Toward a Full Configurational Accuracy Calculation of an Arbitrary Molecule via Fragment Embedding and a Stochastic Solver.

Abstract

We demonstrate the feasibility of using a stochastic solver, full configuration interaction quantum Monte Carlo with the initiator approximation (i-FCIQMC), to converge fragment embedding calculations, namely bootstrap embedding (BE). We first propose and test a general protocol for converging BE-i-FCIQMC calculations and then suggest how the quality of the calculation compares against that of deterministic BE-FCI using different numbers of walkers. We then demonstrate that BE-i-FCIQMC can perform as well as BE-FCI in the large walker limit and how different factors, including the size of the Hilbert space of the fragments, the number of walkers, and the nature of the chemical system, affect the achievable matching error. We finally perform BE-FCI calculations in realistic systems like benzene and cyclohexane using a double-ζ basis set. This work demonstrates the potential of performing FCI quality calculations in realistic systems using BE.