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• W4237386576 startingPage "1407" @default.
• W4237386576 abstract "Raman isotropic, v(C=O) band profiles studied across the whole concentration range for mixtures of DMF-h7 and DMF-d7 show that band broadening occurs with isotopic dilution. This increase in vibrational relaxation rate and the accompanying reduction in non-coincidence splitting, (Δ), must be related to details of intermolecular coupling in the dense fluid. Two models for resonant coupling have been examined. The data are quite well represented by the Logan model which predicts the observed linear dependence of Δ on concentration for an isotopic mixture. In addition, our band shape and width behaviour fit quite well the model of Knapp. We see a distinct band asymmetry to the high frequency side as predicted by this model for strong dipolar coupling. Furthermore, the broadening observed on isotopic dilution may also be accommodated within the model in terms of an excition ‘hopping’ mechanism where the original band profile was motionally narrowed by a rapid intersite exchange process (but keeping the total amount of intermolecular coupling at a particular site fixed). The extent of band asymmetry and the band narrowing process due to resonant coupling strongly imply that the dephasing of this band in the pure liquid is dominated by inhomogeneous processes, due to slowly varying, long ranged interactions." @default.
• W4237386576 created "2022-05-12" @default.
• W4237386576 creator A5053884514 @default.
• W4237386576 creator A5075902141 @default.
• W4237386576 date "1991-04-20" @default.
• W4237386576 modified "2023-09-28" @default.
• W4237386576 title "Raman spectroscopic studies on the interaction and dynamics of N,N-dimethylformamide in the liquid phase. The effect of isotopic dilution" @default.
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• W4237386576 doi "https://doi.org/10.1080/00268979100100991" @default.
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