Zero-Variance Zero-Bias Principle for Observables in quantum Monte Carlo: Application to Forces

A simple and stable method for computing accurate expectation values of observable with Variational Monte Carlo (VMC) or Diffusion Monte Carlo (DMC) algorithms is presented. The basic idea consists in replacing the usual bare'' estimator associated with the observableby an improved orrenormalized'' estimator. Using this estimator more accurate averages are obtained:Not only the statistical fluctuations are reduced but alsothe systematic error (bias) associated with the approximate VMC or (fixed-node) DMC probability densities. It is shown that improved estimators obey a Zero-Variance Zero-Bias (ZVZB) property similar to the usual Zero-Variance Zero-Bias property of the energy with the local energy as improved estimator. Using this property improved estimators can be optimized and the resulting accuracy on expectation values may reach the remarkable accuracy obtained for total energies. As an important example, we present the application of our formalism to the computation of forces in molecular systems. Calculations of the entire force curve of the H$_2$,LiH, and Li$_2$ molecules are presented. Spectroscopic constants $R_e$ (equilibrium distance)and $\omega_e$ (harmonic frequency) are also computed.The equilibrium distances are obtained with a relative error smaller than 1$\%$, while the harmonic frequencies are computed with an error of about 10$\%$.

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Source https://hal.science/hal-00000683
Author Assaraf, Roland, Caffarel, Michel
Maintainer CCSD
Last Updated May 23, 2026, 09:27 (UTC)
Created May 23, 2026, 09:27 (UTC)
Identifier hal-00000683
Language en
Rights https://about.hal.science/hal-authorisation-v1/
contributor Laboratoire de chimie théorique (LCT) ; Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut de Chimie - CNRS Chimie (INC-CNRS)-Centre National de la Recherche Scientifique (CNRS)
creator Assaraf, Roland
date 2003-10-07T00:00:00
harvest_object_id 1577b1db-bdfa-4c34-be2d-cff7c5623a39
harvest_source_id 3374d638-d20b-4672-ba96-a23232d55657
harvest_source_title test moissonnage SELUNE
metadata_modified 2024-04-11T00:00:00
relation info:eu-repo/semantics/altIdentifier/arxiv/physics/0310035
set_spec type:UNDEFINED