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Journal Article

Quantum equilibration of the double-proton transfer in a model system porphine


Albareda Piquer,  G.
Theory Group, Theory Department, Max Planck Institute for the Structure and Dynamics of Matter, Max Planck Society;
Center forFree-Electron Laser Science;
Institute of Theoretical and Computational Chemistry, Universitat de Barcelona;

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Albareda Piquer, G., Riera, A., Gonzalez, M., Bofill, J. M., de Moreira, I. P. R., Valero, R., et al. (2020). Quantum equilibration of the double-proton transfer in a model system porphine. Physical Chemistry Chemical Physics, 22(39), 22332-22341. doi:10.1039/D0CP02991B.

Cite as: http://hdl.handle.net/21.11116/0000-0005-464D-7
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 (∼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.