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

Béla J. Szekeres

doi:10.1021/acs.jctc.8b00368

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

2018-06-26

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DOI：10.1021/acs.jctc.8b00368

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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.

Keywords:

POTENTIAL-ENERGY SURFACE

HIGH-TEMPERATURE

MOLECULES

WATER

SIMULATIONS

METHANE

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

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