2026-04-13T07:39:56Zhttps://recercat.cat/oai/request

oai:recercat.cat:2445/1758882025-11-19T20:35:35Zcom_2072_1057col_2072_478796col_2072_478917col_2072_478933

00925njm 22002777a 4500 dc Albareda, Guillermo author Riera, Arnau author González Pérez, Miguel author Bofill i Villà, Josep M. author Moreira, Ibério de Pinho Ribeiro author Valero Montero, Rosendo author Tavernelli, Ivano author 2021-03-30T15:33:07Z 2021-03-30T15:33:07Z 2020-09-14 2021-03-30T15:33:07Z There is a renewed interest in the derivation of statistical mechanics from the dynamics of closed quantum systems. A central part of this program is to understand how closed quantum systems, i.e., in the absence of a thermal bath, initialized far-from-equilibrium can share a dynamics that is typical to the relaxation towards thermal equilibrium. Equilibration dynamics has been traditionally studied with a focus on the so-called quenches of large-scale many-body systems. We consider here the equilibration of a two-dimensional molecular model system describing the double proton transfer reaction in porphine. Using numerical simulations, we show that equilibration indeed takes place very rapidly (about 200 fs) for initial states induced by pump-dump laser pulse control with energies well above the synchronous barrier. The resulting equilibration state is characterized by a strong delocalization of the probability density of the protons that can be explained, mechanistically, as the result of (i) an initial state consisting of a large superposition of vibrational states, and (ii) the presence of a very effective dephasing mechanism. Química quàntica Dinàmica molecular Termodinàmica Quantum chemistry Molecular dynamics Thermodynamics Quantum equilibration of the double-proton transfer in a model system Porphine