Excited-state calculations with quantum Monte Carlo

Abstract

Quantum Monte Carlo methods are first-principle approaches that approximately solve the Schrödinger equation stochastically. As compared to traditional quantum chemistry methods, they offer important advantages such as the ability to handle a large variety of many-body wave functions, the favorable scaling with the number of particles, and the intrinsic parallelism of the algorithms which are particularly suitable to modern massively parallel computers. In this chapter, we focus on the two quantum Monte Carlo approaches most widely used for electronic structure problems, namely, the variational and diffusion Monte Carlo methods. We give particular attention to the recent progress in the techniques for the optimization of the wave function, a challenging and important step to achieve accurate results in both the ground and the excited state. We conclude with an overview of the current status of excited-state calculations for molecular systems, demonstrating the potential of quantum Monte Carlo methods in this field of applications.