A calculation of the spectrum for the excitation of the van der Waals modes in ArHCN is reported. The coupled electron pair approximation is used to compute an abinitio potential energy surface for the interaction of Ar with rigid HCN. The rovibrational bound states for the complex are calculated using a variational coupled‐basis set method in which a self‐consistent field approach is used to optimize simultaneously the basis sets for both the intermolecular bending and stretching motions in the van der Waals molecule. The calculations are compared with experimental results, including a measurement of the infrared spectrum of ArHCN in the region of the CH stretching vibration. The calculations predict that several bending modes with frequencies less than 20 cm−1 should have excitation intensities large enough to be observed. These low frequency bending modes arise from the small rotational constant of the HCN molecule and are not due to special features of the Ar–HCN potential energy surface.

1.
Structure and Dynamics of Weakly Bound Complexes, edited by A. Weber (Reidel, Dordrecht, 1987);
Dynamics of Polyatomic Van der Waals Complexes, edited by N. Halberstadt and K. C. Janda (Plenum, New York, 1990).
2.
D. J.
Nesbitt
,
Chem. Rev.
88
,
843
(
1988
).
3.
R. J.
Le Roy
and
J. S.
Carley
,
Adv. Chem. Phys.
42
,
353
(
1980
).
4.
J. M.
Hutson
,
J. Chem. Phys.
89
,
4550
(
1988
).
5.
J. M.
Hutson
,
J. Chem. Phys.
91
,
4448
(
1989
).
6.
J. M.
Hutson
,
J. Chem. Phys.
91
,
4455
(
1989
).
7.
D. J.
Nesbitt
,
M. S.
Child
, and
D. C.
Clary
,
J. Chem. Phys.
90
,
4855
(
1989
).
8.
S. E.
Novick
,
P.
Davies
,
S. J.
Harris
, and
W.
Klemperer
,
J. Chem. Phys.
59
,
2273
(
1973
).
9.
M. D.
Marshall
,
A.
Charo
,
H. O.
Leung
, and
W.
Klemperer
,
J. Chem. Phys.
83
,
4924
(
1985
).
10.
D.
Ray
,
R. L.
Robinson
,
D.‐H.
Gwo
, and
R. J.
Saykally
,
J. Chem. Phys.
84
,
1171
(
1986
);
D.
Ray
,
R. L.
Robinson
,
D.‐H.
Gwo
, and
R. J.
Saykally
,
R. L.
Robinson
,
D.
Ray
,
D.‐H.
Gwo
, and
R. J.
Saykally
,
J. Chem. Phys.
87
,
5156
(
1987
); ,
J. Chem. Phys.
R. L.
Robinson
,
D.‐H.
Gwo
,
D.
Ray
, and
R. J.
Saykally
,
J. Chem. Phys.
86
,
5211
(
1987
); ,
J. Chem. Phys.
R. L.
Robinson
,
D.‐H.
Gwo
, and
R. J.
Saykally
,
J. Chem. Phys.
87
,
5156
(
1987
).,
J. Chem. Phys.
11.
C. M.
Lovejoy
and
D. J.
Nesbitt
,
J. Chem. Phys.
91
,
2790
(
1989
).
12.
C. M.
Lovejoy
and
D. J.
Nesbitt
,
Chem. Phys. Lett.
146
,
582
(
1988
).
13.
C. M.
Lovejoy
and
D. J.
Nesbitt
,
Chem. Phys. Lett.
147
,
490
(
1988
).
14.
D. C.
Clary
and
D. J.
Nesbitt
,
J. Chem. Phys.
90
,
7000
(
1989
).
15.
D. C.
Clary
,
C. M.
Lovejoy
,
S. V.
ONeil
, and
D. J.
Nesbitt
,
Phys. Rev. Lett.
61
,
1576
(
1988
);
S. V.
ONeil
,
D. J.
Nesbitt
,
R.
Rosmus
,
H.‐J.
