Molecular dynamic simulations of N<SUB>2</SUB>-broadened methane line shapes and comparison with experiments - INSU - Institut national des sciences de l'Univers Access content directly
Journal Articles Journal of Chemical Physics Year : 2017

Molecular dynamic simulations of N2-broadened methane line shapes and comparison with experiments


Absorption spectra of methane transitions broadened by nitrogen have been calculated for the first time using classical molecular dynamic simulations. For that, the time evolution of the auto-correlation function of the dipole moment vector, assumed along a C-H axis, was computed using an accurate site-site intermolecular potential for CH4-N2. Quaternion coordinates were used to treat the rotation of the molecules. A requantization procedure was applied to the classical rotation and spectra were then derived as the Fourier-Laplace transform of the auto-correlation function. These computed spectra were compared with experimental ones recorded with a tunable diode laser and a difference-frequency laser spectrometer. Specifically, nine isolated methane lines broadened by nitrogen, belonging to various vibrational bands and having rotational quantum numbers J from 0 to 9, were measured at room temperature and at several pressures from 20 to 945 mbar. Comparisons between measured and calculated spectra were made through their fits using the Voigt profile. The results show that ab initio calculated spectra reproduce with very high fidelity non-Voigt effects on the measurements and that classical molecular dynamic simulations can be used to predict spectral shapes of isolated lines of methane perturbed by nitrogen.

Dates and versions

insu-03727073 , version 1 (19-07-2022)



Tuong Le, José-Luis Doménech, Muriel Lepère, Ha Tran. Molecular dynamic simulations of N2-broadened methane line shapes and comparison with experiments. Journal of Chemical Physics, 2017, 146, ⟨10.1063/1.4976978⟩. ⟨insu-03727073⟩
5 View
0 Download



Gmail Facebook X LinkedIn More