The potential energy surface for the electronic ground state of PH3 was calculated at the CCSD(T) level using aug-cc-pV(Q+d)Z and aug-cc-pVQZ basis sets for P and H, respectively, with scalar relativistic corrections included. A parametrized function was fitted through these ab initio points, and one parameter of this function was empirically adjusted. This analytical PES was employed in variational calculations of vibrational energies with the newly developed program TROVE. The convergence of the calculated vibrational energies with increasing vibrational basis set size was improved by means of an extrapolation scheme analogous to the complete basis set limit schemes used in ab initio electronic structure calculations. The resulting theoretical energy values are in excellent agreement with the available experimentally derived values.

1.
S. N.
Yurchenko
,
M.
Carvajal
,
P.
Jensen
,
F.
Herregodts
, and
T. R.
Huet
,
Chem. Phys.
290
,
59
(
2003
).
2.
S. N.
Yurchenko
,
W.
Thiel
,
S.
Patchkovskii
, and
P.
Jensen
,
Phys. Chem. Chem. Phys.
7
,
573
(
2005
).
3.
S. N.
Yurchenko
,
M.
Carvajal
,
W.
Thiel
, and
P.
Jensen
,
J. Mol. Spectrosc.
239
,
71
(
2006
).
4.
S. N.
Yurchenko
,
M.
Carvajal
,
P.
Jensen
,
H.
Lin
,
J. J.
Zheng
, and
W.
Thiel
,
Mol. Phys.
103
,
359
(
2005
).
5.
S. N.
Yurchenko
,
W.
Thiel
,
M.
Carvajal
,
H.
Lin
, and
P.
Jensen
,
Adv. Quantum Chem.
48
,
209
(
2005
).
6.
D.
Wang
,
Q.
Shi
, and
Q. -S.
Zhu
,
J. Chem. Phys.
112
,
9624
(
2000
).
7.
P.
Jensen
,
G.
Osmann
, and
I. N.
Kozin
, in
Vibration-Rotational Spectroscopy and Molecular Dynamics
, edited by
D.
Papoušek
(
World Scientific
,
Singapore
,
1997
).
8.
P. R.
Bunker
and
P.
Jensen
,
Molecular Symmetry and Spectroscopy
, 2nd ed. (
NRC
,
Ottawa
,
1998
).
9.
S. N.
Yurchenko
,
W.
Thiel
, and
P.
Jensen
,
J. Mol. Spectrosc.
245
,
126
(
2007
).
10.
P. R.
Bunker
and
P.
Jensen
,
Fundamentals of Molecular Symmetry
(
IOP
,
Bristol
,
2004
).
11.
R. I.
Ovsyannikov
,
W.
Thiel
,
S. N.
Yurchenko
,
M.
Carvajal
, and
P.
Jensen
,
J. Mol. Spectrosc.
(in press).
12.
G. A.
Petersson
,
A.
Bennett
,
T. G.
Tensfeldt
,
M. A.
Al-Laham
,
W. A.
Shirley
, and
J.
Mantzaris
,
J. Chem. Phys.
89
,
2193
(
1988
).
13.
G. A.
Petersson
and
M. A.
Al-Laham
,
J. Chem. Phys.
94
,
6081
(
1991
).
14.
G. D.
Purvis
and
R. J.
Bartlett
,
J. Chem. Phys.
76
,
1910
(
1982
).
15.
M.
Urban
,
J.
Noga
,
S. J.
Cole
, and
R. J.
Bartlett
,
J. Chem. Phys.
83
,
4041
(
1985
).
16.
K.
Raghavachari
,
G. W.
Trucks
,
J. A.
Pople
, and
M.
Head-Gordon
,
Chem. Phys. Lett.
157
,
479
(
1989
).
17.
MOLPRO, a package of ab initio programs written by
H. -J.
Werner
and
P. J.
Knowles
, version 2002.3 and 2002.6, with contributions from
R. D.
Amos
,
A.
Bernhardsson
,
A.
Berning
 et al
18.
C.
Hampel
,
K.
Peterson
, and
H. -J.
Werner
,
Chem. Phys. Lett.
190
,
1
(
1992
), and references therein;
the program to compute the perturbative triples corrections has been developed by
M. J. O.
Deegan
and
P. J.
Knowles
,
Chem. Phys. Lett.
227
,
321
(
1994
).
19.
T. H.
Dunning
,
J. Chem. Phys.
90
,
1007
(
1989
).
20.
D. E.
Woon
and
T. H.
Dunning
,
J. Chem. Phys.
98
,
1358
(
1993
).
21.
R. A.
Kendall
,
T. H.
Dunning
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
).
22.
A. K.
Wilson
and
T. H.
Dunning
,
J. Chem. Phys.
119
,
11712
(
2003
).
23.
S. -G.
He
,
J. J.
Zheng
,
S. -M.
Hu
,
H.
Lin
,
Y.
Ding
,
X. -H.
Wang
, and
Q. -S.
Zhu
,
J. Chem. Phys.
114
,
7018
(
2001
).
24.
G.
Tarrago
,
N.
Lacome
,
A.
Lévy
,
G.
Guelachvili
,
B.
Bézard
, and
P.
Drossart
,
J. Mol. Spectrosc.
154
,
30
(
1992
).
25.
O. N.
Ulenikov
,
E. S.
Bekhtereva
,
V. A.
Kozinskaia
,
J. J.
Zheng
,
S. -G.
He
,
S. -M.
Hu
,
Q. -S.
Zhu
,
C.
Leroy
, and
L.
Pluchart
,
J. Mol. Spectrosc.
215
,
295
(
2002
).
26.
R. A.
Butler
,
L.
Sagui
,
L.
Kleiner
, and
L. R.
Brown
,
J. Mol. Spectrosc.
238
,
178
(
2006
).
27.
D.
Feller
,
J. Chem. Phys.
96
,
6104
(
1992
).
28.
D.
Feller
,
J. Chem. Phys.
98
,
7059
(
1993
).
29.
H. -S.
Lee
and
J. C.
Light
,
J. Chem. Phys.
118
,
3458
(
2003
).
30.
R.
Dawes
and
T.
Carrington
,
J. Chem. Phys.
122
,
134101
(
2005
).
31.
M. S.
Child
and
L.
Halonen
,
Adv. Chem. Phys.
57
,
1
(
1984
).
32.
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