Parallel Calculation of Electron-Transfer and Resonance Matrix Elements of Hartree—Fock and Generalized Valence Bond Wave Functions.

Abstract

We review the theory for the computation of the Hamiltonian matrix element between two distinct electronic wave functions ψA and ψB sharing the same nuclear configuration but differing electronic density distributions. For example, ψA and ψB might describe two endpoints in an electron transfer reaction or two configurations in a resonance description of a molecule. In such cases the calculation of the rate of electron transfer or resonance energy requires evaluation of <ψA\Ĥ\ψB> = HAB matrix elements. Because the orbitals of ψA and ψB have complicated (non-orthogonal) relationships, the calculation of HAB had been computationally intensive. In this paper we consider ψA, ψB having the form of closed or open-shell Hartree-Fock or Generalized Valence Bond wave functions and show the parallel structure of the theory. Using this parallel structure we present an efficient computational implementation for shared memory multiprocessors.

Group Members

William A. Goddard III

Charles and Mary Ferkel Professor