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  • American Institute of Physics (AIP)  (4)
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  • 1
    Electronic Resource
    Electronic Resource
    Spectroscopy of matrix-isolated methylnitrene (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 86 (1987), S. 25-32 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The methylnitrene radical CH3N has been produced by the interaction of metastable molecular nitrogen and methylazide, and has been trapped in solid nitrogen at 10 K. The IR and UV absorption spectra are consistent with gas phase emission results, and also show transitions to several additional vibrational levels in the A 3E excited electronic state. The UV band system consists chiefly of a progression in the C–N stretching mode, possibly complicated by additional unresolved vibrational structure. These observations indicate that the absence of extensive hot band structure in the gas phase work is not due to rapid dissociation or isomerization from the upper state, which is bound by at least 3500 cm−1. The ESR signals previously attributed to CH3N cannot be produced under the same experimental conditions, but require additional photolysis. This observation suggests that a reexamination of previous ESR data is warranted.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.452775
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  • 2
    Electronic Resource
    Electronic Resource
    Vibrational frequencies in the A˜ 3E state of methylnitrene (1991)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 94 (1991), S. 4678-4679 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: New observations have enabled the identification of another excited state vibration in the A˜ 3E –X˜ 3A2 ultraviolet absorption spectrum of matrix-isolated methylnitrene. Two progressions in the C–N stretching frequency ν3 were detected in both CH3N and CD3N, with average intervals of 710 and 695 cm−1, respectively. For each isotopomer, corresponding lines in the pair of progressions are offset by frequencies appropriate for a methyl vibration. This provides the first clear evidence for excitation of the CH3 symmetric deformation (umbrella mode) ν2 in the upper state of the transition, with vibrational frequencies of 1166 cm−1 for CH3N and 1044 cm−1 for CD3N. These observations confirm earlier speculation on the absorption spectrum of matrix-isolated CH3N, and correlate with unidentified lines in the gas phase emission spectrum. The use of a new precursor, methyl isocyanate, in the generation of this radical is also of interest.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.460600
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  • 3
    Electronic Resource
    Electronic Resource
    ESR and optical spectroscopy of matrix-isolated ethylnitrene (1987)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 87 (1987), S. 2421-2425 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The ethylnitrene radical CH3CH2N has been produced by the interaction of gaseous ethylazide with metastable N2 or Ar generated in a microwave discharge, and has been trapped in N2 and Ar matrices at 10 K. The UV absorption spectrum in solid nitrogen consists of a series of 11 bands beginning at 335 nm with an average vibrational interval of 320 cm−1. Intensity alternations suggest that two different vibrations are excited in the transition, probably a C–C–N bend corresponding to the observed spacing and a C–N stretch with vibrational frequency near 640 cm−1. The electron spin resonance (ESR) spectrum at 8300 G indicates that ethylnitrene has a triplet ground state with zero-field splitting parameters D=1.67 cm−1, and E=0.0035 cm−1 in a nitrogen matrix. The hyperfine splittings differ slightly in the x and y lines and have the average values of 16.0 G for N and 30.6 G for the methylene H. The spectral features associated with ethylnitrene were not observed through direct photolysis of the parent ethylazide either during or after deposition. The data lend support to the conclusion that earlier assignments of the ESR spectrum of methylnitrene, CH3N, are incorrect, and may provide a lower limit to ||D|| for that molecule in the matrix.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.453132
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  • 4
    Electronic Resource
    Electronic Resource
    Improved predictions of equilibrium properties for spin-polarized atomic nitrogen (1986)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 85 (1986), S. 1201-1202 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: A reanalysis of several equilibrium properties of electron spin-polarized atomic nitrogen is presented, utilizing parameters from a new and improved theoretical calculation of the 7Σ+u state of molecular nitrogen which represents the interaction potential between two such spin-polarized atoms. The new potential well is significantly more shallow than previously assumed, resulting in substantial changes in the critical and triple point pressures and temperatures as calculated in the quantum theorem of corresponding states framework. The corresponding molar volumes are only slightly affected because the hard sphere radius is unchanged. Bulk samples are not expected to exhibit significant quantum behavior. Earlier conclusions on the relative stability of this material to single spin-flip processes remain unaltered.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.451318
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