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Published on: June 8, 2018
Explicitly correlated second order perturbation theory: introduction of a rational generator and numerical
1Graduate School of Information Science, Nagoya University, Chikusa-ku Nagoya 464-8601, Japan. tenno@info.human.nagoya-u.ac.jp
Abstract:
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.
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