Abstract
The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.
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Literature cited
V. L. Ermolaev, E. M. Bodunov, E. B. Sveshnikova, and T. A. Shakhverdov, Radiationless Transfer of Electronic Excitation Energy [in Russian], Nauka, Leningrad (1977).
A. A. Krasnovskii, “Luminescence in photosensitized formation of singlet oxygen in solutions,” in: Excited Molecules. Kinetics of Conversions [in Russian], Nauka, Leningrad (1982), pp. 32–60.
B. M. Dzhagarov, K. M. Salokhiddinov, and S. L. Bondarev, “Quenching of singlet and triplet states of porphyrins by molecular oxygen,” Biofizika,23, No. 5, 762–767 (1978).
B. M. Dzhagarov, G. P. Gurinovich, V. E. Novichenkov, et al., “Photosensitized formation of oxygen and quantum yield of intercombinational conversion in molecules of porphyrins and metalloporphyrins,” Khim. Fiz.,6, No. 7, 919–928 (1987).
B. M. Dzhagarov, E. I. Sagun, V. A. Ganzha, and G. P. Gurinovich, “Mechanism of quenching of triplet state of chlorophyll and related compounds by molecular oxygen,” Khim. Fiz.,6, No. 8, 1069–1078 (1987).
W. R. Ware, “Oxygen quenching of fluorescence in solution: An experimental study of the diffusion process,” J. Phys. Chem.,66, No. 3, 455–458 (1962).
J. B. Birks, Photophysics of Aromatic Molecules, Wiley-Interscience, New York (1970).
E. Wilhelm and R. Battino, “Thermodynamic functions of the solubilities of gases in liquids at 25°C,” Chem. Rev.,73, No. 1, 1–9 (1973).
V. B., Kogan, V. M. Fridman, and V. V. Kafarov, Handbook of Solubilities [in Russian], Nauka, Moscow (1961), Vol. 1, Book 1.
Ya. I. Gerasimov, V. P. Dreving, E. N. Eremin, et al., Course in Physical Chemistry [in Russian], Vol. 1, Khimiya, Moscow (1970).
A. Weissberger and E. Proskauer, Organic Solvents, 2nd edn., revised by J. A. Riddick and E. E. Toops, Wiley-Interscience, New York (1955).
R. C. Reed, J. M. Prausnitz, and T. K. Sherwood, Properties of Gases and Liquids [Russian translation], Khimiya, Leningrad (1982).
H. Sovova, “A correlation of diffusivities of gases in liquids,” Coll. Czech. Chem. Commun.,41, No. 12, 3715–3723 (1976).
A. I. Burshtein, “Concentration quenching of noncoherent excitations in solutions,” Usp. Fiz. Nauk,143, No. 4, 553–600 (1984).
S. G. Éntelis and R. P. Tiger, Kinetics of Reactions in the Liquid Phase [in Russian], Khimiya, Moscow (1973).
A. B. Doktorov and A. I. Burshtein, “Quantum theory of long-range transfer accelerated by diffusion,” Zh. Éksp. Teor. Fiz.,68, No. 4, 1349–1362 (1975).
K. I. Zamarev, R. F. Khairutdinov, and V. P. Zhdanov, Electron Tunneling in Chemistry [in Russian], Nauka, Novosibirsk (1985).
N. M. Bazhin, N. P. Gritsan, V. V. Korolev, and S. V. Kamyshin, “Quenching of fluorescence and phosphorescence of phenanthrene by oxygen in a solid matrix,” Khim. Fiz.,5, No. 8, 1037–1043 (1986).
E. I. Kapinus and V. P. Staryi, “Influence of solvent on kinetics of deactivation of triplet molecules by electron acceptors,” Teor. Éksp. Khim.,17, No. 1, 35–43 (1981).
A. I. Burshtein, “Molecular-kinetic aspects of chemical physics of the condensed state,” Usp. Khim.,47, No. 2, 212–234 (1978).
A. I. Burshtein and B. I. Yakobson, “Long-range theory of transfer reactions in condensed media,” Khim. Vys. Énerg.,14, No. 4, 291–306 (1980).
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Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.
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Kapinus, E.I., Ganzha, V.A., Dzhagarov, B.M. et al. Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin. Theor Exp Chem 25, 146–151 (1989). https://doi.org/10.1007/BF01135003
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DOI: https://doi.org/10.1007/BF01135003