Analytical Hartree-Fock wave functions subject to cusp and asymptotic constraints: He to Xe, Li+ to Cs+, H? to I?

Abstract

Analytical, variational approximations to Hartree–Fock wave functions are constructed for the ground states of all the neutral atoms from He to Xe, the cations from Li+ to Cs+, and the stable anions from H− to I−. The wave functions are constrained so that each atomic orbital agrees well with the electron–nuclear cusp condition and has good long-range behavior. Painstaking optimization of the exponents and principal quantum numbers of the Slater-type basis functions allows us to reach this goal while obtaining total energies that, at worst, are a few microHartrees above the numerical Hartree–Fock limit values. The wave functions are freely available by anonymous ftp from okapi.chem.unb.ca or upon request to the authors. ©1999 John Wiley & Sons, Inc. Int J Quant Chem 71: 491–497, 1999