Theoretical expressions for the luminescence polarization and absorption dichroism of polyatomic molecular complexes in the gas phase were obtained. It was shown that a non-equilibrium rotational distribution arose because of the conservation of total angular momentum during complex formation. The characteristics of orientational relaxation and the kinetics of the polarization response could change substantially depending on the stereodynamics of the complexation process. Ranges of dynamic parameters in which the polarization could increase several times compared to that of the free molecules were found. The polarization could sometimes even change sign during the relaxation process.
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Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 80, No. 1, pp. 58–64, January–February, 2013.
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Blokhin, A.P. Manifestation of the formation process in the polarization characteristics of free molecular complexes. J Appl Spectrosc 80, 54–60 (2013). https://doi.org/10.1007/s10812-013-9720-9
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DOI: https://doi.org/10.1007/s10812-013-9720-9