Quantum mechanical single molecule partition function from path integral Monte Carlo simulations

Shaji Chempath; Cristian Predescu; Alexis T Bell

doi:10.1063/1.2196885

Quantum mechanical single molecule partition function from path integral Monte Carlo simulations

J Chem Phys. 2006 Jun 21;124(23):234101. doi: 10.1063/1.2196885.

Authors

Shaji Chempath¹, Cristian Predescu, Alexis T Bell

Affiliation

¹ Department of Chemical Engineering, University of California-Berkeley, Berkeley, CA 94720, USA.

PMID: 16821901
DOI: 10.1063/1.2196885

Abstract

An algorithm for calculating the partition function of a molecule with the path integral Monte Carlo method is presented. Staged thermodynamic perturbation with respect to a reference harmonic potential is utilized to evaluate the ratio of partition functions. Parallel tempering and a new Monte Carlo estimator for the ratio of partition functions are implemented here to achieve well converged simulations that give an accuracy of 0.04 kcal/mol in the reported free energies. The method is applied to various test systems, including a catalytic system composed of 18 atoms. Absolute free energies calculated by this method lead to corrections as large as 2.6 kcal/mol at 300 K for some of the examples presented.