Minimum Energy Pathways via Quantum Monte Carlo

Abstract

We perform quantum Monte Carlo (QMC) calculations to determine minimum energy pathways of simple chemical reactions, and compare the computed geometries and reaction barriers with those obtained with density functional theory (DFT) and quantum chemistry methods. We find that QMC performs in general significantly better than DFT, being also able to treat cases in which DFT is inaccurate or even unable to locate the transition state. Since the wave function form employed here is particularly simple and can be transferred to larger systems, we suggest that a QMC approach is both viable and useful for reactions difficult to address by DFT and system sizes too large for high level quantum chemistry methods.

5 pages, 1 table, 2 figures

References in corpus (5)

• Inhomogeneous backflow transformations in quantum Monte Carlo calculations
• Beyond the locality approximation in the standard diffusion Monte Carlo method
• Algorithmic differentiation and the calculation of forces by quantum Monte Carlo
• Approaching Chemical Accuracy with Quantum Monte Carlo
• Diffusion quantum Monte Carlo study of the equation of state and point defects in aluminum

Cited by in corpus (4)

• Static and dynamical correlation in diradical molecules by Quantum Monte Carlo using the Jastrow Antisymmetrized Geminal Power ansatz
• Towards Quantum Monte Carlo Forces on Heavier Ions: Scaling Properties
• Error Cancellation in Diffusion Monte Carlo Calculations of Surface Chemistry
• Generalizing the self-healing diffusion Monte Carlo approach to finite temperature: a path for the optimization of low-energy many-body bases