Explicitly correlated second order perturbation theory: introduction of a rational generator and numerical quadratures.
A rational generator, which fulfills the cusp conditions for singlet and triplet electron pairs, is proposed and applied to explicitly correlated second order Møller-Plesset perturbation theory calculations. It is shown that the generator in conjunction with frozen geminals improves the convergence of correlation energy without introducing any variational parameters in explicitly correlated functions. A new scheme for three-electron integrals based on numerical quadratures is also illustrated. The method is tested for the convergence of reaction enthalpies with various basis sets.
Ten-no
Seiichiro
S
Graduate School of Information Science, Nagoya University, Chikusa-ku Nagoya 464-8601, Japan. tenno@info.human.nagoya-u.ac.jp