Noncoincidence Effects of Dimethyl Carbonate in Binary Mixtures Probed by Raman Spectroscopy: Experimental and DFT Calculations

Abstract

The components of isotropic Raman and anisotropic Raman for dimethyl carbonate (DMC) dispersed in cyclohexane and acetone at different volume fractions were recorded separately. The noncoincidence effects (NCE) of the ν 7 (C=O) stretching mode were calculated accordingly. The NCE values (Δν NCE ) of the ν 7 (C=O) versus DMC volume fractions in the DMC/C 6 H 12 mixtures exhibits a convex (upward) curvature pattern, while the Δν NCE vs concentration in the DMC/CH 3 COCH 3 mixtures exhibits a concave (downward) curvature. These different NCE behaviors in the different binary mixtures may arise from the solvent-induced aggregation character. Thus, monomer and dimer structures of DMC were optimized and the vibration spectra were obtained using density functional theory (DFT) calculations. An aggregation model was suggested to expound the DMC’s characteristic NCE behavior and concentration effect. We found that the theoretical spectra from DFT/polarizable continuum model calculation based on the aggregation model is in accordance with our experimental data. Solvent-dependent experiments show the Δν NCE values increase with the decrease of the solvent dielectric constant under the identical volume fractions.

The noncoincidence phenomenon of acetonylacetone CO stretching in a binary mixture and the aggregation-induced split theory

“…The AIS model can explain most of the NCE phenomena. 25,26,[29][30][31] In this work, 2,5-hexanedione was chosen to investigate the C]O coupling behavior and the NCE phenomenon. 2,5-Hexanedione contains two carbonyl groups, and there are two possible C]O interactions,.intramolecular and intermolecular.…”