@misc{10481/88989,
year = {2008},
month = {5},
url = {https://hdl.handle.net/10481/88989},
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.},
organization = {IACT},
publisher = {American Chemical Society},
title = {DFT Research on the Dehydroxylation Reaction of Pyrophyllite 1. First-Principle Molecular Dynamics Simulations},
doi = {10.1021/jp711278s},
author = {Molina Montes, María Ester and Donadio, Davide and Hernández Laguna, Alfonso and Sainz Díaz, Claro Ignacio and Parrinello, Michele},
}