In this thesis work, the results of microwave investigation and structural determination for benzonitrile and some of its fluorinated derivatives are presented. The pure rotational spectra of the studied compounds including benzonitrile, 2-fluorobenzonitrile, 3-fluorobenzonitrile, 2,3-difluorobenzonitrile, 2,4-difluorobenzonitrile and pentafluorobenzonitrile were investigated. Measuring the rotational spectra of the parent molecules and the minor 13C and 15N isotopic species allowed the derivation of the substitution and effective structures for these molecules. Using the effective and the calculated ab initio structures, the geometries of the fluorinated derivatives were compared to that of the reference compound (benzonitrile) and the effect of single, double and full fluorination on the geometry of benzonitrile was examined. The observed distortions in the BN geometry caused by single, double and full fluorination were interpreted by hybridization theory and intramolecular non-bonded interactions. / February 2015

A source-modulation microwave spectrograph was utilized to measure line width parameters for several spectral lines in the pure rotational spectrum of formaldehyde (H₂CO). The spectrograph featured high-gain ac amplification and phase-sensitive detection, and was capable of measuring microwave lines having absorption coefficients as small as 10⁻⁷ cm⁻¹ with a frequency resolution on the order of 30 kHz. Center frequencies of the measured lines varied from 4,830 MHz to 72,838 MHz; hence, most of the observations were made on transitions between K-doublets in the rotational spectrum. Corrections were applied to the measured line width parameters to account for Doppler broadening and, where possible, for deviations due to magnetic hyperfine structure in some of the K-doubled lines. Low modulation voltages and low microwave power levels were used to minimize modulation and saturation broadenings; other extraneous broadenings were found to be insignificant. The primary broadening mechanism at low gas pressure is pressure broadening, and a review of this topic is included. Line width parameters for the several observed transitions were determined by graphing half-widths versus pressure for each spectral line, and performing a linear least-squares fit to the data points. Repeatability measurements indicated the accuracy of the line width parameters to be better than ±10 percent. The reasons for this repeatability spread are discussed, Broadening of each line was measured for self- and foreign-gas broadening by atomic helium and diatomic hydrogen. Effective collision diameters were calculated for each broadening interaction, based on the observed rates of broadening.

Measurement of the line width parameters of a molecule is of interest because collision diameters can be calculated from them. This gives an effective size of the molecule when it is involved in interactions with other molecules. Further, specific types of interactions can be inferred from detailed information about the dependence of the line width upon pressure. In this paper, an experiment for measuring line width parameters for methyl cyanide is described and the results of the experiment are analyzed. This investigation was successful in obtaining precise values for the line width parameter for the J-J' = 0-1, J-J'= 1-2, and J-J' = 2-3 transitions of methyl cyanide which agree with experimental values of other researchers where available. It was found that standing waves were the dominant effect in the measurement of center frequency shift.

Contributions to the second order collision efficiency function S ⁽²⁾ (b), used in semiclassical perturbation approaches to pressure broadening of microwave and infrared spectra, due to several leading terms, dipole and quadrupole components, in the expansion of the intermolecular interaction energy are derived by method of irreducible spherical tensor operators for molecules of arbitrary symmetry. Results are given explicitly in terms of dipole and quadrupole line strengths. General expressions for dipole moment line strength in the asymmetric rotor basis as well as quadrupole moment line strength for the special case of molecules with two independent quadrupole moment components are derived. Computer programs for calculating linewidth parameters in the rotational spectrum of ¹⁴NO₂ based on Anderson and Murphy and Boggs theories are presented.