On Weak-Field (One-Photon) Coherent Control of Photoisomerization

Abstract

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Describing the photo-isomerization of a retinal chromophore model with coupled and quantum trajectories

“…The model Hamiltonian [47] used in this work allows us to describe the 11-cis to all-trans isomerization of the retinal chromophore in rhodopsin [30,[56][57][58][59][60][61][62][63][64][65][66][67]. Photoabsorption takes the cis conformer from the electronic ground state S 0 to the first excited state S 1 , thus initiating an isomerization reaction towards the trans conformer.…”

Quantum molecular dynamics simulations of the effect of secondary modes on the photoisomerization of a retinal chromophore model

“…At the cis geometry (ϕ cis = 0), the excitation energy ∆E ex to induce a S 0 -to-S 1 transition at q = 0 lies in the visible domain, being ∆E ex = 2.48 eV (λ ex = 500 nm). The model is parametrized to reproduce features observed in Raman and time-resolved experiments [17], and was for long time the preferred choice to study the ultrafast relaxation process of the photo-excited retinal based on quantum-dynamical simulations [18,[56][57][58][59][60][61][62][63][64][65][66][67].…”

Relaxation dynamics through a conical intersection: Quantum and quantum–classical studies

“…Capturing energy transfer from the quantum electronic system, that is excited at the initial time with visible light, to the classical nuclear vibrations is a challenging task. One can only guess that, considering a larger number of degrees of freedom, i.e., with the inclusion of an environment in the model 9,40,43 or by performing atomistic simulations of the whole molecule 2,13,30,99 , might result in a more classical behavior of the whole system, and in a better description of the energy transfer process based on quantum-classical simulations.…”

“…Electronic ground (S 0 ) and first-excited (S 1 ) singlet states present a conical intersection at some geometry, as will be shown in the following. The reduced dimensionality of the model, and the fact that it is parametrized to reproduce features observed in Raman and time-resolved experiments 38 , made it for long time the preferred choice to study the ultrafast relaxation process of the photo-excited retinal based on quantum-dynamical simulations 11,[40][41][42][43][44][45][46][47][48][49][50][51] . To our knowledge, however, trajectory-based methods have not yet been employed, systematically, in combination with this model 44,49,52 .…”