Relativistic diffusion Monte Carlo method: Zeroth-order regular approximation-diffusion Monte Carlo method in a spin-free formalism

摘要

A diffusion Monte Carlo (DMC) method for the relativistic zeroth-order regular approximation (ZORA) is proposed. In this scheme, a novel approximate Greens function is derived for the spin-free ZORA Hamiltonian. Several numerical tests on atoms and small molecules showed that by combining with the relativistic cusp-correction scheme, the present approach can include both relativistic and electron-correlation effects simultaneously. The correlation energies recovered by the ZORA-DMC method are comparable with the nonrelativistic DMC results and superior to the coupled cluster singles and doubles with perturbative triples correction results when the correlation-consistent polarized valence triple-zeta Douglas-Kroll basis set is used. For the heavier CuH molecule, the ZORA-DMC estimation of its dissociation energy agrees with the experimental value within the error bar.