We propose a modification to the popular basis set, which has recently been extended to cover first-row transition metals [Rassolov et al., J. Chem. Phys. 109, 1223 (1998)]. As demonstrated by a number of calculations, the existing basis performs poorly for many transition metals, particularly those toward the end of the series (Co, Ni, and especially Cu). The reason for this lies primarily with the shell, which lacks a sufficiently diffuse exponent. A reoptimization of the -shell exponents and coefficients by a two-step procedure, keeping the rest of the basis unchanged, corrects the problem, giving a basis set that performs uniformly well across the entire first-row transition metal series from scandium to copper.
REFERENCES
1.
W. J. Hehre, L. Radom, P. v. R. Schleyer, and J. A. Pople, Ab Initio Molecular Orbital Theory (Wiley, New York, 1986).
2.
W. J.
Hehre
, R.
Ditchfield
, and J. A.
Pople
, J. Chem. Phys.
56
, 2257
(1972
).3.
4.
5.
M. M.
Francl
, W. J.
Pietro
, W. J.
Hehre
, J. S.
Binkley
, M. S.
Gordon
, D. J.
DeFrees
, and J. A.
Pople
, J. Chem. Phys.
77
, 3654
(1982
).6.
7.
T.
Clark
, J.
Chandrasekhar
, G. W.
Spitznagel
, and P. v. R.
Schleyer
, J. Comput. Chem.
4
, 294
(1983
).8.
9.
10.
A.
Schäfer
, H.
Horn
, and R.
Ahlrichs
, J. Chem. Phys.
97
, 2571
(1992
).11.
V. A.
Rassolov
, J. A.
Pople
, M. A.
Ratner
, and T. L.
Windus
, J. Chem. Phys.
109
, 1223
(1998
).12.
V. A.
Rassolov
, M. A.
Ratner
, J. A.
Pople
, P. C.
Redfern
, and L. A.
Curtiss
, J. Comput. Chem.
22
, 976
(2001
).13.
14.
15.
16.
J. S.
Binkley
, J. A.
Pople
, and W. J.
Hehre
, J. Am. Chem. Soc.
102
, 339
(1980
).17.
C. C. J. Roothaan and P. S. Bagus, in Methods in Computational Physics, edited by B. Alder, S. Fernbach, and M. Rotenberg (Academic, New York, 1963), Vol. 2, pp. 47–94.
18.
19.
B. Roos, C. Salez, A. Veillard, and E. Clementi, IBM Technical Report RJ518, San Jose, CA, 1968.
20.
A. V.
Mitin
, G.
Hirsch
, and R. J.
Buenker
, J. Mol. Struct.: THEOCHEM
362
, 283
(1996
).21.
A. V.
Mitin
, G.
Hirsch
, and R. J.
Buenker
, Chem. Phys. Lett.
259
, 151
(1996
).22.
A. V.
Mitin
, G.
Hirsch
, and R. J.
Buenker
, J. Comput. Chem.
18
, 1200
(1997
).23.
Parallel Quantum Solutions, Fayetteville, Arkansas; http://www.pqs-chem.com; sales@pqs-chem.com
24.
25.
26.
M. J. Frisch, Æ. Frisch, and J. B. Foresman, GAUSSIAN 94 User’s Reference, Pittsburgh, PA, 1994, p. 61.
27.
J.
Baker
, A.
Scheiner
, and J.
Andzelm
, Chem. Phys. Lett.
216
, 380
(1993
).28.
29.
30.
M. C.
Holthausen
, M.
Mohr
, and W.
Koch
, Chem. Phys. Lett.
240
, 245
(1995
).31.
D. B.
Grotjahn
, M. A.
Brewster
, and L. M.
Ziurys
, J. Am. Chem. Soc.
124
, 5895
(2002
).32.
33.
34.
C. W.
Bauschlicher
and S. R.
Langhoff
, Chem. Phys. Lett.
145
, 205
(1988
).35.
36.
S.
Yanagisawa
, T.
Tsuneda
, and K.
Hirao
, J. Chem. Phys.
112
, 545
(2000
).37.
C. E. Moore, Ionization Potential and Ionization from the Analysis of Optical Spectra, Natl. Bur. Stand. Ref. Data Ser. Circ.#34 (USGPO, Washington, D.C., 1970).
38.
C. E. Moore, Atomic Energy Levels, Natl. Bur. Stand. Ref. Data Ser. Circ. #467 (USGPO, Washington D.C., 1949).
39.
K. P. Huber and G. Herzberg, Constants of Diatomic Molecules (Van Nostrand-Reinhold, New York, 1979).
40.
41.
J. H. Callomon, E. Hirita, K. Kuchitsu, W. J. Lafferty, A. G. Maki, and C. S. Pote, Structure Data on Free Polyatomic Molecules, Landolt-Börnstein, New Series, Group II, Vol. 7 (Springer, Berlin, 1976).
42.
A.
Almenningen
, S.
Samdal
, and D.
Christen
, J. Mol. Struct.
48
, 69
(1978
).43.
M.
Bencheikh
, R.
Koivisto
, O.
Launila
, and J. P.
Flament
, J. Chem. Phys.
106
, 6231
(1997
).44.
CRC Handbook of Chemistry and Physics, 78th ed., edited by D. R. Linde (CRC, Boca Raton, FL, 1997).
45.
46.
L.
Hedberg
, T.
Ijima
, and K.
Hedberg
, J. Chem. Phys.
70
, 3224
(1979
).47.
C. J.
Whitham
, H.
Ozeki
, and S.
Saito
, J. Chem. Phys.
112
, 641
(2000
).48.
R. J. H.
Clark
, B. K.
Hunter
, and D. M.
Rippon
, Inorg. Chem.
11
, 56
(1972
).49.
R. J. H.
Clark
and P. D.
Mitchell
, J. Chem. Soc. Dalton Trans.
1972
, 2429
.50.
L. H.
Jones
, R. S.
McDowell
, and M.
Goldblatt
, J. Chem. Phys.
48
, 2663
(1968
).
This content is only available via PDF.
© 2003 American Institute of Physics.
2003
American Institute of Physics
You do not currently have access to this content.
