The Ultrafast Photoisomerizations of Rhodopsin and Bathorhodopsin Are Modulated by Bond Length Alternation and HOOP Driven Electronic Effects
Citations Over TimeTop 10% of 2011 papers
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 π-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 π-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.
Related Papers
- → Ab Initio Study of Cis−Trans Photoisomerization in Stilbene and Ethylene(2003)267 cited
- → The Different Photoisomerization Efficiency of Azobenzene in the Lowest nπ* and ππ* Singlets: The Role of a Phantom State(2008)223 cited
- → Stereoselective Excited-State Isomerization and Decay Paths in cis-Cyclobiazobenzene(2019)9 cited
- → Photoisomerization mechanism of 4-methylpyridine explored by electronic structure calculations and nonadiabatic dynamics simulations(2011)12 cited
- → Delayed Ring-Opening in 1,3-Cyclohexadiene upon Photoexcitation to a Higher State Probed by Time-Resolved Soft X-Ray Absorption(2021)