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Testing the ab initio quantum‐scattering calculations for the D 2 –He benchmark system with stimulated Raman spectroscopy
Author(s) -
Martínez Raúl Z.,
Bermejo Dionisio,
Thibault Franck,
Wcisło Piotr
Publication year - 2018
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.5391
Subject(s) - raman spectroscopy , ab initio , raman scattering , ab initio quantum chemistry methods , chemistry , atomic physics , molecular physics , x ray raman scattering , spectral line , spectroscopy , line (geometry) , physics , molecule , optics , quantum mechanics , geometry , mathematics , organic chemistry
This work presents a comparison between experimental and calculated values for the collisional line broadenings and shifts of the S 0 (0), S 0 (1), and S 0 (2) lines of the rotational Raman spectrum of D 2 perturbed by He at 77, 195, and 300 K. The pure rotational Raman spectra were obtained by means of a stimulated Raman spectroscopy experimental setup. Close coupling dynamical calculations were performed on the most recent ab initio H 2 –He potential energy surface. The resulting scattering matrix elements implemented in the general Hess method allow us to provide pressure broadening, pressure shifting, and Dicke coefficients from 10 to 400 K. Experimental and calculated values agree well with each other.