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Effects of Solute-Solvent Interactions on Radiationless Decay of Thioketones Excited to Their S_{2}- and T_{1}-States

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Szymański M., Balicki M., Binkowski M., Kubicki J., Maciejewski A., Pawłowska E., Wróżowa T.
Acta Physica Polonica A
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1996
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vol. 89
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issue 4
527-546
EN
Spectral and photophysical properties of a few aromatic thioketones in their S_{2}- and T_{1}-states, in particular those determined by their interactions with solvents, are discussed. The reasons for a drastically different behaviour of thioketones in interactions with benzene as well as saturated hydrocarbons and perfluoroalkanes are analysed in more detail. Results of the time-resolved transient absorption measurements in the pico- and nanosecond time scale are given. An analysis of these results proves that a product of the decay of the S_{2}-state of xanthione in benzene is a new transient (τ_{1/e} ≥ 60 ps) individuum which, regarding the system properties and the conditions of the experiment, has been identified as an exciplex in S_{2}-state formed as a result of an efficient interaction with benzene molecule. Also in xanthione//alkane systems the involvement of a transient individuum was proved. Most probably, this individuum was a thioketyl radical which could be formed by hydrogen abstraction from a hydrocarbon molecule by xanthione in the S_{2}-state. Such individua act as intermediates in passing excitation to the triplet states of thioketones and are effective channels of the S_{2}-state decay. The changes observed in the transient absorption spectra of xanthione in C_{6}H_{6} in the time range of 10^{-7}-10^{-6} s can be attributed to the formation of an excimer in the T_{1}-state as a result of the T_{1}-state selfquenching.
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