Characterization of the conical intersection of the visual pigment rhodopsin at the CASPT2//CASSCF/AMBER level of theory

• The branching plane associated with the conical intersection controlling the photochemical Z -> E isomerization reaction of rhodopsin has been mapped using a CASPT2//CASSCF/ AMBER quantum mechanics-molecular mechanics method. The nature of the derivative coupling and gradient difference vectors spanning the branching plane has been investigated, showing that the conical intersection is not only associated with the isomerization process but also to a charge transfer along the retinal backbone. Using a simple Landau-Zener model, the paper discusses the possible effects of the documented conical intersection topologies on the efficiency of the reactive process. It is argued that the peculiar shape of the conical intersection favours decay at structures that are geometrically displaced towards the photoproduct bathorhodopsin.

Ämnesord

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

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