Large Scale Parallelization in Stochastic Coupled Cluster

Abstract

Coupled cluster theory is a vital cornerstone of electronic structure theory and is being applied to ever-larger systems. Stochastic approaches to quantum chemistry have grown in importance and offer compelling advantages over traditional deterministic algorithms in terms of computational demands, theoretical flexibility or lower scaling with system size. We present a highly parallelizable algorithm of the coupled cluster Monte Carlo method involving sampling of clusters of excitors over multiple time steps. The behaviour of the algorithm is investigated on the uniform electron gas and the water dimer at CCSD, CCSDT and CCSDTQ levels. We also describe two improvements to the original sampling algorithm, full non-composite and multi-spawn sampling. A stochastic approach to coupled cluster results in an efficient and scalable implementation at arbitrary truncation levels in the coupled cluster expansion.