Nonadiabatic simulation study of photoisomerization of azobenzene: detailed mechanism and load-resisting capacity

J Chem Phys. 2008 Oct 28;129(16):164111. doi: 10.1063/1.3000008.

Abstract

Nonadiabatic dynamical simulations were carried out to study cis-to-trans isomerization of azobenzene under laser irradiation and/or external mechanical loads. We used a semiclassical electron-radiation-ion dynamics method that is able to describe the coevolution of the structural dynamics and the underlying electronic dynamics in a real-time manner. It is found that azobenzene photoisomerization occurs predominantly by an out-of-plane rotation mechanism even under a nontrivial resisting force of several tens of piconewtons. We have repeated the simulations systematically for a broad range of parameters for laser pulses, but could not find any photoisomerization event by a previously suggested in-plane inversion mechanism. The simulations found that the photoisomerization process can be held back by an external resisting force of 90-200 pN depending on the frequency and intensity of the lasers. This study also found that a pure mechanical isomerization is possible from the cis-to-trans state if the azobenzene molecule is stretched by an external force of approximately 1250-1650 pN. Remarkably, the mechanical isomerization first proceeds through a mechanically activated inversion, and then is diverted to an ultrafast downhill rotation that accomplishes the isomerization. Implications of these findings to azobenzene-based nanomechanical devices are discussed.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Azo Compounds / chemistry*
  • Electrons
  • Hot Temperature
  • Lasers
  • Models, Chemical*
  • Photochemical Processes*
  • Stereoisomerism
  • Stress, Mechanical*

Substances

  • Azo Compounds
  • azobenzene