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 Moller-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. (C) 2004 American Institute of Physics.