Engineering topics
Publications and source records attributed to Durig, J. R..
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The Raman spectra of gaseous, liquid and solid, and infrared spectra of gaseous and solid isopropylamine-d sub 0 and -d sub 2 was investigated between 4000 and 50 cm superscript -1. Differences between the spectrum of the solid phase and that of the fluid phases were interpreted in terms of an equilibrium between low energy s-trans and high energy gauche conformers, and a complete vibrational assignment was proposed for the s-trans conformer. The far infrared spectra of the gaseous compounds contained bands due to the asymmetric amino and coupled methyl torsions; the assignment of these bands was aided by observation of a number of two quantum transitions for each vibrational mode. The asymmetric potential functions were calculated, which resulted in values for the enthalpy differences between conformers in the gaseous phase of 446 and 523 callmole for the sub 0 -d and -d sub 2 compounds, respectively. The methyl torsional potential function of isopropylamine-d sub 0 was calculated which led to a value for the barrier height to internal rotation of the methyl rotors of 4.23 + or - 0.06 kcal/mole. Values for the ideal gas thermodynamic functions were calculated over a range of temperatures.
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The Raman spectra of 1,2-dimethyldiphosphine have been recorded in the liquid and solid phases to 4000 per cm. The infrared spectrum of the solid phase was also recorded from 4000 to 200 per cm. The spectra were consistent with the presence of both the trans and gauche meso conformers and presumably the gauche conformer of the d,l isomer in the liquid phase. The gauche meso conformer was absent from the solid phase. A tentative vibrational assignment is proposed for the molecule.
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Raman spectra of gaseous isobutene (CH3)2C=CH2 and isobutene-d6 have been recorded between 100 and 500/cm with a resolution of 1/cm, and the far-IR spectra of the same compounds have been recorded over the same frequency range with a resolution of 0.5/cm. Several torsional transitions have been observed for both molecules and these data have been used to determine the torsional potential function based on a semirigid model. Values of average effective barrier were determined for the molecules.
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The Raman spectra of gaseous propane-d0 and -d3 have been recorded between 50 and 3500 cm. Considerable torsional data are reported and used to characterize the torsional potential function based on a semirigid model. The average 'effective' V3 for the propanes is found to be 1139 plus or minus 10/cm. The sine-sine coupling term is similar in magnitude but opposite in sign to the cosine-cosine coupling term in propane-d0.
The Raman spectra of gaseous dimethylamine-d0, -d3, and -d6 have been recorded between 0 and 4000/cm. The far-infrared spectra have been recorded between 300 and 100/cm. Considerable torsional data are reported and used to characterize the torsional potential function based on a semi-rigid model. The average effective V3 for the dimethylamines was found to be 1052 plus or minus 12/cm. The cos-cos coupling term was approximately 15% of the effective V3, whereas the sine-sine coupling term was of an order of magnitude smaller for (CH3)2NH and (CD3)2NH. However, for the mixed isotope the sine-sine term was found to be negligible and the cos-cos about one-half the value obtained for the other two isotopes.
The torsional far infrared and Raman spectra of gaseous CH3OCH3, CD3OCH3, and CD3OCD3 are presented. They are analyzed using a computer program which is based on the results of an extensive investigation of the isometric groups and of the symmetry groups of the rotation-internal rotation Hamiltonians of a series of semirigid two-top models. Four or more Fourier coefficients of the potential functions in two variables could be determined for each isotope. Strong evidence was found for Fermi-resonance-type interactions with the COC bending mode.