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Updated: Jun 14, 2026

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Quantum effects on the free energy of ionic aqueous clusters evaluated by nonequilibrium computational methods
Lisandro Hernández de la Peña1, Gilles H Peslherbe
1Centre for Research in Molecular Modeling and Department of Chemistry & Biochemistry, Concordia University, Montreal, Canada.
Abstract:
Nonequilibrium simulation methods and rigid-body path-integral techniques are combined to estimate the relevance of protonic quantum effects in the free energy of ion-water clusters. The Crooks' fluctuation relation is used to quantitatively characterize the impact of quantum effects on the dissociation free energy of the paradigm I(-)(H(2)O)(5). By use of a rigorous smoothing procedure in the calculation of the work distributions, the effects are found to be about 11% and therefore non-negligible. Quantum effects on the potential of mean force of Na(+)(H(2)O)(12) were also evaluated using Jarzynski's work theorem for a reaction coordinate, and they were also found to be significant. The results suggest that quantization should play a significant role in the kinetics of ionic transport in aqueous environments.
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