Line mixing effects in isotropic Raman spectra of pure N2: A classical trajectory study

Sergey V. Ivanov (1) , Christian Boulet (2) , Oleg G. Buzykin (3) , Franck Thibault (4)

1 ILIT - Institute on Laser and Information Technologies
2 PPM - Laboratoire de Photophysique Moléculaire
3 TSAGI - Central Aerohydrodynamic Institute
4 IPR - Institut de Physique de Rennes

Line mixing effects in the Q branch of pure N2 isotropic Raman scattering are studied at room temperature using a classical trajectory method. It is the first study using an extended modified version of Gordon's classical theory of impact broadening and shift of rovibrational lines. The whole relaxation matrix is calculated using an exact 3D classical trajectory method for binary collisions of rigid N2 molecules employing the most up-to-date intermolecular potential energy surface (PES). A simple symmetrizing procedure is employed to improve off-diagonal cross-sections to make them obeying exactly the principle of detailed balance. The adequacy of the results is confirmed by the sum rule. The comparison is made with available experimental data as well as with benchmark fully quantum close coupling [F. Thibault, C. Boulet, and Q. Ma, J. Chem. Phys. 140, 044303 (2014)] and refined semi-classical Robert-Bonamy [C. Boulet, Q. Ma, and F. Thibault, J. Chem. Phys. 140, 084310 (2014)] results. All calculations (classical, quantum and semi-classical) were made using the same PES. The agreement between classical and quantum relaxation matrices is excellent, opening the way to the analysis of more complex molecular systems.

Mots clés: line mixing; nitrogen; raman spectra; clasical methods

Domaines: Physique [physics]; Agrégats Moléculaires et Atomiques [physics.atm-clus]

Sergey V. Ivanov, Christian Boulet, Oleg G. Buzykin, Franck Thibault. Line mixing effects in isotropic Raman spectra of pure N2: A classical trajectory study. Journal of Chemical Physics, 2014, 141 (18), pp.184306. ⟨10.1063/1.4901084⟩. ⟨hal-01082110⟩