Dynamic effects of the bridged structure on the quantum yield of the cis → trans photoisomerization of azobenzene
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Abstract
A nonadiabatic molecular dynamics simulation was performed for the cis → trans photoisomerization of diindane diazocine to determine how its bridged structure results in the highest reported quantum yield for this isomerization. Similar to azobenzene, when diindane diazocine is excited to the S1 state, it isomerizes to the trans form by a pedal motion of the -NN- moiety passing through the S1/S0 conical intersection. However, due to the faster intramolecular vibrational energy redistribution, the excited state lifetime of diindane diazocine is shorter. The bridged structure reduces the degrees of freedom, other than those that drive the isomerization. Therefore, the kinetic energy is selectively distributed to the specific normal mode for the pedal motion of the -NN- moiety, and it is efficiently utilized for the isomerization to the trans form, which is considered a major reason for the increased isomerization yield.
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