Comparative study of perturbative methods for computing electron transfer tunneling matrix elements with a nonorthogonal basis set

Abstract

The authors consider the problem of computing tunneling matrix elements for bridge-mediated electron transfer reactions using the Lowdin [J. Math. Phys. 3, 969 (1962); J. Mol. Spectrosc. 13, 326 (1964)] projection-iteration technique with a nonorthogonal basis set. They compare the convergence properties of two different Lowdin projections, one containing the overlap matrix S and the other containing the inverse S-1 in the projected Hamiltonian. It was suggested in the literature that the projected Hamiltonian with S-1 has better convergence properties compared to the projected Hamiltonian with S. The authors test this proposal using a simple analytical model, and ab initio Hartree-Fock calculations on different molecules with several types of basis sets. Their calculations show that, for Gaussian-type basis sets, the projected Hamiltonian containing S has the best convergence properties, especially for diffuse basis sets and in the strong coupling limit. The limit of diffuse basis sets is relevant to tunneling matrix element calculations involving excited states and anionic electron transfer.