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DFT Research on the Dehydroxylation Reaction of Pyrophyllite 1. First-Principle Molecular Dynamics Simulations
dc.contributor.author | Molina Montes, María Ester | |
dc.contributor.author | Donadio, Davide | |
dc.contributor.author | Hernández Laguna, Alfonso | |
dc.contributor.author | Sainz Díaz, Claro Ignacio | |
dc.contributor.author | Parrinello, Michele | |
dc.date.accessioned | 2024-02-12T08:27:33Z | |
dc.date.available | 2024-02-12T08:27:33Z | |
dc.date.issued | 2008-05-20 | |
dc.identifier.uri | https://hdl.handle.net/10481/88989 | |
dc.description.abstract | The dehydroxylation of pyrophyllite involves the reaction of OH groups and elimination of water molecules through two possible mechanisms, one involving the bridging hydroxyl groups of an octahedral Al3+ pair and the other two hydroxyl groups reacting across the dioctahedral vacancy. First-principles molecular dynamics simulations at the density functional theory level are used together with the metadynamics algorithm to explore the free-energy surface (FES) of the initial step of the dehydroxylation. We observe that the two possible dehydroxylation mechanisms yield similar activation energies at 0 K, but at high temperatures, the cross mechanism has lower free energy than that of the on-site one. The dehydroxylation process produces different semidehydroxylated intermediates that should be taken into account. The role of the temperature in favoring a dehydroxylation nonconcerted chain mechanism over another is here elucidated, and a novel competitive mechanism, which is assisted by the structural apical oxygens in the high-temperature regime, is proposed. | es_ES |
dc.description.sponsorship | IACT | es_ES |
dc.language.iso | eng | es_ES |
dc.publisher | American Chemical Society | es_ES |
dc.rights | Creative Commons Attribution-NonCommercial-NoDerivs 3.0 License | es_ES |
dc.rights.uri | http://creativecommons.org/licenses/by-nc-nd/3.0/ | es_ES |
dc.title | DFT Research on the Dehydroxylation Reaction of Pyrophyllite 1. First-Principle Molecular Dynamics Simulations | es_ES |
dc.type | journal article | es_ES |
dc.rights.accessRights | open access | es_ES |
dc.identifier.doi | 10.1021/jp711278s | |
dc.type.hasVersion | AO | es_ES |