in the small clusters, with N as low as 5. The librational peaks in the pentamer spectra are shown to redshift with increasing temperature.

1.
A.
Rahman
and
F. H.
Stillinger
,
J. Chem. Phys.
55
,
3336
(
1971
).
2.
O. F.
Nielsen
,
Chem. Phys. Lett.
60
,
515
(
1979
).
3.
(a)
G. E.
Walrafen
,
M. R.
Fisher
,
M. S.
Hokmabadi
, and
W.-H.
Yang
,
J. Chem. Phys.
85
,
6970
(
1986
);
(b) G. E. Walrafen and M. R. Fisher, in Biomembranes, A Volume of Methods of Enzymology, edited by L. Packer (Academic, New York, 1986);
(c)
G. E.
Walrafen
,
M. S.
Hokmabadi
, and
W.-H.
Yang
,
J. Chem. Phys.
88
,
4555
(
1988
).
4.
A.
De Santis
,
R.
Frattini
,
M.
Sampoli
,
V.
Mazzacurati
,
M.
Nardone
,
M. A.
Ricci
, and
G.
Ruocco
,
Mol. Phys.
61
,
1199
(
1987
);
P.
Benassi
,
V.
Mazzacurati
,
M.
Nardone
,
M. A.
Ricci
,
G.
Ruocco
,
A.
De Santis
,
R.
Frattini
, and
M.
Sampoli
,
Mol. Phys.
62
,
1467
(
1987
); ,
Mol. Phys.
P.
Benassi
,
V.
Mazzacurati
,
M.
Nardone
,
M. A.
Ricci
,
G.
Ruocco
, and
G.
Signorelli
,
J. Chem. Phys.
88
,
4553
(
1988
).
5.
M. H.
Brooker
,
G.
Hancock
,
B. C.
Rice
, and
J.
Shapter
,
J. Raman Spectrosc.
20
,
683
(
1989
).
6.
G. E.
Walrafen
,
J. Phys. Chem.
94
,
2237
(
1990
).
7.
K.
Mizoguchi
,
Y.
Hori
, and
Y.
Tominaga
,
J. Chem. Phys.
97
,
1961
(
1992
).
8.
P. A.
Madden
and
R. W.
Impey
,
Chem. Phys. Lett.
123
,
502
(
1986
);
R. W.
Impey
,
P. A.
Madden
, and
I. R.
McDonald
,
Mol. Phys.
46
,
513
(
1982
).
9.
(a)
M. A.
Ricci
,
G.
Ruocco
, and
M.
Sampoli
,
Mol. Phys.
67
,
19
(
1989
);
(b)
V.
Mazzacurati
,
M. A.
Ricci
,
G.
Ruocco
, and
M.
Sampoli
,
Chem. Phys. Lett.
159
,
383
(
1989
).
10.
O.
Matsuoka
,
E.
Clementi
, and
M.
Yoshimine
,
J. Chem. Phys.
64
,
1351
(
1976
).
11.
W. L.
Jorgensen
,
J.
Chandrasekhar
,
J. M.
Madura
,
R. W.
Impey
, and
M. L.
Klein
,
J. Chem. Phys.
79
,
926
(
1983
).
12.
I.
Ohmine
and
M.
Sasai
,
Prog. Theor. Phys. Suppl.
103
,
61
(
1991
), and references contained therein.
13.
B.
Guillot
,
J. Chem. Phys.
95
,
1543
(
1991
).
14.
H. J. Berendsen, J. P. M. Postma, W. F. Van Gusteren, and J. Hermans, in Intermolecular Forces, edited by B. Pullman (Reidel, Dordrecht, 1981), p. 331.
15.
X.
Yang
and
A. W.
Castleman
,
J. Geophys. Res.-Atmosph.
96
,
2573
(
1991
).
16.
P. L. M.
Plummer
and
T. S.
Chen
,
J. Chem. Phys.
86
,
7149
(
1987
).
17.
P. L. M.
Plummer
and
T. S.
Chen
,
J. Phys. Chem.
87
,
4190
(
1983
).
18.
I. P.
Bufifey
,
W. B.
Brown
, and
H. A.
Gebbie
,
J. Chem. Soc. Faraday Trans.
86
,
2357
(
1990
).
19.
