Tests of Monte Carlo perturbation theory for the free energy of liquid copper

Abstract

Monte Carlo perturbation theory, in which terms in the thermodynamic perturbation series are evaluated by Monte Carlo averaging, has potentially large advantages in efficiency for calculating free energies of liquids from ab initio potential surfaces. In order to test the accuracy of perturbation theory for liquid metals, a series of calculations has been done on liquid copper, modeled by an embedded atom potential. A simple 1/r(12) pair potential is used as the reference system. The free energy is calculated to third order in perturbation theory, and the results are compared to an exact formula. It is found that for optimal reference potential parameters, second order perturbation theory is essentially exact. Second and third order theories give accurate results for significantly nonoptimal reference parameters. The relation between perturbation theory and reweighting is discussed, and an approximate formula is derived that shows an exponential dependence of the efficiency of reweighting on the second order free energy correction. Finally, techniques for application to ab initio potentials are discussed. It is shown that with samples of 100 configurations, it is possible to obtain accuracy and precision at the level of approximately 1 meV/atom.