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

MPS-Authors
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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;

External Ressource
Fulltext (public)

d0cp02991b.pdf
(Publisher version), 6MB

Supplementary Material (public)

suppl.zip
(Supplementary material), 11MB

Citation

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
Abstract
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.