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dc.contributor.authorVidela, Pablo E.
Rossky, Peter J.
Laria, Daniel
dc.date.accessioned 2018-07-16T18:43:46Z
dc.date.available 2018-07-16T18:43:46Z
dc.date.issued 2018
dc.identifier.citation Videla, Pablo E., Rossky, Peter J. and Laria, Daniel. "Isotopic equilibria in aqueous clusters at low temperatures: Insights from the MB-pol many-body potential." The Journal of Chemical Physics, 148, no. 8 (2018) AIP Publishing: https://doi.org/10.1063/1.5019377.
dc.identifier.urihttps://hdl.handle.net/1911/102429
dc.description.abstract By combining path-integrals molecular dynamics simulations with the accurate MB-pol potential energy surface, we investigate the role of alternative potential models on isotopic fractionation ratios between H and D atoms at dangling positions in water clusters at low temperatures. Our results show clear stabilizations of the lighter isotope at dangling sites, characterized by free energy differences ΔG that become comparable to or larger than kBT for temperatures below ∼75 K. The comparison between these results to those previously reported using the empirical q-TIP4P/F water model [P. E. Videla et al., J. Phys. Chem. Lett. 5, 2375 (2014)] reveals that the latter Hamiltonian overestimates the H stabilization by ∼25%. Moreover, predictions from the MB-pol model are in much better agreement with measured results reported for similar isotope equilibria at ice surfaces. The dissection of the quantum kinetic energies into orthogonal directions shows that the dominant differences between the two models are to be found in the anharmonic characteristics of the potential energy surfaces along OH bond directions involved in hydrogen bonds.
dc.language.iso eng
dc.publisher AIP Publishing
dc.rights Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
dc.title Isotopic equilibria in aqueous clusters at low temperatures: Insights from the MB-pol many-body potential
dc.type Journal article
dc.citation.journalTitle The Journal of Chemical Physics
dc.citation.volumeNumber 148
dc.citation.issueNumber 8
dc.type.dcmi Text
dc.identifier.doihttps://doi.org/10.1063/1.5019377
dc.identifier.pmid 29495769
dc.type.publication publisher version
dc.citation.articleNumber 084303


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