Issue 16, 1994

Vibrational relaxation of the ν(C[double bond, length as m-dash]O) mode of ethyl trichloroacetate in solution

Abstract

An analysis of the IR and Raman band shapes corresponding to the carbonyl stretching mode, ν(C[double bond, length as m-dash]O), of ethyl trichloroacetate in hexane, carbon tetrachloride, carbon disulfide and chloroform solutions provides the vibrational and reorientational correlation functions. The vibrational processes in the relaxation of this mode seem to be dominant on long timescales (from ca. 0.4 ps), the vibrational width increases when the solvent changes in the order C6H14 < CS2 < CCI4 < CHCI3. An intermediate modulation regime is observed. The isolated binary collision (IBC) model does not account for the values of the vibrational width, but it predicts the observed trend in non-polar solvents. The reorientational motion is less hindered in CS2 and C6H14, but its contribution to the relaxation in CHCI3 solution is negligible at long times. A comparative study on the esters CX3CO2Et (X = H, F and Cl) reveals that the relaxation is increasingly efficient when the CX3 group varies in the order CCl3 < CF3 < CH3.

Article information

Article type
Paper

J. Chem. Soc., Faraday Trans., 1994,90, 2325-2330

Vibrational relaxation of the ν(C[double bond, length as m-dash]O) mode of ethyl trichloroacetate in solution

R. Navarro, A. Hernanz and I. Bratu, J. Chem. Soc., Faraday Trans., 1994, 90, 2325 DOI: 10.1039/FT9949002325

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