Self-consistent phonons revisited. II. A general and efficient method for computing free energies and vibrational spectra of molecules and clusters

Abstract

The self-consistent phonons (SCP) method provides a consistent way to include anharmonic effects when treating a many-body quantum system at thermal equilibrium. The system is then described by an effective temperature-dependent harmonic Hamiltonian, which can be used to estimate the system's properties, such as its free energy or its vibrational spectrum. The numerical bottleneck of the method is the evaluation of Gaussian averages of the potential energy and its derivatives. Several algorithmic ideas/tricks are introduced to reduce the cost of such integration by orders of magnitude, e.g., relative to that of the previous implementation of the SCP approach by Calvo et al. [J. Chem. Phys. 133, 074303 (2010)]. One such algorithmic improvement is the replacement of standard Monte Carlo integration by quasi-Monte Carlo integration utilizing low-discrepancy sequences. The performance of the method is demonstrated on the calculation of vibrational frequencies of pyrene. It is then applied to compute the free energies of five isomers of water hexamer using the WHBB potential of Bowman and co-workers [J. Chem. Phys. 134, 094509 (2011)]. The present results predict the hexamer prism being thermodynamically most stable, with the free energy of the hexamer cage being about 0.2 kcal mol(-1) higher at all temperatures below T = 200 K.