Date of Original Version
The numerical advantage of quantum Monte Carlo simulations of rigid bodies relative to the flexible simulations is investigated for some simple systems. The results show that if high frequency modes in molecular condensed matter are predominantly in the ground state, the convergence of path integral simulations becomes nonuniform. Rigid body quantum parallel tempering simulations are necessary to accurately capture thermodynamic phenomena in the temperature range where the dynamics are influenced by intermolecular degrees of freedom; the stereographic projection path integral adapted for quantum simulations of asymmetric tops is a significantly more efficient strategy compared with Cartesian coordinate simulations for molecular condensed matter under these conditions. The reweighted random series approach for stereographic path integral Monte Carlo is refined and implemented for the quantum simulation of water clusters treated as an assembly of rigid asymmetric tops.
Langley, Stephen F., E. Curatto, D. L. Freeman and J. D. Doll. ʺRigid Quantum Monte Carlo Stimulations of Condensed Molecular Matter: Water Clusters in the n=2 - > B Range.ʺ Journal of Chemical Physics. 126(8):084506. February 28, 2007.