Self- and N2-broadening of CH3Br ro-vibrational lines in the ν2 band: The J and K dependence

Abstract

Methyl bromide (CH3Br) is the major source of inorganic bromine in the atmosphere and contributes significantly to ozone depletion. Indeed, CH3Br is dissociated by UV radiation, producing Br radicals that catalyze the destruction of ozone. In this paper, we report measured Lorentz self- and N2-broadening coefficients of CH3Br in the ν2 fundamental band using a mono-spectrum non-linear least squares fitting of Voigt profiles which appeared to properly model the observed molecular line shapes within the noise level. These measurements were made by analyzing 12 laboratory absorption spectra recorded at high resolution (0.005, 0.003 or 0.002cm−1) using the Fourier transform spectrometer Bruker IF125HR located at the LISA facility in Créteil. The spectra were obtained at room temperature using a White-type multipass cell with an optical path of 0.849m and various pressures. We have been able to determine the self- and N2-broadening coefficients of 948 ν2 transitions with quantum numbers as high as J=49 and K=10. The measured self-broadening coefficients range from 0.1542 to 0.4930cm−1atm−1 and the N2-broadening coefficients range from 0.0737 to 0.1284cm−1atm−1 at 295K. The accuracy of the broadening coefficients measured in this work is between 4% and 8%, depending on the studied transition. Comparisons with measurements taken in the ν5 and ν6 bands of CH3Br did not show any clear vibrational dependence. The J and K dependences of the self- and N2-broadening coefficients have been observed and the rotational K dependence has been modeled using empirical polynomial expression. On average, the empirical expression reproduce the measured broadening coefficients to within 6%. The data obtained represent a significant contribution to the determination of broadening coefficients of CH3Br useful for atmospheric remote sensing and applications.