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

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 (1 & LE; Z & LE; 35, where Z is the atomic number). 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(eq)) and harmonic frequencies (omega) very close to the experimental values for all dimers, improving the corresponding VMC results. The LRDMC forces with the RE approximation improve the VMC forces, implying that it is worth computing the DMC forces beyond VMC despite the higher computational cost. The LRDMC forces with the VD approximations also show improvement, which unfortunately comes at a much higher computational cost in all-electron calculations. 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 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.& nbsp;(c) 2022 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Automated summary

In this study, the accuracy of all-electron variational Monte Carlo (VMC) and lattice-regularized diffusion Monte Carlo (LRDMC) forces for various mono- and heteronuclear dimers is benchmarked. The results show that the LRDMC forces with appropriate regularization techniques improve the VMC forces, indicating the value of computing the DMC forces beyond VMC. The computational costs of QMC energy and forces scale differently, but applying the space-warp coordinate transformation (SWCT) makes the ratio of costs independent of the atomic number.