The rotational spectra of the 2-cyano-2-propyl and d⁶-2·cyano-2-propyl radicals were observed using a Stark modulated spectrometer. The radicals were generated in the gas phase by UV irradiation of sublimed azoisobisbutyronitrile. They were detectable in the cell for approximately one hour. Thirty-three transitions were assigned for (CH₃)₂CCN and twenty-one for (CD₃)₂CCN. The rigid rotor rotational constants determined by calculation of the hypothetical unsplit rotational transitions are A=8276.7, B=3919.7, C=2751.5Mhz for (CH₃)₂CCN and A=6241.3, B=3490.7, C=2372.6Mhz for (CD₃)₂CCN.
A program to calculate the fine splittings and hyperfine splittings due to the ¹⁴N nucleus and six protons was written. The spin rotation constants determined for the two species were E<sub>aa</sub>=-69.9, E<sub>bb</sub>=-36.1, E<sub>cc</sub>=2.7Mhz and E<sub>aa</sub>=-55.4, E<sub>bb</sub>=-32.6 Mhz for (CH₃)₂CCN and (CD₃)₂CCN respectively. The hyperfine coupling constants for ¹⁴N are identical for both isotopic species and were found to be T<sub>aa</sub>=-17.2, T<sub>bb</sub>=-17.1 and T<sub>cc</sub>=34.4 Mhz. The proton and deuteron hyperfine splittings were not resolved. The structural parameters determined from an <r₀> fit of the moments are r<sub>CN</sub>=1.18A, r<sub>CC</sub>=1.42A, r<sub>CMe</sub>=1.50A and CCMe=119.3°. The C₄N skeletal framework was found to be planar. / Ph. D.
| Identifer | oai:union.ndltd.org:VTETD/oai:vtechworks.lib.vt.edu:10919/53935 |
| Date | January 1988 |
| Creators | Claytor, Robinson C. P. |
| Contributors | Chemistry, Graybeal, Jack D., Field, Paul E., Schug, John C., Tanko, James M., Viers, Jimmy W. |
| Publisher | Virginia Polytechnic Institute and State University |
| Source Sets | Virginia Tech Theses and Dissertation |
| Language | en_US |
| Detected Language | English |
| Type | Dissertation, Text |
| Format | ix, 159 leaves, application/pdf, application/pdf |
| Rights | In Copyright, http://rightsstatements.org/vocab/InC/1.0/ |
| Relation | OCLC# 18484368 |
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