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Mechanism of the cooperative vibronic emission of1δg singlet oxygen in solutions

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Abstract

The mechanism for inducing the probability of theα 1Δg-X3∑g − transition in an oxygen molecule with the simultaneous excitation of a vibration state of the solvent has been considered. The intensification of the 0-0 band of this transition under the influence of the solvent is attributed to the induction of the electric dipole moment of the b1∑g +-α 1Δg (mba) transition during a collision between O2 and solvent molecules. It has been shown that mba is strongly dependent on the intermolecular distance and, consequently, on the normal coordinate of the vibrations of the solvent (Q) at a given collision parameter. Calculation of the derivative ∂mba/∂Q (with consideration of the strong spin-orbit coupling of the b1∑g + and X3∑g − states) makes it possible to account for the intensity of the new luminescence band of1Δg singlet oxygen, which is shifted toward longer wavelengths relative to the 0-0 band of theα 1Δg-X3∑g − by the value of the vibrational quantum of the solvent.

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Authors and Affiliations

  1. Karagand University, USSR

    B. F. Minaev

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  1. B. F. Minaev
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 21, No. 5, pp. 594–596, September–October, 1985.

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Minaev, B.F. Mechanism of the cooperative vibronic emission of1δg singlet oxygen in solutions. Theor Exp Chem 21, 567–569 (1985). https://doi.org/10.1007/BF00944093

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  • DOI: https://doi.org/10.1007/BF00944093

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