Direct Computation of the Quantum Partition Function by Path-Integral Nested Sampling.

In the present work we introduce a computational approach to the absolute rovibrational quantum partition function using the path-integral formalism of quantum mechanics in combination with the nested sampling technique. The numerical applicability of path-integral nested sampling is demonstrated for small molecules of spectroscopic interest. The computational cost of the method is determined by the evaluation time of a point on the potential energy surface (PES). For efficient PES implementations, the path-integral nested sampling method can be a viable alternative to the direct-Boltzmann-summation technique of variationally computed rovibrational energies, especially for medium-sized molecules and at elevated temperatures.