Structure and microwave spectrum of the 2-cyano-2-propyl radical

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_aa=-69.9, E_bb=-36.1, E_cc=2.7Mhz and E_aa=-55.4, E_bb=-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_aa=-17.2, T_bb=-17.1 and T_cc=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_CN=1.18A, r_CC=1.42A, r_CMe=1.50A and CCMe=119.3°. The C₄N skeletal framework was found to be planar.

Name thesis:degree_name

Ph. D.

Level thesis:degree_level

doctoral

Discipline thesis:degree_discipline

Chemistry

Department dc:contributor.department

Chemistry

Grantor dc:publisher

Virginia Polytechnic Institute and State University

Year dc:date.issued

1988

Author dc:creator

• Claytor, Robinson C. P.

Chair dc:contributor.committeechair

• Graybeal, Jack D.

Committee members dc:contributor.committeemember

• Field, Paul E.
• Schug, John C.
• Tanko, James M.
• Viers, Jimmy W.

Statement dc:rights

• In Copyright

Licence dc:rights.uri

• http://rightsstatements.org/vocab/InC/1.0/

Language dc:language.iso

en_US

Handle dc:identifier.uri

http://hdl.handle.net/10919/53935

OAI identifier oai:identifier

oai:vtechworks.lib.vt.edu:10919/53935