Please use this identifier to cite or link to this item: http://hdl.handle.net/2445/175904
Title: Refined metadynamics through canonical sampling using time-invariant bias potential: A study of polyalcohol dehydration in hot acidic solutions
Author: Kondo, Tomomi
Sasaki, Takehiko
Ruiz-Barragan, Sergi
Ribas Ariño, Jordi
Shiga, Motoyuki
Keywords: Aigua
Altes temperatures
Dinàmica molecular
Water
High temperatures
Molecular dynamics
Issue Date: 29-Oct-2020
Publisher: Wiley
Abstract: We propose a canonical sampling method to refine metadynamics simulations a posteriori, where the hills obtained from metadynamics are used as a time‐invariant bias potential. In this way, the statistical error in the computed reaction barriers is reduced by an efficient sampling of the collective variable space at the free energy level of interest. This simple approach could be useful particularly when two or more free energy barriers are to be compared among chemical reactions in different or competing conditions. The method was then applied to study the acid dependence of polyalcohol dehydration reactions in high‐temperature aqueous solutions. It was found that the reaction proceeds consistently via an SN2 mechanism, whereby the free energy of protonation of the hydroxyl group created as an intermediate is affected significantly by the acidic species. Although demonstration is shown for a specific problem, the computational method suggested herein could be generally used for simulations of complex reactions in the condensed phase.
Note: Versió postprint del document publicat a: https://doi.org/10.1002/jcc.26443
It is part of: Journal of Computational Chemistry, 2020, vol. 42, num. 3, p. 156-165
URI: http://hdl.handle.net/2445/175904
Related resource: https://doi.org/10.1002/jcc.26443
ISSN: 0192-8651
Appears in Collections:Articles publicats en revistes (Ciència dels Materials i Química Física)

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