A systematic procedure for refining gradient corrections in Kohn–Sham exchange-correlation functionals is presented. The procedure is based on least-squares fitting to accurate thermochemical data. In this first application of the method, we use the G2 test set of Pople and co-workers to generate what we believe to be an optimum GGA/exact-exchange density-functional theory (i.e., generalized gradient approximation with mixing of exactly computed exchange).
REFERENCES
1.
L. A.
Curtiss
, K.
Raghavachari
, G. W.
Trucks
, and J. A.
Pople
, J. Chem. Phys.
94
, 7221
(1991
).2.
L. A.
Curtiss
, K.
Raghavachari
, P. C.
Redfern
, and J. A.
Pople
, J. Chem. Phys.
106
, 1063
(1997
).3.
4.
5.
6.
M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. W. Wong, J. B. Foresman, M. A. Robb, M. Head-Gordon, E. S. Replogle, R. Gomperts, J. L. Andres, K. Raghavachari, J. S. Binkley, C. Gonzalez, R. L. Martin, D. J. Fox, D. L. Defrees, J. Baker, J. J. P. Stewart, and J. A. Pople,GAUSSIAN 92/DFT, Rev. G. 2, Gaussian, Inc., Pittsburgh, PA, 1993.
7.
8.
A. D.
Becke
, J. Chem. Phys.
104
, 1040
(1996
).Note that integral signs were mistakenly omitted from many equations in this reference, thus leading to possible confusion between energies and energy densities. 9.
10.
11.
12.
13.
14.
H.
Stoll
, C. M. E.
Pavlidou
, and H.
Preuss
, Theor. Chim. Acta
49
, 143
(1978
);15.
J. P.
Perdew
and Y.
Wang
, Phys. Rev. B
45
, 13
244
(1992
). Note that in this reference, and many others in the physical literature, denotes correlation energy per particle. We work instead with ,, the energy density per unit volume. The two are related by. Similar notation is used for exchange.16.
17.
P. M. W.
Gill
, B. G.
Johnson
, J. A.
Pople
, and M. J.
Frisch
, Int. J. Quantum Chem. Quantum Chem. Symp.
26
, 319
(1992
).18.
H. B.
Shore
, J. H.
Rose
, and E.
Zaremba
, Phys. Rev. B
15
, 2858
(1977
);19.
Geometries of Ref. 17, provided by P. M. W. Gill.
20.
S. J.
Chakravorty
, S. R.
Gwaltney
, E. R.
Davidson
, F. A.
Parpia
, and C.
Froese Fischer
, Phys. Rev. A
47
, 3649
(1993
).
This content is only available via PDF.
© 1997 American Institute of Physics.
1997
American Institute of Physics
You do not currently have access to this content.
