Diffusion quantum Monte Carlo approach to the polaritonic ground state
Braden M. Weight, Sergei Tretiak, Yu Zhang
Abstract
Making and using polaritonic states (i.e., hybrid electron-photon states) for chemical applications has recently become one of the most prominent and active fields that connects the communities of chemistry and quantum optics. Modeling of such polaritonic phenomena using ab initio approaches calls for new methodologies, leading to the reinvention of many commonly used electronic structure methods, such as Hartree-Fock, density functional, and coupled cluster theories. In this work, we explore the formally exact diffusion quantum Monte Carlo approach to obtain numerical solutions to the polaritonic ground state during the dissociation of the ${\mathrm{H}}_{2}$ molecular system. We examine various electron-nuclear-photon properties throughout the dissociation, such as changes to the minimum of the cavity Born-Oppenheimer surface, the localization of the electronic wave function, and the average mode occupation. Finally, we directly compare our results to that obtained with state-of-the-art, yet approximate, polaritonic coupled cluster approaches.