Excited-state diffusion Monte Carlo calculations: a simple and efficient two-determinant ansatz

Abstract

We perform excited-state variational Monte Carlo and diffusion Monte Carlo calculations using a simple and efficient wave function ansatz. This ansatz follows the recent variation-after-response formalism, accurately approximating a configuration interaction singles wave function as a sum of only two non-orthogonal Slater determinants, and further including important orbital relaxation. The ansatz is used to perform diffusion Monte Carlo calculations with large augmented basis sets, comparing to benchmarks from near-exact quantum chemical methods. The significance of orbital optimization in excited-state diffusion Monte Carlo is demonstrated, and the excited-state optimization procedure is discussed in detail. Diffuse excited states in water and formaldehyde are studied, in addition to the formaldimine and benzonitrile molecules.