The equilibrium geometries and binding energies of the van der Waals (vdW) complexes benzene–neon and benzene–argon have been calculated at the level of second‐order Mo/ller–Plesset perturbation theory (MP2). Terms linear in the interelectronic distances r12 were used in the MP2 treatment to converge fast to the one‐particle basis set limit. This new method, MP2‐R12 as implemented in the sore program, was applied with high quality basis sets derived from Dunning’s aug‐cc‐pVXZ (X=D,T,Q,5) sets. In reward of the efforts to reach the basis set limit, it is found that the calculated binding energies for the vdW complexes were computed virtually free of a basis set superposition error (BSSE). The key MP2‐R12 results are De=154 cm−1 and re=3.32 Å for benzene–neon and De=553 cm−1 and re=3.41 Å for benzene–argon. The permanent dipole moments of the vdW complexes have been computed by finite field perturbation theory. Coupled‐cluster calculations of type CCSD(T), although performed with considerably smaller basis sets than the MP2‐R12 calculations, show that, to improve the MP2‐R12 results, it is inevitable to consider correlation effects due to connected triple excitations which go beyond the MP2 description.

1.
Th.
Brupbacher
,
J.
Makarewicz
, and
A.
Bauder
,
J. Chem. Phys.
101
,
9736
(
1994
).
2.
Th.
Brupbacher
and
A.
Bauder
,
Chem. Phys. Lett.
173
,
435
(
1990
).
3.
T. D.
Klots
,
T.
Emilsson
, and
H. S.
Gutowsky
,
J. Chem. Phys.
97
,
5335
(
1992
).
4.
Th.
Brupbacher
,
H. P.
Lüthi
, and
A.
Bauder
,
Chem. Phys. Lett.
195
,
482
(
1992
).
5.
W.
Klopper
and
W.
Kutzelnigg
,
Chem. Phys. Lett.
134
,
17
(
1986
).
6.
W.
Kutzelnigg
and
W.
Klopper
,
J. Chem. Phys.
94
,
1985
(
1991
).
7.
W.
Klopper
,
Chem. Phys. Lett.
186
,
583
(
1991
).
8.
P.
Hobza
,
H. L.
Selzle
, and
E. W.
Schlag
,
J. Chem. Phys.
95
,
391
(
1991
).
9.
P.
Hobza
,
O.
Bludský
,
H. L.
Selzle
, and
E. W.
Schlag
,
J. Chem. Phys.
97
,
335
(
1992
).
10.
P.
Hobza
,
O.
Bludský
,
H. L.
Selzle
, and
E. W.
Schlag
,
J. Chem. Phys.
98
,
6223
(
1993
).
11.
P.
Hobza
,
H. L.
Selzle
, and
E. W.
Schlag
,
J. Phys. Chem.
97
,
3937
(
1993
).
12.
P.
Hobza
,
H. L.
Selzle
, and
E. W.
Schlag
,
J. Chem. Phys.
99
,
2809
(
1993
).
13.
W.
Klopper
and
J.
Almlöf
,
J. Chem. Phys.
99
,
5167
(
1993
).
14.
SORE (second-order r12 energy), written by W. Klopper.
15.
M.
Häser
,
J.
Almlöf
, and
M.
Feyereisen
,
Theor. Chim. Acta
79
,
115
(
1991
).
16.
R.
Ahlrichs
,
M.
Bär
,
M.
Häser
,
H.
Horn
, and
C.
Kölmel
,
Chem. Phys. Lett.
162
,
165
(
1989
).
17.
W.
Klopper
and
R.
Röhse
,
Theor. Chim. Acta
83
,
441
(
1992
).
18.
HERMIT (one- and two-electron integral generator), written by T. U. Helgaker.
19.
DISCO, a direct SCF and MP2 program, written by J. Almlöf, K. Fægri, M. W. Feyereisen, T. H. Fischer, K. Korsell, and H. P. Lüthi.
20.
ACES II (Version 1.0), written by J. F. Stanton, J. Gauss, J. D. Watts, W. J. Lauderdale, and R. J. Bartlett, University of Florida, Gainesville.
21.
MOLECULE-SWEDEN, an electronic structure program, written by J. Almlöf, C. W. Bauschlicher, M. R. A. Blomberg, D. P. Chong, A. Heiberg, S. R. Langhoff, P.-Å. Malmqvist, A. P. Rendell, B. O. Roos, P. E. M. Siegbahn, and P. R. Taylor.
22.
COMENIUS, a coupled-cluster code with linear r12 terms, written by J. Noga.
23.
J.
Noga
,
W.
Kutzelnigg
, and
W.
Klopper
,
Chem. Phys. Lett.
199
,
497
(
1992
).
24.
J. Noga and W. Kutzelnigg, J. Chem. Phys. (in press).
25.
S. F.
Boys
and
F.
Bernardi
,
Mol. Phys.
19
,
553
(
1970
).
26.
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
).
27.
R. A.
Kendall
,
T. H.
Dunning
, Jr.
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
).
28.
D. E.
Woon
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
98
,
1358
(
1993
).
29.
D. E. Woon, K. A. Peterson, and T. H. Dunning, Jr. (unpublished).
30.
J. R.
Flores
,
J. Chem. Phys.
98
,
5642
(
1993
).
31.
V.
Termath
,
W.
Klopper
, and
W.
Kutzelnigg
,
J. Chem. Phys.
94
,
2002
(
1991
).
32.
A.
Kumar
and
W. J.
Meath
,
Can. J. Chem.
63
,
1616
(
1985
).
33.
M. P. Boogaard and B. J. Orr, MTP International Review of Science, Physical Chemistry, edited by A. D. Buckingham (Butterworth, London, 1975), Ser. 2, Vol. 2.
34.
J. E.
Rice
,
G. E.
Scuseria
,
T. J.
Lee
,
P. R.
Taylor
, and
J.
Almlöf
,
Chem. Phys. Lett.
191
,
23
(
1992
).
35.
D. E.
Woon
,
Chem. Phys. Lett.
204
,
29
(
1993
).
36.
P.
Lazzeretti
,
M.
Malagoli
, and
R.
Zanasi
,
J. Mol. Struct. (THEOCHEM)
234
,
127
(
1991
).
37.
P.
Lazzeretti
,
M.
Malagoli
, and
R.
Zanasi
,
Chem. Phys. Lett.
167
,
101
(
1990
).
38.
D. E. Woon (private communication).
39.
R.
Eggenberger
,
S.
Gerber
,
H.
Huber
, and
D.
Searles
,
Chem. Phys. Lett.
156
,
395
(
1991
).
40.
R. Eggenberger, S. Gerber, H. Huber, and M. Welker (to be published; private communication).
41.
R. J.
Gdanitz
,
Chem. Phys. Lett.
210
,
253
(
1993
).
42.
P.-O.
Widmark
,
P.-Å.
Malmqvist
, and
B. O.
Roos
,
Theor. Chim. Acta
77
,
291
(
1990
).
43.
H. P. Lüthi (unpublished).
44.
H.-J. Werner (private communication).
45.
H.
Krause
and
H. J.
Neusser
,
J. Chem. Phys.
99
,
6278
(
1993
).
46.
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