Torsional dynamics of molecules on barrierless potentials in liquids. I. Temperature and wavelength dependent picosecond studies of triphenyl-methane dyes

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Abstract
The nonradiative decay dynamics of crystal violet, and other triphenyl‐methane dyes, dissolved in a variety of solvents, are studied as a function of temperature. A linear viscosity dependence of the excited state absorption decay time in n‐alcohol solvents is found at several constant temperatures. The temperature dependence at constant viscosity is anomalously negative over the entire viscosity range (0.6 to 8.0 cP) of these experiments. Various possible mechanisms for the observed behavior are critically discussed. Two color excite‐and‐probe studies reveal ground state bleach recovery times which are independent of excitation wavelength but strongly dependent on probe wavelength. The faster decay on the red side of the ground state absorption is shown to be the result of stimulated emission rather than the influence of a second state.