Modelling Time-Resolved Two-Dimensional Electronic Spectroscopy of the Primary Photoisomerization Event in Rhodopsin - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry B Année : 2014

Modelling Time-Resolved Two-Dimensional Electronic Spectroscopy of the Primary Photoisomerization Event in Rhodopsin

Ivan Rivalta
Oliver Weingart
  • Fonction : Auteur
Marco Garavelli
Shaul Mukamel

Résumé

Time-resolved two-dimensional (2D) electronic spectra (ES) tracking the evolution of the excited state manifolds of the retinal chromophore have been simulated along the photoisomerization pathway in bovine rhodopsin, using a state-of-the-art hybrid QM/MM approach based on multiconfigurational methods. Simulations of broadband 2D spectra provide a useful picture of the overall detectable 2D signals from the near-infrared (NIR) to the near-ultraviolet (UV). Evolution of the stimulated emission (SE) and excited state absorption (ESA) 2D signals indicates that the S1 → SN (with N ≥ 2) ESAs feature a substantial blue-shift only after bond inversion and partial rotation along the cis → trans isomerization angle, while the SE rapidly red-shifts during the photoinduced skeletal relaxation of the polyene chain. Different combinations of pulse frequencies are proposed in order to follow the evolution of specific ESA signals. These include a two-color 2DVis/NIR setup especially suited for tracking the evolution of the S1 → S2 transitions that can be used to discriminate between different photochemical mechanisms of retinal photoisomerization as a function of the environment. The reported results are consistent with the available time-resolved pump–probe experimental data, and may be used for the design of more elaborate transient 2D electronic spectroscopy techniques.

Dates et versions

hal-01121386 , version 1 (28-02-2015)

Identifiants

Citer

Ivan Rivalta, Artur Nenov, Oliver Weingart, Giulio Cerullo, Marco Garavelli, et al.. Modelling Time-Resolved Two-Dimensional Electronic Spectroscopy of the Primary Photoisomerization Event in Rhodopsin. Journal of Physical Chemistry B, 2014, 118 (28), pp.8396-8405. ⟨10.1021/Jp502538m⟩. ⟨hal-01121386⟩
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