Optimum and efficient sampling for variational quantum Monte Carlo

Abstract

Quantum mechanics for many-body systems may be reduced to the evaluation of integrals in 3N dimensions using Monte-Carlo, providing the Quantum Monte Carlo ab initio methods. Here we limit ourselves to expectation values for trial wavefunctions, that is to Variational quantum Monte Carlo. Almost all previous implementations employ samples distributed as the physical probability density of the trial wavefunction, and assume the Central Limit Theorem to be valid. In this paper we provide an analysis of random error in estimation and optimisation that leads naturally to new sampling strategies with improved computational and statistical properties. A rigorous lower limit to the random error is derived, and an efficient sampling strategy presented that significantly increases computational efficiency. In addition the infinite variance heavy tailed random errors of optimum parameters in conventional methods are replaced with a Normal random error, strengthening the theoretical basis of optimisation. The method is applied to a number of first-row systems, and compared with previously published results.

20 pages, 4 figures

References in corpus (11)

• Continuum variational and diffusion quantum Monte Carlo calculations
• Jastrow correlation factor for atoms, molecules, and solids
• Inhomogeneous backflow transformations in quantum Monte Carlo calculations
• Full optimization of Jastrow-Slater wave functions with application to the first-row atoms and homonuclear diatomic molecules
• Stable liquid Hydrogen at high pressure by a novel ab-initio molecular dynamics
• Ground state wave function and energy of the lithium atom
• Energies of the first row atoms from quantum Monte Carlo
• Heavy-tailed random error in quantum Monte Carlo
• Methods for calculating forces within quantum Monte Carlo simulations
• The Fermion Monte Carlo revisited
• Alternative sampling for variational quantum Monte Carlo