Toward improved density functionals for the correlation energy.
Eleven density functionals, including some of the most widely used ones, are tested on their ability to predict nonrelativistic, electron correlation energies for the 17 atoms from He to Ar, the 17 cations from Li(+) to K(+), and 11 (1)S state atoms from Ca to Rn. They all lead to relatively poor predictions for the heavier atoms. Reparametrization of these functionals improves their performance for light atoms but does not alleviate their problems with the heavier, closed-shell atoms. Several novel, few-parameter, density functionals for the correlation energy are developed heuristically. Four new functionals lead to qualitatively improved predictions for the heavier atoms without unreasonably compromising accuracy for the lighter atoms. Further progress would be facilitated by reliable estimates of electron correlation energies for more atoms, particularly heavy ones.
Thakkar
Ajit J
AJ
Department of Chemistry, University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada. ajit@unb.ca
McCarthy
Shane P
SP