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dc.contributor.authorLaria, D
dc.contributor.authorMartí Rabassa, Jordi
dc.contributor.authorGuàrdia Manuel, Elvira
dc.contributor.otherUniversitat Politècnica de Catalunya. Departament de Física i Enginyeria Nuclear
dc.identifier.citationLaria, D.; Marti, J.; Guardia, E. Protons in supercritical water: a multistate empirical valence bond study. "Journal of the American Chemical Society", Febrer 2004, vol. 126, núm. 7, p. 2125-2134.
dc.description.abstractMolecular dynamics simulations have been performed to analyze microscopic details related to aqueous solvation of excess protons along the supercritical T = 673 K isotherm, spanning a density interval from a typical liquid down to vapor environments. The simulation methodology relies on a multistate empirical valence bond Hamiltonian model that includes a proton translocation mechanism. Our results predict a gradual stabilization of the solvated Eigen cation [H3O·(H2O)3]+ at lower densities, in detriment of the symmetric Zundel dimer [H·(H2O)2]+. At all densities, the average solvation structure in the close vicinity of the hydronium is characterized by three hydrogen bond acceptor water molecules and presents minor changes in the solute water distances. Characteristic times for the proton translocation jumps have been computed using population relaxation time correlation functions. Compared to room temperature results, the rates at high densities are 4 times faster and become progressively slower in steamlike environments. Diffusion coefficients for the excess proton have also been computed. In agreement with conductometric data, our results show that contributions from the Grotthus mechanism to the overall proton transport diminish at lower densities and predict that in steamlike environments, the proton diffusion is almost 1 order of magnitude slower than that for pure water. Spectroscopic information for the solvated proton is accordant to the gradual prevalence of proton localization in Eigen-like structures at lower densities.
dc.format.extent10 p.
dc.rightsAttribution-NonCommercial-NoDerivs 3.0 Spain
dc.subjectÀrees temàtiques de la UPC::Física
dc.subject.lcshMolecular dynamics--Simulation methods
dc.titleProtons in supercritical water: a multistate empirical valence bond study
dc.subject.lemacDinàmica molecular
dc.contributor.groupUniversitat Politècnica de Catalunya. SIMCON - First-principles approaches to condensed matter physics: quantum effects and complexity
dc.rights.accessRestricted access - publisher's policy
dc.description.versionPostprint (published version)
local.citation.authorLaria, D.; Marti, J.; Guardia, E.
local.citation.publicationNameJournal of the American Chemical Society

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