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Dynamic Solvent Effects on Equilibrium Isomerization: Kramers Theory Revisited with 2DIR Chemical Exchange

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Abstract

Using ultrafast two dimensional infrared chemical exchange spectroscopy we monitored the equilibrium exchange between two dicobalt octacarbonyl isomers in linear alkane solvents. Results were inconsistent with a Markovian hydrodynamic viscosity implicating Kramers-Hubbard and/or frequency-dependent friction.

© 2010 Optical Society of America

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