K. S.
Kim
,
M.
Dupuis
,
G. C.
Lie
, and
E.
Clementi
,
Chem. Phys. Lett.
131
,
451
(
1986
).
20.
J. R.
Reimers
and
R. O.
Watts
,
Chem. Phys.
85
,
83
(
1984
).
21.
P. L. M.
Plummer
,
J. Mol. Struct.
237
,
47
(
1990
).
22.
C. E.
Dykstra
,
J. Chem. Phys.
91
,
6472
(
1989
).
23.
E.
Honegger
and
S.
Leutwyler
,
J. Chem. Phys.
88
,
2582
(
1988
);
R.
Knochenmuss
and
S.
Leutwyler
,
J. Chem. Phys.
96
,
5233
(
1992
).,
J. Chem. Phys.
24.
F. H.
Stillinger
and
A.
Rahman
,
J. Chem. Phys.
68
,
666
(
1978
).
25.
M. F.
Vernon
,
D. J.
Krajnovich
,
H. S.
Kwok
,
J. M.
Lisy
,
Y. R.
Shen
, and
Y. T.
Lee
,
J. Chem. Phys.
77
,
47
(
1982
);
D. F.
Coker
,
R. E.
Miller
, and
R. O.
Watts
,
J. Chem. Phys.
82
,
3554
(
1985
).,
J. Chem. Phys.
26.
S.
Wuelfert
,
D.
Herren
, and
S.
Leutwyler
,
J. Chem. Phys.
86
,
3751
(
1987
).
27.
N.
Pugliano
and
R. J.
Saykally
,
Science
257
,
1937
(
1992
);
N.
Pugliano
and
R. J.
Saykally
,
J. Chem. Phys.
96
,
1832
(
1992
).
28.
W. F.
Murphy
,
J. Chem. Phys.
67
,
5877
(
1977
).
29.
C.
Huiszoon
,
Mol. Phys.
58
,
865
(
1986
).
30.
P.
Raeymaekers
,
H. P.
Figeys
, and
P.
Geerlings
,
Mol. Phys.
65
,
925
(
1988
).
31.
G.
Maroulis
,
J. Chem. Phys.
94
,
1182
(
1991
).
32.
N. Scherer and G. Fleming (private communication);
R. J. D. Miller and S. Palese (private communication).
33.
W. F.
Murphy
,
M. H.
Brooker
,
O. F.
Nielsen
,
E.
Praestgaard
, and
J. E.
Bertie
,
J. Raman Spectrosc.
20
,
695
(
1989
).
34.
L. C.
Geiger
and
B. M.
Ladanyi
,
Chem. Phys. Lett.
159
,
413
(
1989
).
35.
L. E.
Fried
,
N.
Bernstein
, and
S.
Mukamel
,
Phys. Rev. Lett.
68
,
1842
(
1992
).
36.
L. E.
Fried
and
S.
Mukamel
,
J. Chem. Phys.
96
,
116
(
1992
).
37.
H. J. C.
Berendsen
,
J. R.
Grigera
, and
T. P.
Straatsma
,
J. Phys. Chem.
91
,
6269
(
1987
).
38.
M. P. Allen and D. J. Tildesley, Computer Simulation of Liquids (Clarenden, Oxford, 1987).
39.
N. G. Van Kampen, Stochastic Processes in Physics and Chemistry (North-Holland, New York, 1981).
40.
J.
Borysow
,
M.
Moraldi
, and
L.
Frommhold
,
Mol. Phys.
56
,
913
(
1985
).
41.
P.
Egelstaff
,
Adv. Phys.
11
,
203
(
1962
).
42.
G. E. Walrafen (private communication).
43.
R. A.
Kuharski
and
P. J.
Rossky
,
J. Chem. Phys.
82
,
5164
(
1985
).
44.
K.
Watanabe
and
M. L.
Klein
,
Chem. Phys.
131
,
157
(
1989
).
45.
R. W.
Hellwarth
,
Prog. Quantum Electron.
5
,
1
(
1977
).
46.
W. Bosma, Ph.D. thesis, University of Rochester, 1992.
47.
See, for example,
P.
Ahlström
,
A.
Wallqvst
,
S.
Engström
, and
B.
Jönsson
,
Mol. Phys.
68
,
563
(
1989
).
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