The possibility of population of the lowest-lying triplet state (T(1)) in the early events of the photochemical isomerization process of a model chromophore of Rhodopsin (Rh) has been analyzed using multireference perturbation theory (CASPT2//CASSCF) methods. It is shown that the characteristics of the isomerization process namely small S(1)-T(1) gap, presence of hydrogen out of plane active vibrational modes, and existence of a dense manifold of vibrational states, render possible the fulfilment of the conditions needed for the population of T(1). The possible consequences for the photochemistry and photophysics of Rh are also discussed.
R. González-Luque, G. Olaso-González, M. Merchán, P. B. Coto, L. Serrano-Andrés, M. Garavelli (2011). On the role of the triplet state in the cis/trans isomerization of rhodopsin: A CASPT2//CASSCF study of a model chromophore. INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY, 111, 3431-3437 [10.1002/qua.23079].
On the role of the triplet state in the cis/trans isomerization of rhodopsin: A CASPT2//CASSCF study of a model chromophore
GARAVELLI, MARCO
2011
Abstract
The possibility of population of the lowest-lying triplet state (T(1)) in the early events of the photochemical isomerization process of a model chromophore of Rhodopsin (Rh) has been analyzed using multireference perturbation theory (CASPT2//CASSCF) methods. It is shown that the characteristics of the isomerization process namely small S(1)-T(1) gap, presence of hydrogen out of plane active vibrational modes, and existence of a dense manifold of vibrational states, render possible the fulfilment of the conditions needed for the population of T(1). The possible consequences for the photochemistry and photophysics of Rh are also discussed.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
