Infinitesimal differential diffusion quantum Monte Carlo: Diatomic molecular properties

Abstract

We show how to estimate, for a given molecule, the first and higher derivatives of the expected value of an operator with respect to one or more physical parameters. This is done with high accuracy achieved by sampling to within a certain approximation from the exact electron distribution, compatible with the Hellmann–Feynman theorem. Finite difference approximations are avoided. The required derivatives of the unknown exact wave function are determined by averaging expressions involving only the total serial correlation of known quantities. The operator is not restricted to the case of the molecular Hamiltonian. This allows for computation of virtually all ground‐state properties of a molecule by a single, relatively trivial computer program. Our formulas are presented and applied in the context of a diatomic molecule (LiH), but they can be readily extended to polyatomics.