Claytor, Robinson C. P.2015-06-292015-06-291988http://hdl.handle.net/10919/53935The 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.ix, 159 leavesapplication/pdfen-USIn CopyrightLD5655.V856 1988.C578Radicals (Chemistry)Microwave spectroscopyDissertation