Werner
, and
D. C.
Clary
,
J. Chem. Phys.
91
,
711
(
1989
);
D. J.
Nesbitt
,
C. M.
Lovejoy
,
T. G.
Lindeman
,
S. V.
ONeil
, and
D. C.
Clary
,
J. Chem. Phys.
91
,
722
(
1989
).,
J. Chem. Phys.
16.
A. S.
Pine
,
W. J.
Lafferty
, and
B. J.
Howard
,
J. Chem. Phys.
81
,
2929
(
1984
);
B. J.
Howard
and
A. S.
Pine
,
Chem. Phys. Lett.
122
,
1
(
1985
).
17.
E. J.
Campbell
,
L. W.
Buxton
, and
A. C.
Legon
,
J. Chem. Phys.
78
,
3483
(
1983
).
18.
K. R.
Leopold
,
G. T.
Fraser
,
F. J.
Lin
,
D. D.
Nelson
, Jr.
, and
W.
Klemperer
,
J. Chem. Phys.
81
,
4922
(
1984
).
19.
T. D.
Klots
,
C. E.
Dykstra
, and
H. S.
Gutowsky
,
J. Chem. Phys.
90
,
30
(
1989
).
20.
R. E.
Bumgarner
and
G. A.
Blake
,
Chem. Phys. Lett.
161
,
308
(
1989
).
21.
G. T.
Fraser
and
A. S.
Pine
,
J. Chem. Phys.
91
,
3319
(
1989
).
22.
D. C.
Clary
and
P. J.
Knowles
,
J. Chem. Phys.
93
,
6334
(
1990
).
23.
C.
Chakravarty
,
D. C.
Clary
,
A.
Degli Esposti
, and
H.‐J.
Werner
,
J. Chem. Phys.
93
,
3367
(
1990
).
24.
D. C. Clary, C. Chakravarty, and A. R. Tiller, in Dynamics of Polyatomic Van der Waals Complexes, edited by N. Halberstadt and K. C. Janda (Plenum, New York, 1990), p. 355.
25.
W.
Meyer
,
J. Chem. Phys.
58
,
1017
(
1973
).
26.
J. M.
Bowman
,
Acc. Chem. Res.
19
,
202
(
1986
).
27.
M. A.
Ratner
and
R. B.
Gerber
,
J. Phys. Chem.
90
,
20
(
1986
).
28.
P. R.
Bunker
,
T.
Carrington
Jr.
,
P. C.
Gomez
,
M. D.
Marshall
,
M.
Kofranek
,
H.
Lischka
, and
A.
Karpfen
,
J. Chem. Phys.
91
,
5154
(
1989
).
29.
C. G. Gray and K. E. Gubbins, The Theory of Molecular Fluids (Clarendon, Oxford, 1984).
30.
A. M.
Arthurs
and
A.
Dalgarno
,
Proc. R. Soc. London Ser. A
256
,
540
(
1960
).
31.
S. F.
Boys
and
F.
Bernadi
,
Mol. Phys.
19
,
553
(
1970
).
32.
A. D.
Buckingham
,
P. W.
Fowler
, and
J. M.
Hutson
,
Chem. Rev.
88
,
963
(
1988
).
33.
I. P.
Hamilton
and
J. C.
Light
,
J. Chem. Phys.
84
,
306
(
1986
).
34.
D. M. Brink and G. R. Satchler, Angular Momentum (Clarendon, Oxford, 1968).
35.
J. M. Hutson, in Advances in Molecular Vibrations and Collision Dynamics (to be published).
36.
D. J.
Nesbitt
,
Faraday Discuss. Chem. Soc.
86
,
33
(
1988
).
37.
S.
Bratoz
and
M. L.
Martin
,
J. Chem. Phys.
42
,
1051
(
1965
).
38.
G. Herzberg, Infrared and Raman Spectra (Van Nostrand, New York, 1945).
This content is only available via PDF.
You do not currently have access to this content.