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Sample records for 1,2,4,5-tetramethylbenzene

  1. Role of energy exchange in vibrational dephasing processes in liquids and solids

    International Nuclear Information System (INIS)

    Three theories which claim relevance to the dephasing of molecular vibrations in condensed phase matter are presented. All of these theories predict (in certain limiting cases) that the widths and shifts of molecular vibrations will obey an Arrhenius temperature dependence. The basic tenets of the theories are detailed so that the differences between them may be used in an experiment to distinguish between them. One model, based on intermolecular energy exchange of low-frequency modes, results in dephasing the high-frequency modes when anharmonic coupling is present. A computer analysis of temperature dependent experimental lineshapes can result in the extraction of various parameters such as the anharmonic shifts and the exchange rates. It is shown that, in order to properly assess the relative validity of the three models, other evidence must be obtained such as the spectral parameters of the low-frequency modes, the combination bands, and the isotopic dilution behavior. This evidence is presented for d14-durene (perdeutero-1,2,4,5-tetramethylbenzene) and compared to previous data obtained on pure h14-durene. An extension of the (HSC) intermolecular energy exchange model which allows for the possibility of partial delocalization of the low-frequency modes gives an adequate description of the experimental evidence. Isotopic dilution experiments, in particular, have resulted in a detailed picture of the energy transfer dynamics of the low-frequency modes. A section in which some spontaneous Raman spectra support a model of inhomogeneous broadening in liquids based on results of picosecond stimulated Raman spectroscopy is presented. The model is that a distribution of environmental sites is created by a distribution in the local density and thus creates inhomogeneous broadening

  2. Effect of nuclear spin on chemical reactions and internal molecular rotation

    International Nuclear Information System (INIS)

    Part I of this dissertation is a study of the magnetic isotope effect, and results are presented for the separation of 13C and 12C isotopes. Two models are included in the theoretical treatment of the effect. In the first model the spin states evolve quantum mechanically, and geminate recombination is calculated by numerically integrating the collision probability times the probability the radical pair is in a singlet state. In the second model the intersystem crossing is treated via first-order rate constants which are average values of the hyperfine couplings. Using these rate constants and hydrodynamic diffusion equations, an analytical solution, which accounts for all collisions, is obtained for the geminate recombination. The two reactions studied are photolysis of benzophenone and toluene and the photolytic decomposition of dibenzylketone (1,3-diphenyl-2-propanone). No magnetic isotope effect was observed in the benzophenone reaction. 13C enrichment was observed for the dibenzylketone reaction, and this enrichment was substantially enhanced at intermediate viscosities and low temperatures. Part II of this dissertation is a presentation of theory and results for the use of Zeeman spin-lattice relaxation as a probe of methyl group rotation in the solid state. Experimental results are presented for the time and angular dependences of rotational polarization, the methyl group magnetic moment, and methyl-methyl steric interactions. The compounds studied are 2,6-dimethylphenol, methyl iodide, 1,4,5,8-tetramethylanthracene, 1,4,5,8-tetramethylnaphthalene, 1,2,4,5-tetramethylbenzene, and 2,3-dimethylmaleicanhydride