A double modulation microwave spectrometer is used to evaluate the linewidth parameters for some excited rotational components in the bending vibration v_8 of 13CH3 13C 15N and 13CH3C15N isotopomers of methyl cyanide. The linewidth parameters for self-broadening of the ΔJ=2←1 rotational components for the ground v_8 , 1v_8, and the 2v_8 vibrations were determined over a pressure range of 1 to 13 mtorr and at a temperature of 300 K. The double modulation technique is used to explore the high eighth derivative of the line shape profile of the spectral line. This technique proved to give good signal-to-noise ratios and enabled the recovery of weak signals. An experimental method is developed to correct for source modulation broadening. The tests of the ratios of the two inner peak's separation of the eighth derivative of the line showed that they were up to 95% similar to those for a Lorentzian line shape function. The line shapes were assumed to be Lorentzian for the theoretical analysis of the derivative profiles and comparisons were made between experiment and theory on this basis. Dipole moments for vibrationally excited states were calculated from linewidth parameters and show systematic decrease with the increase of excitation. Impact parameters were calculated using the "hard sphere" model of the kinetic theory of gases. The results were many times larger than the size of the molecule itself. This suggests that the dominant interaction is a long range dipole-dipole force interaction.

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.

The shape of collision-broadened microwave absorption lines is reviewed, along with a number of other broadening mechanisms. The Anderson and Murphy-Boggs linewidth theories are reviewed in detail. Several published modifications to these theories are reviewed. Computer programs which numerically evaluate linewidths and lineshifts are presented. Approximations are made to reduce the need for extensive use of the modified Bessel functions, thereby reducing computation time. Only dipole-dipole forces are considered.