Theoretical study on the excited-state intramolecular proton transfer in the aromatic schiff base salicylidene methylamine: An electronic structure and quantum dynamical approach

Juan Manuel Ortiz-Sánchez, Ricard Gelabert, Miquel Moreno, José M. Lluch

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58 Citations (Scopus)

Abstract

The proton-transfer dynamics in the aromatic Schiff base salicylidene methylamine has been theoretically analyzed in the ground and first singlet (π,π*) excited electronic states by density functional theory calculations and quantum wave-packet dynamics. The potential energies obtained through electronic calculations that use the time-dependent density functional theory formalism, which predict a barrierless excited-state intramolecular proton transfer, are fitted to a reduced three-dimensional potential energy surface. The time evolution in this surface is solved by means of the multiconfiguration time-dependent Hartree algorithm applied to solve the time-dependent Schrödinger equation. It is shown that the excited-state proton transfer occurs within 11 fs for hydrogen and 25 fs for deuterium, so that a large kinetic isotope effect is predicted. These results are compared to those of the only previous theoretical work published on this system [Zgierski, M. Z.; Grabowska, A. J. Chem. Phys. 2000, 113, 7845], reporting a configuration interaction singles barrier of 1.6 kcal mol-1 and time reactions of 30 and 115 fs for the hydrogen and deuterium transfers, respectively, evaluated with the semiclassical instanton approach. © 2006 American Chemical Society.
Original languageEnglish
Pages (from-to)4649-4656
JournalJournal of Physical Chemistry A
Volume110
Issue number14
DOIs
Publication statusPublished - 13 Apr 2006

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