Accelerating Stochastic Quantum Chemistry

TL;DR

This paper introduces a quasi-Newton propagation method to significantly accelerate convergence in stochastic quantum chemistry algorithms like FCIQMC and CCMC, with minimal additional computational cost, demonstrated on large model systems and real molecules.

Contribution

It presents a novel quasi-Newton propagation technique that accelerates stochastic quantum chemistry calculations with negligible extra computational effort.

Findings

Accelerates FCIQMC convergence by over an order of magnitude.

Effective on large Hilbert spaces up to 10^40.

Achieves highly accurate energies for the chromium dimer.

Abstract

The convergence of full configuration interaction quantum Monte Carlo (FCIQMC) is accelerated using a quasi-Newton propagation (QN) which can also be applied to coupled cluster Monte Carlo (CCMC). The computational scaling of this optimised propagation is O(1), keeping the additional computational cost to a bare minimum. Its effects are investigated deterministically and stochastically on a model system, the uniform electron gas, with Hilbert space size up to $10^{40}$ and shown to accelerate convergence of the instantaneous projected energy by over an order of magnitude in the FCIQMC test case. Its capabilities are then demonstrated with FCIQMC on an archetypical quantum chemistry problem, the chromium dimer, in an all-electron basis set with Hilbert space size of about $10^{22}$ yielding highly accurate FCI energies.