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Article Dans Une Revue Journal of Chemical Theory and Computation Année : 2020

Quantum and Quantum-Classical Studies of the Photoisomerization of a Retinal Chromophore Model

Résumé

We report an in-depth analysis of the photo-induced isomerization of the 2-cis-penta-2,4-dieniminium cation: a minimal model of the 11-cis retinal protonated Schiff base chromophore of the dim-light photoreceptor rhodopsin. Based on recently-developed three-dimensional potentials parametrized on ab initio multi-state multi-con-figurational second-order perturbation theory data, we perform quantum-dynamical studies. In addition, simulations based on various quantum-classical methods, among which Tully surface hopping and the coupled-trajectory approach derived from the exact factorization, allow us to validate their performance against vibronic-wavepacket propagation and, therefore, a purely quantum treatment. Quantum-dynamics results uncover qualitative differences with respect to the two-dimensional Hahn-Stock potentials , widely-used as model potentials for the isomerization of the same chromophore, due to the increased dimensionality and three-mode correlation. Quantum-classical simulations show, instead, that three-dimensional model potentials are capable of capturing a number of features revealed by atomistic simulations and experimental observations. In particular, a recently reported vibrational phase relationship between double-bond torsion and hydrogen-out-of-plane modes critical for rhodopsin isomerization efficiency is correctly reproduced.
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Dates et versions

hal-02994954 , version 1 (10-11-2020)

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Emanuele Marsili, Massimo Olivucci, David Lauvergnat, Federica Agostini. Quantum and Quantum-Classical Studies of the Photoisomerization of a Retinal Chromophore Model. Journal of Chemical Theory and Computation, 2020, 16 (10), pp.6032-6048. ⟨10.1021/acs.jctc.0c00679⟩. ⟨hal-02994954⟩
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