Structure and microwave spectrum of the 2-cyano-2-propyl radical
| dc.contributor.author | Claytor, Robinson C. P. | en |
| dc.contributor.committeechair | Graybeal, Jack D. | en |
| dc.contributor.committeemember | Field, Paul E. | en |
| dc.contributor.committeemember | Schug, John C. | en |
| dc.contributor.committeemember | Tanko, James M. | en |
| dc.contributor.committeemember | Viers, Jimmy W. | en |
| dc.contributor.department | Chemistry | en |
| dc.date.accessioned | 2015-06-29T22:07:12Z | en |
| dc.date.available | 2015-06-29T22:07:12Z | en |
| dc.date.issued | 1988 | en |
| dc.description.abstract | 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. | en |
| dc.description.degree | Ph. D. | en |
| dc.format.extent | ix, 159 leaves | en |
| dc.format.mimetype | application/pdf | en |
| dc.identifier.uri | http://hdl.handle.net/10919/53935 | en |
| dc.language.iso | en_US | en |
| dc.publisher | Virginia Polytechnic Institute and State University | en |
| dc.relation.isformatof | OCLC# 18484368 | en |
| dc.rights | In Copyright | en |
| dc.rights.uri | http://rightsstatements.org/vocab/InC/1.0/ | en |
| dc.subject.lcc | LD5655.V856 1988.C578 | en |
| dc.subject.lcsh | Radicals (Chemistry) | en |
| dc.subject.lcsh | Microwave spectroscopy | en |
| dc.title | Structure and microwave spectrum of the 2-cyano-2-propyl radical | en |
| dc.type | Dissertation | en |
| dc.type.dcmitype | Text | en |
| thesis.degree.discipline | Chemistry | en |
| thesis.degree.grantor | Virginia Polytechnic Institute and State University | en |
| thesis.degree.level | doctoral | en |
| thesis.degree.name | Ph. D. | en |
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