Line mixing effects in isotropic Raman spectra of pure N2: a classical trajectory study.
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.
Institute on Laser and Information Technologies, Russian Academy of Sciences (ILIT RAS), 2, Pionerskaya Str., 142190 Moscow, Troitsk, Russia.
Sergey V
SV
Ivanov
Institut des Sciences Moléculaires d'Orsay (ISMO), CNRS (UMR8214) and Université Paris-Sud, Bât. 350, Campus d'Orsay F-91405, France.
Christian
C
Boulet
Central Aerohydrodynamic Institute (TsAGI), Zhukovski, Moscow Region 140160, Russia.
Oleg G
OG
Buzykin
Institut de Physique de Rennes, UMR CNRS 6251, Université de Rennes 1, Campus de Beaulieu, Bât. 11B, F-35042 Rennes, France.
Franck
F
Thibault