Raman and NMR study of parallel reorientational diffusion in nitromethane |
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| Institution: | 1. The Bredesen Center for Interdisciplinary Research and Graduate Education, University of Tennessee, Knoxville, TN, 37996, USA;2. Materials Science & Technology Division, Oak Ridge National Laboratory, Oak Ridge, TN, 37831, USA;3. Department of Materials Science & Engineering, The University of Tennessee, Knoxville, TN, 37996, USA;4. Department of Nuclear Engineering, University of Tennessee, Knoxville, TN, 37996, USA;1. Department of Chemical Engineering & Biotechnology, Ariel University, 40700 Ariel, Israel;2. Departamento de Ingeniería Química, Universidad de Concepción, Concepción, Chile;1. Institute of Subsurface Energy Systems, Clausthal University of Technology, Clausthal-Zellerfeld, Germany;2. Process Systems Engineering, Graz University of Technology, Graz, Austria |
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| Abstract: | Raman spectral bandshapes of the ν7, antisymmetric CD3 stretching mode, and deuterium spin-lattice relaxation times in nitromethane-d3 were measured as a function of temperature in the liquid-phase. Perpendicular diffusion coefficients (D⊥) calculated from dielectric and 14N relaxation times in the literature were in excellent agreement at all temperatures. Unlike earlier studies in acetonitrile and iodomethane, parallel diffusion constants (Dz.snfc;) determined from the Raman lineshape were substantially greater than those calculated from T1(2D), possibly resulting from broadening of the vibrational band due to hydrogen bond interactions. Also in contrast to the earlier investigations, values of Dz.snfc; obtained from both methods were substantially lower than coefficients calculated from the Free Rotor model of reorientation, providing clear evidence that intermolecular self-association slows the spinning motion of nitromethane in the liquid-phase. |
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