An ab initio path integral Monte Carlo simulation method for molecules and clusters: application to Li_4 and Li_5^+

Abstract

A novel method for simulating the statistical mechanics of molecular systems in which both nuclear and electronic degrees of freedom are treated quantum mechanically is presented. The scheme combines a path integral description of the nuclear variables with a first-principles adiabatic description of the electronic structure. The electronic problem is solved for the ground state within a density functional approach, with the electronic orbitals expanded in a localized (Gaussian) basis set. The discretized path integral is computed by a Metropolis Monte Carlo sampling technique on the normal modes of the isomorphic ring-polymer. An effective short-time action correct to order $\tau^4$ is used. The validity and performance of the method are tested in two small Lithium clusters, namely Li$_4$ and Li$_5^+$. Structural and electronic properties computed within this fully quantum-mechanical scheme are presented and compared to those obtained within the classical nuclei approximation. Quantum delocalization effects are significant but tunneling turns out to be irrelevant at low temperatures.