Probing the partition function for temperature-dependent potentials with nested sampling

Abstract

Thermodynamic properties can be in principle derived from the partition function, which, in many-atom systems, is hard to evaluate as it involves a sum on the accessible microscopic states. Recently, the partition function has been computed via nested sampling, relying on Bayesian statistics, which is able to provide the density of states as a function of the energy in a single run, independently of the temperature. This appealing property is lost whenever the potential energy that appears in the partition function is temperature-dependent: for instance, mean-field effective potential energies or the quantum partition function in the path-integral formalism. For these cases, the nested sampling must be carried out at each temperature, which results in a massive increase of computational time. Here, we introduce and implement a new method, that is based on an extended partition function where the temperature is considered as an additional parameter to be sampled. The extended partition function can be evaluated by nested sampling in a single run, so to restore this highly desirable property even for temperature-dependent effective potential energies. We apply this original method to compute the quantum partition function for harmonic potentials and Lennard-Jones clusters at low temperatures and show that it outperforms the straightforward application of nested sampling for each temperature within several temperature ranges.