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Many-body study of the photoisomerization of the minimal model of the retinal protonated Schiff base

TitleMany-body study of the photoisomerization of the minimal model of the retinal protonated Schiff base
Publication TypeJournal Article
Year of Publication2011
AuthorsConte, A., Guidoni L., del Sole R., & Pulci O.
KeywordsTDDFT
Abstract

We investigate the optical properties of the tZt-penta-3,5-dieniminium cation, a simplified model for the protonated Schiff base of 11-cis retinal in rhodopsin, along the isomerization pathway by ab-initio calculations based on Many-Body Perturbation Theory using the GW method and the Bethe–Salpeter equation. Our calculations are carried out on a few significant CASSCF geometrical configurations of the isomerization minimal energy path taken from the literature. Our excitation energies are qualitatively in agreement with previous Quantum Monte Carlo and post-Hartree–Fock calculations. We also employ TDDFT based methods, and investigate the outcome of using different approximations and several exchange–correlation functionals. ► We theoretically studied the photoisomerization of the PSBMM by GW-BSE methods. ► We found that the photoisomerization follows the two-state model. ► This description agrees with previous CASPT2 and Quantum Montecarlo results. ► All TDDFT calculations predict an energy barrier along the isomerization path. ► Using hybrid exchange–correlation functionals in TDDFT reduces this gap.

JournalChemical Physics Letters
Volume515
Issue4-6
Pagination290 - 295
URLhttp://dx.doi.org/10.1016/j.cplett.2011.09.041
Date Published10/2011
User Project

UP71

Citation Key1260
ISBN Number00092614