Journal
JOURNAL OF PHYSICAL CHEMISTRY A
Volume 114, Issue 32, Pages 8190-8201Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jp103253b
Keywords
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Funding
- Japan Society for the Promotion of Science (JSPS) [20608003, 19350013]
- Kyoto University Fukui Institute for Fundamental Chemistry
- Kyoto University
- Grants-in-Aid for Scientific Research [19350013, 20608003] Funding Source: KAKEN
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The dynamics of the photoisomerization of a model protonated Schiff base of 9-cis retinal in isorhodopsin is investigated using nonadiabatic molecular dynamics simulation combined with ab initio quantum chemical calculations on-the-fly. The quantum chemical part is treated at the complete-active space self-consistent field level for six electrons in six active pi orbitals with the 6-31G basis set (CASSCF(6,6)/6-31G). The probabilities of nonadiabatic transitions between the S-1 ((1)pi pi*) and S-0 states are estimated in light of the Zhu-Nakamura theory. The photoinduced cis-trans isomerization of 9-cis retinal proceeds slower than that of its 11-cis analogue and at a lower quantum yield, confirming experimental observations. An energetic barrier in the excited state impedes the elongation and twist of the C-9=C-10 stretch and torsion coordinates, respectively, resulting in the trapping of trajectories before transition. Consequently, the isomerization takes longer time and the transition more often occurs at smaller twist angle of =C-8-C-9=C-10-C-11=, which leads to regeneration of the 9-cis reactant. Thus, neither the smaller twist observed in the X-ray crystal nor the slower movement of nuclei in the transition region would be the main reason for the longer reaction time and lower yield. A well-known space-saving asynchronous bicycle pedal or crankshaft photoisomerization mechanism is found to be operational in 9-cis retinal. The simulation in vacuo suggests that the excited-state barrier and the photoisomerization itself are intrinsic properties of the visual chromophore and not triggered mainly by the protein environment that surrounds the chromophore.
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