LAUSR

Abstract Quantum chemical calculations of a potent class of photoswitches acylhydrazones have been carried out with the goal to describe their thermal cis → trans isomerization. The effects of substituents, in particular their number, position and nature of the substituents (electron donating/withdrawing groups (EDGs/EWGs)), on activation energies incorporating solvent effects have been systematically researched with the ultimate goal to illuminate the isomerization process. Our results show that most parameters are highly dependent on the substitution pattern on the crucial positions (R1 and R2 position) of the backbone fragment, which in turn has a significant impact on the absorption spectra, the energy levels of molecular orbitals, the transition properties for the trans/cis isomers, the half-lives τ1/2 and the rate constants for the thermal cis → trans isomerization of the compounds. In summary, both relative strength of the donor/accept groups and solvent polarity have significant impact on the electric properties. Finally, the nature of the transition state(s) and its dependence on substituents and the environment are discussed. An ingenious approach to the construction of reaction path was realized, and energy barriers were determined from two-dimensional potential energy surfaces of the ground states.