Exchange Monte Carlo for Molecular Simulations with Monoelectronic Hamiltonians

摘要

We introduce a general Monte Carlo scheme for achieving atomistic simulationswith monoelectronic Hamiltonians including the thermalization of both nuclearand electronic degrees of freedom. The kinetic Monte Carlo algorithm is used toobtain the exact occupation numbers of the electronic levels at canonicalequilibrium, and comparison is made with Fermi-Dirac statistics in infinite andfinite systems. The effects of a nonzero electronic temperature on thethermodynamic properties of liquid silver and sodium clusters are presented.