Space-warp coordinate transformation for efficient ionic force calculations in quantum Monte Carlo

TL;DR

This paper introduces a space-warp coordinate transformation (SWCT) that significantly improves the efficiency of ionic force calculations in quantum Monte Carlo methods, enabling larger system simulations without increased computational cost.

Contribution

The study demonstrates that applying SWCT to QMC force calculations results in cost scaling independent of atomic number, enhancing the feasibility of large-scale simulations.

Findings

LRDMC forces yield more accurate bond lengths and frequencies than VMC.

SWCT makes the cost ratio of force to energy calculations independent of atomic number.

Forces computed with SWCT scale similarly to total energy, enabling larger system simulations.

Abstract

Ab-initio quantum Monte Carlo (QMC) methods are a state-of-the-art computational approach to obtaining highly accurate many-body wave functions. Although QMC methods are widely used in physics and chemistry to compute ground-state energies, calculation of atomic forces is still under technical/algorithmic development. Very recently, force evaluation has started to become of paramount importance for the generation of machine-learning force-field potentials. Nevertheless, there is no consensus regarding whether an efficient algorithm is available for the QMC force evaluation, namely one that scales well with the number of electrons and the atomic numbers. In this study, we benchmark the accuracy of all-electron variational Monte Carlo (VMC) and lattice-regularized diffusion Monte Carlo (LRDMC) forces for various mono- and heteronuclear dimers. The VMC and LRDMC forces were calculated with and without the so-called space-warp coordinate transformation (SWCT) and appropriate regularization techniques to remove the infinite variance problem. The LRDMC forces were computed with the Reynolds (RE) and variational-drift (VD) approximations. The potential energy surfaces obtained from the LRDMC energies give equilibrium bond lengths ($r_{\rm eq}$) and harmonic frequencies ($\omega$) very close to the experimental values for all dimers, improving the corresponding VMC results. The LRDMC forces improve the VMC forces, implying that it is worth computing the DMC forces beyond VMC in spite of the higher computational cost. We find that the ratio of computational costs between QMC energy and forces scales as $Z^{\sim 2.5}$ without the SWCT. In contrast, the application of the SWCT makes the ratio {\it independent} of $Z$. As such, the accessible QMC system size is not affected by the evaluation of ionic forces but governed by the same scaling as the total energy one.