Direct computation of the quantum partition function by path-integral nested sampling
Quantum Physics
2018-06-22 v2 Chemical Physics
Computational Physics
Abstract
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.
Cite
@article{arxiv.1804.05987,
title = {Direct computation of the quantum partition function by path-integral nested sampling},
author = {Bela Szekeres and Livia B. Partay and Edit Matyus},
journal= {arXiv preprint arXiv:1804.05987},
year = {2018}
}