Accelerated Molecular Dynamics Study of Z/E Isomerization of Azobenzene: Kramers%26apos; Theory Validation

作者：Shigemitsu Yasuhiro^*; Ohga Yasushi

来源：Journal of Solution Chemistry, 2014, 43(9-10): 1746-1754.

DOI：10.1007/s10953-014-0237-5

• Molecular dynamics
• Azobenzene
• Z/E isomerization rate constant
• Kramers%26apos
• theory
• Dynamic solvent effect

The reaction rate in a condensed phase is retarded by solvent friction and deviates from the transition state theory (TST) in a highly viscous solvent. The Z/E isomerization kinetics of 4-dimethylamino-4%26apos;-nitroazobenzene in solution have been experimentally analyzed in a wide range of pressure in our previous studies. Herein the non-TST behaviors of the rate constant were theoretically modelled by means of Kramers%26apos; theory and its extensions and by molecular dynamics (MD) simulations. The Z/E isomerization takes place in milliseconds or longer and so is not reachable by normal MD simulations. The accelerated MD method was employed to simulate the rare events using a biased isomerization potential barrier.

• 出版日期2014-10