Anisotropy of ensembles of free polyatomic photoisomers
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In order to describe the polarization response of an ensemble of molecules undergoing structural transformations (photoisomerization) under collisionless conditions, we have calculated the orientational correlation functions. We assume that changes in molecular structure can be considered as instantaneous on the molecular rotation scale. We have obtained general expressions for the anisotropy when the original molecule and the photoisomer are asymmetric tops. We have performed anisotropy calculations for steady-state experimental conditions and a number of limiting situations, when the characteristic times of the photoreaction are much shorter or much longer than the molecular reorientation times and when the original molecule and the photoisomer are planar tops. We have shown that detecting the polarization response allows us to estimate the characteristic times of the photoreaction and to determine the intramolecular orientation of the transition dipole moments for transitions with absorption and emission of light.
Key wordspolyatomic molecules photoisomerization anisotropy orientational correlation functions
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