Stereographic projection path-integral simulations of (HF)n clusters.
We perform several quantum canonical ensemble simulations of (HF)(n) clusters. The HF stretches are rigid, and the stereographic projection path-integral method is employed for the simulation in the resulting curved configuration space. We make use of the reweighted random series techniques to accelerate the convergence of the path-integral simulation with respect to the number of path coefficients. We develop and test estimators for the total energy and heat capacity based on a finite difference approach for non-Euclidean spaces. The quantum effects at temperatures below 400 K are substantial for all sizes. We observe interesting thermodynamic behaviors in the quantum simulations of the octamer and the heptamer.
Avilés
Michael W
MW
Department of Chemistry and Physics, Arcadia University, Glenside, Pennsylvania 19038, USA.
Gray
Philip T
PT
Curotto
E
E