Testing the ab initio quantum‐scattering calculations for the D2–He benchmark system with stimulated Raman spectroscopy

Abstract

AbstractThis work presents a comparison between experimental and calculated values for the collisional line broadenings and shifts of the S0(0), S0(1), and S0(2) lines of the rotational Raman spectrum of D2 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 H2–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.