Analysis of self-broadened pure rotational and rovibrational lines of methyl chloride at room temperature

Rovibrational absorption spectra of methyl chloride in the spectral region between 2800 and 3200 cm−1 were recorded with a high-resolution Fourier transform spectrometer. A multispectrum fitting procedure was used to analyze 527 transitions of the ν1 band and to retrieve the self-broadening coefficients for various J- and K-values with an estimated accuracy around 8%. Pure rotational transitions of CH3Cl in the submillimeter/terahertz region (0.2-1.4 THz) were also investigated using two complementary techniques of frequency-multiplication and continuous-wave photomixing. Forty-three pure rotational self-broadening coefficients were extracted with the accuracy between 3 and 5%. The whole set of measured values was used to model the J- and K-rotational dependences of the self-broadening coefficients by second-order polynomials. In addition, semi-classical calculations were performed, based on the real symmetric-top geometry of the active molecule, an intermolecular potential model including not only the dominant electrostatic but also the short-range forces, as well as on an exact classical treatment of the relative translational motion of the colliding partners. Comparison of all experimental and theoretical results shows similar rotational dependences and no significant vibrational dependence, so that extrapolations to other spectral regions should be straightforward.

► Self-broadening coefficients of methyl chloride transitions. ► J- and K-rotational dependences. ► J up to 50 and K up to 12. ► IR and THz measurements. ► Empirical and semi-classical calculations.