Advanced ab initio [coupled cluster theory through quasiperturbative triple excitations (CCSD(T))] and density functional (B3LYP) computational chemistry approaches were used in combination with the standard and augmented correlation consistent polarized valence basis sets [cc-pVnZ and aug-cc-pVnZ, where n=D(2), T(3), Q(4), and 5] to investigate the energetic and structural properties of small molecules containing third-row (Ga–Kr) atoms. These molecules were taken from the Gaussian-2 (G2) extended test set for third-row atoms. Several different schemes were used to extrapolate the calculated energies to the complete basis set (CBS) limit for CCSD(T) and the Kohn–Sham (KS) limit for B3LYP. Zero point energy and spin orbital corrections were included in the results. Overall, CCSD(T) atomization energies, ionization energies, proton affinities, and electron affinities are in good agreement with experiment, within 1.1 kcal/mol when the CBS limit has been determined using a series of two basis sets of at least triple zeta quality. For B3LYP, the overall mean absolute deviation from experiment for the three properties and the series of molecules is more significant at the KS limit, within 2.3 and 2.6 kcal/mol for the cc-pVnZ and aug-cc-pVnZ basis set series, respectively.

1.
K. A.
Peterson
,
A. K.
Wilson
,
D. E.
Woon
, and
T. H.
Dunning
, Jr.
,
Theor. Chem. Acc.
97
,
251
(
1997
).
2.
K. A.
Peterson
,
R. A.
Kendall
, and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
99
,
1930
(
1993
).
3.
K. A.
Peterson
,
R. A.
Kendall
, and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
99
,
9790
(
1993
).
4.
D. E.
Woon
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
101
,
8877
(
1994
).
5.
T.
van Mourik
,
A. K.
Wilson
, and
T. H.
Dunning
, Jr.
,
Mol. Phys.
96
,
529
(
1999
).
6.
J. A.
Pople
,
M.
Head-Gordon
,
D. J.
Fox
,
K.
Raghavachari
, and
L. A.
Curtiss
,
J. Chem. Phys.
90
,
5622
(
1988
).
7.
L. A.
Curtiss
,
K.
Raghavachari
,
G. W.
Trucks
, and
J. A.
Pople
,
J. Chem. Phys.
94
,
7221
(
1991
).
8.
L. A.
Curtiss
,
K.
Raghavachari
,
P. C.
Redfern
,
V.
Rassolov
, and
J. A.
Pople
,
J. Chem. Phys.
109
,
7764
(
1998
).
9.
J. A.
Montgomery
Jr.
,
M. J.
Frisch
,
J. W.
Ochterski
, and
G. A.
Petersson
,
J. Chem. Phys.
110
,
2822
(
1999
).
10.
J. W.
Ochterski
,
G. A.
Petersson
, and
J. A.
Montgomery
, Jr.
,
J. Chem. Phys.
104
,
2598
(
1996
).
11.
L. A.
Curtiss
,
M. P.
McGrath
,
J.-P.
Blaudeau
,
N. E.
Davis
,
R. C.
Binning
, Jr.
, and
L.
Radom
,
J. Chem. Phys.
103
,
6104
(
1995
).
12.
J.-P.
Blaudeau
,
M. P.
McGrath
,
L. A.
Curtiss
, and
L.
Radom
,
J. Chem. Phys.
107
,
5016
(
1997
).
13.
P. C.
Redfern
,
J.-P.
Blaudeau
, and
L. A.
Curtiss
,
J. Phys. Chem. A
101
,
8701
(
1997
).
14.
B. J.
Duke
and
L.
Radom
,
J. Chem. Phys.
109
,
3352
(
1998
).
15.
L. A.
Curtiss
,
P. C.
Redfern
,
V.
Rassolov
,
G.
Kedziora
, and
J. A.
Pople
,
J. Chem. Phys.
114
,
9287
(
2001
).
16.
V.
Ramakrishna
and
B. J.
Duke
,
J. Chem. Phys.
118
,
6137
(
2003
).
17.
A. K. Wilson and T. H. Dunning, Jr. (unpublished).
18.
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
90
,
1007
(
1989
).
19.
D. E.
Woon
and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
98
,
1358
(
1992
).
20.
R. A.
Kendall
,
T. H.
Dunning
, Jr.
, and
R. J.
Harrison
,
J. Chem. Phys.
96
,
6796
(
1992
).
21.
A. K.
Wilson
,
D. E.
Woon
,
K. A.
Peterson
, and
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
110
,
7667
(
1999
).
22.
T.
Azzam
,
R.
Schinke
,
S. C.
Farantos
,
M.
Joyeux
, and
K. A.
Peterson
,
J. Chem. Phys.
118
,
9643
(
2003
).
23.
D. A.
Dixon
,
W. A.
de Jong
,
K. A.
Peterson
, and
J. S.
Francisco
,
J. Phys. Chem. A
106
,
4725
(
2002
).
24.
K. A.
Peterson
,
B. A.
Flowers
, and
J. S.
Francisco
,
J. Chem. Phys.
115
,
7513
(
2001
).
25.
R.
Vetter
,
T.
Ritschel
,
L.
Zulicke
, and
K. A.
Peterson
,
J. Phys. Chem. A
107
,
1405
(
2003
).
26.
L.
Sari
,
Y.
Yamaguchi
, and
H. F.
Schaefer
III
,
J. Chem. Phys.
115
,
5932
(
2001
).
27.
Q.
Li
,
G.
Li
,
W.
Xu
,
Y.
Xie
, and
H. F.
Schaefer
III
,
J. Chem. Phys.
111
,
7945
(
1999
).
28.
L.
Sari
,
K. A.
Peterson
,
Y.
