Nonadiabatic ab initio dynamics of two models of Schiff base retinal

On-the-fly classical dynamics calculations combined with ab initio quantum chemical computations are carried out for two models of protonated Schiff base retinal in vacuo. The models are the 6pi system of 2-cis-penta-2,4-dieneimminium cation and the 12pi system in which two methyl groups are removed from the Schiff base of retinal. The CASSCF(6,6) level with the 6-31G basis set was employed for the quantum chemical part and the velocity Verlet algorism is utilized for time evolution of trajectories. The probabilities of nonadiabatic transition between the excited and ground state are estimated by the Zhu-Nakamura formulas. The 9-cis form product in addition to the all-trans one is generated in the present gas phase calculation for the 12pi model, despite the 9-cis generation being suppressed in protein. We have found that energy relaxation on the ground state occurs in two steps in the 12pi model. In the first step a metastable intermediate state is formed at approximately 100 fs after photoexcitation at the energy around 20-40 kcal/mol down from the excited potential energy surface, then it further relaxes to the energy around 60-80 kcal/mol from the excited surface, leading to the final state (second step). This relaxation pattern can be seen in all the three pathways to the all-trans, 9-cis, and (reverted) 11-cis form. Fourier transformation analysis reveals that the effective vibrational frequencies of the intermediate state are 1600-2000 cm(-1), which can be attributed to the conjugate CC bond frequencies in the electronic ground state. The two-step relaxation may be due to dynamical barriers. The two-step relaxation is not revealed in the smaller 6pi model. The crank-shaft motion of the C11C12 and C9C10 bonds is found in the isomerization, which indicates the motion is intrinsic in retinal, not due to the surrounding protein. The branching ratio is about 1:1:2 for the all-trans, 9-cis, and 11-cis form generation. The ratio is different from earlier works where Tully's fewest switching scheme was employed. The bond length and the dihedral angle at the transitions are also analyzed to investigate the transition mechanism.