New investigation of the ν 3 C-H stretching region of 12CH4 through the analysis of high temperature infrared emission spectra

B. Amyay (1) , A. Gardez (2) , Robert Georges (2) , Ludovic Biennier (2) , J. Vander Auwera (3) , C. Richard (1) , Vincent Boudon (1)

1 ICB - Laboratoire Interdisciplinaire Carnot de Bourgogne
2 IPR - Institut de Physique de Rennes
3 Service de Chimie Quantique et Photophysique

The ν3 C-H stretching region of methane was reinvestigated in this work using high temperature (620-1715 K) emission spectra recorded in Rennes at Doppler limited resolution. This work follows our recent global analysis of the Dyad system Δn = ±1 (1000-1500 cm-1), with n being the polyad number [B. Amyay et al., J. Chem. Phys. 144, 24312 (2016)]. Thanks to the high temperature, new assignments of vibration-rotation methane line positions have been achieved successfully in the Pentad system and some associated hot bands (Δn = ±2) observed in the spectral region 2600-3300 cm-1. In particular, rotational assignments in the cold band [Pentad-ground state (GS)] and in the first related hot band (Octad-Dyad) were extended up to J = 30 and 27, respectively. In addition, 1525 new transitions belonging to the Tetradecad-Pentad hot band system were assigned for the first time, up to J = 20. The effective global model used to deal with the new assignments was developed to the 6th order for the first three polyads (Monad, Dyad, and Pentad), and to the 5th order for both the Octad and the Tetradecad. 1306 effective parameters were fitted with a dimensionless standard deviation σ = 2.64. The root mean square deviations dRMS obtained are 4.18 × 10-3 cm-1 for the Pentad-GS cold band, 2.48 × 10-3 cm-1 for the Octad-Dyad, and 1.43 × 10-3 cm-1 for the Tetradecad-Pentad hot bands.

Keywords: Infrared emission spectrum; Limited resolution; Emission spectroscopy; Root mean square deviations; Molecular physics; Methane; Ground state; Standard deviation; Stretching region; Vibration rotations; Phase equilibria; Effective parameters; Emission spectrums; CRESU

Domains: Physics [physics]; Chemical Sciences

B. Amyay, A. Gardez, Robert Georges, Ludovic Biennier, J. Vander Auwera, et al.. New investigation of the ν 3 C-H stretching region of 12CH4 through the analysis of high temperature infrared emission spectra. Journal of Chemical Physics, 2018, 148 (13), pp.134306. ⟨10.1063/1.5023331⟩. ⟨hal-01774214⟩