Systematic control of photochemistry: the dynamics of photoisomerization of a model cyanine dye

J Am Chem Soc. 2005 Apr 20;127(15):5720-6. doi: 10.1021/ja045652s.

Abstract

On-the-fly CASSCF nonadiabatic dynamics have been used to model the trans-cis isomerization of a model cyanine dye. Our results show that the photochemical generation of the trans versus cis product is dynamically controlled by the presence of an extended cis-trans conical intersection seam that persists along all torsional angles. This in turn suggests that the photochemistry could be completely controlled by controlling the distribution of momentum components in a wave packet excited by laser photolysis in a coherent control experiment.