Chemistry Faculty Publications
Document Type
Article
Abstract
Rhodopsin (Rh) and bathorhodopsin (bathoRh) quantum-mechanics/molecular-mechanics models based on ab initio multiconfigurational wave functions are employed to look at the light induced pi-bond breaking and reconstitution occurring during the Rh -> bathoRh and bathoRh -> Rh isomerizations. More specifically, semiclassical trajectory computations are used to compare the excited (S-1) and ground (S-0) state dynamics characterizing the opposite steps of the Rh/bathoRh photochromic cycle during the first 200 fs following photoexcitation. We show that the information contained in these data provide an unprecedented insight into the sub-picosecond pi-bond reconstitution process which is at the basis of the reactivity of the protein embedded 11-cis and all-trans retinal chromophores. More specifically, the data point to the phase and amplitude of the skeletal bond length alternation stretching mode as the key factor switching the chromophore to a bonding state. It is also confirmed/found that the phase and amplitude of the hydrogen-out-of-plane mode controls the stereochemical outcome of the forward and reverse photoisomerizations.
Copyright Statement
Publisher PDF
Repository Citation
Schapiro, Igor; Ryazantsev, Mikhail Nikolaevich; Frutos, Luis Manuel; Ferre, Nicolas; Lindh, Roland; and Olivucci, Massimo, "The Ultrafast Photoisomerizations Of Rhodopsin And Bathorhodopsin Are Modulated By Bond Length Alternation And Hoop Driven Electronic Effects" (2011). Chemistry Faculty Publications. 68.
https://scholarworks.bgsu.edu/chem_pub/68
Publication Date
3-2011
Publication Title
Journal Of The American Chemical Society
DOI
https://doi.org/10.1021/ja1056196
Start Page No.
3354
End Page No.
3364
