The sign problem in density matrix quantum Monte Carlo

TL;DR

This paper investigates the sign problem in density matrix quantum Monte Carlo (DMQMC), comparing it with FCIQMC and exploring modifications like IP-DMQMC to reduce computational costs and improve scalability.

Contribution

The study provides a systematic analysis of the sign problem in DMQMC, establishing relationships between critical walker populations and proposing IP-DMQMC as a more efficient alternative.

Findings

N_c for DMQMC is the square of N_c for FCIQMC.

IP-DMQMC's N_c is directly proportional to FCIQMC's N_c.

Asymmetric propagation in IP-DMQMC reduces stochastic error.

Abstract

Density matrix quantum Monte Carlo (DMQMC) is a recently-developed method for stochastically sampling the $N$-particle thermal density matrix to obtain exact-on-average energies for model and \emph{ab initio} systems. We report a systematic numerical study of the sign problem in DMQMC based on simulations of atomic and molecular systems. In DMQMC, the density matrix is written in an outer product basis of Slater determinants and has a size of space which is the square of the number of Slater determinants. In principle this means DMQMC needs to sample a space which scales in the system size, $N$, as $\mathcal{O}[(\exp(N))^2]$. In practice, there is a system-dependent critical walker population ($N_c$) which must be exceeded in order to remove the sign problem, and this imposes limitations by way of storage and computer time. We establish that $N_c$ for DMQMC is the square of $N_c$ for FCIQMC. By contrast, the minimum $N_c$ in the interaction picture modification of DMQMC (IP-DMQMC) only is directly proportionate to the $N_c$ for FCIQMC. We find that this comes from the asymmetric propagation of IP-DMQMC compared to the symmetric propagation of canonical DMQMC. An asymmetric mode of propagation is prohibitively expensive for DMQMC because it has a much greater stochastic error. Finally, we find that the equivalence between IP-DMQMC and FCIQMC seems to extend to the initiator approximation, which is often required to study larger basis sets and other systems. This suggests IP-DMQMC offers a way to ameliorate the cost of moving between a Slater determinant space and an outer product basis.