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Relaxation of Highly Vibrationally Excited Cycloheptatriene in Liquids Studied by Picosecond UV Absorption Spectroscopy

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Abstract

To understand in detail the relaxation of highly vibrationally excited polyatomics in dense fluid media experimental answers on fundamental mechanistic aspects are still urgently needed. It has been demonstrated on the relaxation of azulene that too simple applications of isolated binary collision models do not account for the observed relaxation dynamics in liquid solutions [1] and that e.g. cluster type effects may play a role in media like rare gas liquids [2]. However, much more systematic experimental evidence is necessary to establish how far a gas phase type description of energy transfer rates <ΔE>·Z (with effective collision numbers Z and average amounts of transferred energy <ΔE>) is valid and scales e.g. with D-1 (the inverse self diffusion coefficient of the fluid [3]) as opposed to the onset of basically different energy transfer mechanisms in higher density fluids.

© 1994 Optical Society of America

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