- Pressure and viscosity effects on thermal geometrical isomerization of oxacarbocyanine cations
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Pressure and viscosity effects on the rate of thermal Z/E isomerization of two carbocyanine dyes, 3,3′-diethyloxacarbocyanine iodide (DOCI) and 3,3′-diethyloxadicarbocyanine iodide, (DODCI) were measured in 2-methylpentane-2,4-diol. From the results, the following conclusions are obtained. 1. The medium and the chemical coordinates have to be treated separately, as in the reactions of uncharged species. 2. A positive charge on the reactant seems to induce an earlier deviation from the transition state theory. 3. The most important factors controlling a deviation from the transition state theory are the anisotropy of the characteristic times of reaction and solvent fluctuations, and the strength of the solute-solvent interactions.
- Kim, Jong Chul,Ohga, Yasushi,Asano, Tsutomu,Weinberg, Noham N.,George, Adrian V.
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- The first unequivocal observation of dynamic solvent effects in the thermal geometrical isomerization of 3,3′-diethyloxadicarbocyanine iodide (DODCI)
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Pressure dependence of the rate of thermal geometrical isomerization of 3,3′-diethyloxadicarbocyanine iodide (DODCI) was studied in ethanol and in a highly viscous hydroxylic solvent, 2-methyl-2,4-pentanediol. The kinetic effects of pressure in the two solvents are qualitatively different and the results strongly suggest that the stochastic analysis of the kinetic results in 1-alkanols reported earlier needs to be renounced.
- Kim, Jong Chul,Ohga, Yasushi,Asano, Tsutomu
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p. 301 - 302
(2007/10/03)
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