Direct computation of the quantum partition function by path-integral nested sampling

Understand

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.