Yamaguchi
, and
H. F.
Schaefer
III
,
J. Chem. Phys.
117
,
10008
(
2002
).
29.
L.
Sari
,
Y.
Yamaguchi
, and
H. F.
Schaefer
III
,
J. Chem. Phys.
119
,
8266
(
2003
).
30.
K.
Raghavachari
,
G. W.
Trucks
,
J. A.
Pople
, and
M.
Head-Gordon
,
Chem. Phys. Lett.
157
,
479
(
1989
).
31.
G. D. I.
Purvis
and
R. J.
Bartlett
,
J. Chem. Phys.
76
,
1910
(
1982
).
32.
J. D.
Watts
,
J.
Gauss
, and
R. J.
Bartlett
,
J. Chem. Phys.
98
,
8718
(
1993
).
33.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
).
34.
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
35.
MOLPRO, a package of ab initio programs designed by H.-J. Werner and P. J. Knowles, version 2002.1, R. D. Amos, A. Bernhardsson, A. Berning et al.
36.
M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN 98, Revision A.1x, Gaussian, Inc., Pittsburgh, PA, 2001.
37.
C. E.
Moore
,
Natl. Bur. Stand. Circ. (U. S.)
467
,
1
(
1952
).
38.
J.-P.
Blaudeau
and
L. A.
Curtiss
,
Int. J. Quantum Chem.
61
,
943
(
1997
).
39.
A.
Haliker
,
T.
Helgaker
,
P.
Jorgensen
,
W.
Klopper
,
H.
Koch
,
J.
Olsen
, and
A. K.
Wilson
,
Chem. Phys. Lett.
286
,
243
(
1998
).
40.
D.
Feller
,
J. Chem. Phys.
96
,
6104
(
1992
).
41.
H.
Hofmann
,
E.
Hansele
, and
T.
Clark
,
J. Comput. Chem.
11
,
1147
(
1990
).
42.
S.
Petrie
,
J. Phys. Chem. A
102
,
6138
(
1998
).
43.
D.
Feller
and
K. A.
Peterson
,
J. Chem. Phys.
108
,
154
(
1998
).
44.
D.
Feller
and
D. A.
Dixon
,
J. Chem. Phys.
115
,
3484
(
2001
).
45.
D.
Feller
and
K. A.
Peterson
,
J. Chem. Phys.
110
,
8384
(
1999
).
46.
N. X. Wang and A. K. Wilson (unpublished).
47.
B.
Ruscic
,
M.
Schwarz
, and
J.
Berkowitz
,
J. Chem. Phys.
92
,
1865
(
1990
).
48.
S. R.
Gunn
and
L. G.
Green
,
J. Phys. Chem.
65
,
779
(
1961
).
49.
M. W. Chase, Jr., J. Phys. Chem. Ref. Data Monograph No. 9 (1985). NIST-JANAF Thermochemical Tables, 4th ed.
50.
V. A.
Rassolov
,
M. A.
Ratner
,
J. A.
Pople
,
P. C.
Redfern
, and
L. A.
Curtiss
,
J. Comput. Chem.
22
,
976
(
2001
).
51.
N. Haworth, A. K. Wilson, and L. Radom (unpublished).
52.
K. Huber and G. Herzberg, Molecular Spectra and Molecular Structure 4 (Van Nostrand, Princeton, 1979).
53.
K.
Ohno
,
H.
Matsumura
,
Y.
Endo
, and
E.
Hirota
,
J. Mol. Spectrosc.
118
,
1
(
1986
).
54.
J. H. Callomon, E. Hirota, K. Kuchitsu, W. J. Lafferty, A. G. Maki, and C. S. Pote, Structure Data of Free Polyatomic Molecules, Vol. 7, in Landolt-Bornstein, New Series, Group II (Springer, Berlin, 1976).
55.
M. K.
Gilles
,
M. L.
Polak
, and
W. C.
Lineberger
,
J. Chem. Phys.
96
,
8012
(
1992
).
56.
Y.
Koga
,
H.
Takeo
,
S.
Kondo
,
M.
Sugie
,
C.
Matsumura
,
G. A.
McRae
, and
E. A.
Cohen
,
J. Mol. Spectrosc.
138
,
467
(
1989
).
57.
G.
Graner
,
J. Mol. Spectrosc.
90
,
394
(
1981
).
58.
J.
Berkowitz
,
J. Chem. Phys.
89
,
7065
(
1988
).
59.
S. T.
Gibson
,
J. P.
Greene
, and
J.
Berkowitz
,
J. Chem. Phys.
85
,
4815
(
1986
).
60.
L. V. Gurvich, I. V. Veyts, and C. B. Alcock, Thermodynamic Properties of Individual Substances, 4th ed. (Hemisphere, New York, 1989).
61.
P. A. G.
O’Hare
and
L. A.
Curtiss
,
J. Chem. Thermodyn.
27
,
643
(
1995
).
62.
S. A.
Kudchadker
and
A. P.
Kudchadker
,
J. Phys. Chem. Ref. Data
4
,
457
(
1975
).
63.
B.
Ruscic
and
J.
Berkowitz
,
J. Chem. Phys.
101
,
7795
(
1994
).
64.
S.
Lias
,
J. E.
Bartmess
,
J. F.
Liebman
,
J. L.
Holmes
,
R. D.
Levin
, and
W. G.
Mallard
,
J. Phys. Chem. Ref. Data Suppl.
17
,
1
(
1998
).
65.
M. N.
Glukhovtsev
,
J. E.
Szulejko
,
T. B.
McMahon
,
J. W.
Gauld
,
A. P.
Scott
,
B. J.
Smith
,
A.
Pross
, and
L.
Radom
,
J. Phys. Chem.
98
,
13099
(
1994
).
This content is only available via PDF.
You do not currently have access to this content.