Interfacing Branching Random Walks with Metropolis Sampling: Constraint Release in Auxiliary-Field Quantum Monte Carlo

• Published in: Journal of chemical theory and computation Vol. 19; no. 19; pp. 6782 - 6795
• Main Authors: Xiao, Zhi-Yu, Shi, Hao, Zhang, Shiwei
• Format: Journal Article
• Language: English
• Published: Washington American Chemical Society 10.10.2023
• Subjects: Algorithms; Chain branching; Chemistry; Computation; Condensed Matter, Interfaces, and Materials; Constraints; Correlation; Hamiltonian functions; Markov chains; Physics; Random walk; Sampling; Systematic errors; Wave functions
• ISSN: 1549-9618; 1549-9626; 1549-9626
• DOI: 10.1021/acs.jctc.3c00521

We present an approach to interface branching random walks with Markov chain Monte Carlo sampling and to switch seamlessly between the two. The approach is discussed in the context of auxiliary-field quantum Monte Carlo (AFQMC) but can be applied to other Monte Carlo calculations or simulations. In AFQMC, the formulation of branching random walks along imaginary-time is needed to realize a constraint to control the sign or phase problem. The constraint is derived from an exact gauge condition and is in practice implemented approximately with a trial wave function or trial density matrix, which can break exactness in the algorithm. We use the generalized Metropolis algorithm to sample a selected portion of the imaginary-time path after it has been produced by the branching random walk. This interfacing allows a constraint release to follow seamlessly from constrained-path sampling, which can reduce the systematic error from the latter. It also provides a way to improve the computation of correlation functions and observables that do not commute with the Hamiltonian. We illustrate the method in atoms and molecules, where improvements in accuracy can be clearly quantified and near-exact results are obtained. We also discuss the computation of the variance of the Hamiltonian and propose a convenient way to evaluate it stochastically without changing the scaling of AFQMC.