Path integral ground state study of finite-size systems: Application to small (parahydrogen)N (N=2–20) clusters

Abstract

We use the path integral ground state method to study the energetic and structural properties of small para-H2 clusters of sizes ranging from 2 to 20 molecules. A fourth order formula is used to approximate the short imaginary-time propagator and two interaction potentials are considered. Our results are compared to those of exact basis set calculations and other quantum Monte Carlo methods when available. We find that for all cluster sizes considered, our results show a lower ground state energy than literature values obtained by diffusion Monte Carlo and variational Monte Carlo. For the dimer and trimer, ground state energies are in good agreement with exact results obtained using the discrete variable representation. Structural properties are found to be insensitive to the choice of interaction potential. We explore the use of Pekeris coordinates to analyze the importance of linear arrangement in trimers and for trimers within clusters of larger size.