Equilibrium properties of quantum water clusters by the variational Gaussian wavepacket method

The variational Gaussian wavepacket (VGW) method in combination with the replica-exchange Monte Carlo is applied to calculations of the heat capacities of quantum water clusters, (H(2)O)(8) and (H(2)O)(10). The VGW method is most conveniently formulated in Cartesian coordinates. These in turn require the use of a flexible (i.e., unconstrained) water potential. When the latter is fitted as a linear combination of Gaussians, all the terms involved in the numerical solution of the VGW equations of motion are analytic. When a flexible water model is used, a large difference in the timescales of the inter- and intramolecular degrees of freedom generally makes the system very difficult to simulate numerically. Yet, given this difficulty, we demonstrate that our methodology is still practical. We compare the computed heat capacities to those for the corresponding classical systems. As expected, the quantum effects shift the melting temperatures toward the lower values. (c) 2008 American Institute of Physics.