Abstract
Polar luminescence probe+polar medium subsystems are considered. True minimization parameters of the free energy F are obtained. It is shown that Franck-Condon transitions between F-terms of different electronic states are generally not “vertical”. A complete thermodynamic classification of photoinduced processes of orientational relaxation in the excited S1 and ground S0 states is presented. Depending on the excitation conditions they can be either exo- or endothermic, spontaneous or induced (not spontaneous), and accompanied by an increase or decrease in entropy. Indifferent processes also take place. Regularities of shifts of fluorescence spectral bands and burned holes in time-resolved experiments are discussed.
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References
N. A. Nemkovich, V. I. Matseiko, and V. I. Tomin, Opt. Spektrosk.,49, 274 (1980).
V. S. Pavlovich, Doklady Akad. Nauk BSSR,25, 120 (1981).
A. N. Rubinov, V. I. Tomin, and B. A. Bushuk, J. Lumin,26, 377 (1982).
Yu. T. Mazurenko, Opt. Spektrosk.,55, 471 (1983).
S. K. Gorbatsevich, I. M. Gulis, and A. I. Komyak, Zh. Prikl. Spektrosk.,40, 773 (1984).
G. Van der Zwan and J. T. Hynes, J. Phys. Chem.,89, 4181 (1985).
R. F. Loring, Y. J. Yan, and S. Mukamel, J. Chem. Phys.,87, (1987) 5840.
Yu. T. Mazurenko, in: Solvatochromism [in Russian], ed. N. G. Bakhshiev, Leningrad (1989), pp. 122–190.
H. Murakami, S. Kinoshita, Y. Hirata, T. Okada, and N. Mataga, J. Chem. Phys.,97, 7881 (1992).
N. S. Bayliss and E. G. McRae, J. Phys. Chem.,58, 1002 (1954).
B. S. Neporent, Zh. Fiz. Khim.,30, 1048 (1956).
N. G. Bakhshiev, Opt. Spektrosk.,16, 821 (1964).
N. G. Bakhshiev, Spectroscopy of Intermolecular Interactions [in Russian], Leningrad (1972).
V. S. Pavlovich, Zh. Prikl. Spektrosk.,64, 209 (1997).
B. I. Stepanov, Zh. Prikl. Spektrosk.,17, 92 (1972).
V. S. Pavlovich, Zh. Prikl. Spektrosk.,25, 480 (1976).
W. R. Ware, S. K. Lee, G. J. Brant, and P. Chow, J. Chem. Phys.,54, 4729 (1971).
Yu. T. Mazurenko and V. S. Udal’tsov, Opt. Spektrosk.,44, 714 (1978);45, 909 (1978).
V. T. Koyava, V. S. Pavlovich, V. I. Popechits, and A. M. Sarzhevskii, Zh. Prikl. Spektrosk.,34, 1017 (1981).
V. S. Pavlovich, P. P. Pershukevich, L. G. Pikulik, and S. V. Zablotskii, Doklady Akad. Nauk BSSR,28, 800 (1984).
B. A. Bushuk, A. N. Rubinov, and A. P. Stupak, Experiment. Technik Physik,39, 347 (1991).
W. Jarzeba, G. C. Walker, A. E. Johnson, and P. F. Barbara, Chem. Phys.,152, 57 (1991).
J. D. Simon and S. G. Su, Chem. Phys.,152, 143 (1991).
B. Bingemann and N. P. Ernsting, J. Chem. Phys.,102, 2691 (1995).
V. S. Pavlovich, P. P. Pershukevich, and L. G. Pikulik, Zh. Prikl. Spektrosk.,39, 779 (1983).
S. M. Bystryak, A. I. Kotel’nikov, G. I. Likhtenshtein, and V. I. Nikulin, Zh. Prikl. Spektrosk.,52, 225 (1990).
A. Wagener and R. Richert, Chem. Phys. Lett.,176, 329 (1991).
R. Kubo, Statistical Mechanics [Russian translation], Moscow (1967).
Ch. Kittel, Statistical Thermodynamics [Russian translation], Moscow (1977).
T. Fonseca and B. M. Ladanyi, J. Phys. Chem.,95, 2116 (1991).
K. K. Rebane, Elementary theory of the Vibrational Structure of Spectra of Impurity Crystals [in Russian], Moscow (1968).
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Institute of Molecular and Atomic Physics, Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 64, No. 6, pp. 753–765, November–December, 1997.
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Pavlovich, V.S. Franck-Condon transitions and thermodynamics of photoinduced processes of orientational relaxation in polar solutions. J Appl Spectrosc 64, 764–777 (1997). https://doi.org/10.1007/BF02678859
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DOI: https://doi.org/10.1007/BF02678859