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Pressure effects on N 2 –N 2 rototranslational Raman spectra predicted from leading spectral moments
Author(s) -
Sokolov Andrei,
Buldyreva Jeanna,
Kouzov Alexander
Publication year - 2020
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.5949
Subject(s) - raman spectroscopy , spectral line , computation , atomic physics , chemistry , matrix (chemical analysis) , physics , relaxation (psychology) , molecular physics , statistical physics , computational physics , quantum mechanics , mathematics , algorithm , chromatography , psychology , social psychology
Abstract Non‐Markovian effects having a strong influence on far‐wing intensities of spectroscopic signatures by molecular gases are analyzed theoretically with the use of a non‐Markovian relaxation matrix derived for rapidly colliding linear rotators (J. Chem. Phys. 149, 044305 [2018]) for the benchmark case of rototranslational Raman spectra of molecular nitrogen recorded at high densities up to very far wings (Phys. Lett. A 157, 44 [1991]). This matrix is built here on the base of the translational‐spectrum model of Birnbaum and Cohen and the recently computed, from known potential energy surfaces, two leading classical spectral moments (J. Ram. Spectrosc. 2020, DOI: 10.1002/jrs.5923). Theoretical intensity computations, going beyond the commonly used impact approximation, give much less overestimated values in the far wing and constitute a promising tool for getting accurate theoretical description of broad‐band spectra.