Augmented (4d) and (5d) Gaussian basis sets are presented which provide a balanced description of the 4s23dn−2, 4s3dn−1, and 3dn configurations of transition−metal atoms. When compared to accurate Hartree–Fock calculations, the (4d) and (5d) expansions in the literature, which have been optimized for the 4s23dn−2 configuration, can lead to errors of several eV for states of the latter configurations where the 3d orbitals become more diffuse. The augmented sets reported here consist of a single diffuse basis function added to the original sets, where the orbital exponent of the added function was optimized for the 3dn configuration. Basis sets and contraction schemes are presented for the atoms Sc through Cu.

1.
For a detailed discussion see T. H. Dunning, Jr. and P. J. Hay, “Gaussian Basis Sets for Molecular Calculations,” in Modern Theoretical Chemistry, Vol. 3, edited by H. F. Schaefer III (Plenum, New York, 1976).
2.
A. J. H.
Wachters
,
J. Chem. Phys.
52
,
1033
(
1970
).
3.
B.
Roos
,
A.
Veillard
, and
G.
Vinot
,
Theoret. Chim. Acta
20
,
1
(
1971
).
4.
I. H.
Hillier
and
V. R.
Saunders
,
Mol. Phys.
22
,
1025
(
1971
).
5.
C. F.
Melius
,
B. D.
Olafson
, and
W. A.
Goddard
III
,
Chem. Phys. Lett.
28
,
457
(
1974
).
6.
C. F. Melius, J. W. Moskowitz, A. P. Mortola, M. B. Baillie, and M. A. Ratner, Surface Sci. (to be published).
7.
R. C.
Raffenetti
,
J. Chem. Phys.
58
,
4452
(
1973
).
8.
(a) B. R. Brooks and H. F. Schaefer III, “A Model Transition Metal‐Carbene System. MnCH2,” Mol. Phys. (to be published);
(b) W. C. Swope and H. F. Schaefer III, “Model Studies of π‐Bonded Orgonometallic Systems. MnC2H2 and MnC2H4,” Mol. Phys. (to be published).
9.
T. Smedley and W. A. Goddard III (unpublished calculations, private communication).
10.
A.
Whitaker
and
J. W.
Jeffrey
,
Acta Cryst.
23
,
977
(
1967
).
11.
S.
Huzinaga
,
J. Chem. Phys.
42
,
1293
(
1965
).
12.
T. H.
Dunning
, Jr.
,
J. Chem. Phys.
53
,
2823
(
1970
).
13.
C. E. Moore, Atomic Energy Levels, Vols. 1 and 2, NBS Circular No. 467.
14.
(a)
S. P.
Walch
and
W. A.
Goddard
III
,
J. Am. Chem. Soc.
98
,
7908
(
1976
);
(b) M. J. Sollenberger, W. A. Goddard III, and C. F. Melius, to be published (quoted in Ref. 14a).
15.
P. J. Hay (unpublished calculations).
16.
R. D.
Cowan
and
J. B.
Mann
,
J. Comp. Phys.
16
,
160
(
1974
).
17.
D. C. Griffin, Ph.D. Thesis, Purdue University (1970).
18.
C. F.
Fischer
,
Can. J. Phys.
41
,
1895
(
1963
);
C. F.
Fischer
,
Comp. Phys. Commun.
1
,
151
(
1969
).
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