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• W2169364529 abstract "Frequency-selected vibrational echo experiments were used to investigate the temperature dependences of vibrational dephasing associated with the 0-1 transition of the CO stretching mode of RuTPPCOPy (TPP=5,10,15,20-tetraphenylporphyrin, Py=pyridine) in two solvents: polymethylmethacrylate (PMMA) and 2-methyltetrahydrofuran (2-MTHF). In PMMA, a glass, the echo decay is exponential at all the temperatures studied, and the dephasing rate increases linearly with increasing temperature. In 2-MTHF, there is a change in the functional form of the temperature dependence when the solvent goes through the glass transition temperature (Tg). Below Tg, the dephasing rate increases linearly with temperature, while above Tg, it rises very steeply in a nonlinear manner. In the liquid at higher temperatures, the vibrational echo decays are nonexponential. A model frequency-frequency correlation function (FFCF) is proposed in which the FFCF differs for a glass and a liquid because of the intrinsic differences in the nature of the dynamics. At least two motions, inertial and diffusive, contribute to the vibrational dephasing in the liquids. The different temperature dependences of inertial and diffusive motions are discussed. Comparison of the model calculations of the vibrational echo temperature dependence and the data show reasonable, but not quantitative agreement." @default.
• W2169364529 created "2016-06-24" @default.
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• W2169364529 date "2002-07-24" @default.
• W2169364529 modified "2023-10-11" @default.
• W2169364529 title "Temperature-dependent vibrational dephasing: Comparison of liquid and glassy solvents using frequency-selected vibrational echoes" @default.
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• W2169364529 doi "https://doi.org/10.1063/1.1492280" @default.
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