Theoretical study of CH3Cl-N2 line shapes in the ν1 band. Line mixing effects in QR doublets and QQk sub-branches

Abstract

Line coupling and line mixing effects of CH3Cl lines in the ν1 band perturbed by N2 have been investigated. We have taken into account the non-diagonality of the exp(−S2) operator within specified line spaces as well as the k-degeneracy of the transitions (due to the double degeneracy of the j,k levels with k ≠ 0). These transitions should be considered as doublets coupled by the line mixing process. A new problem appears in the calculation when the atom-atom potential model is introduced. In order to overcome this difficulty, a pragmatic approach is proposed. Comparisons of theoretically calculated matrix elements of W with measurements of QR(j,k) doublets as well as some QQk sub-branches, which are strongly affected by line mixing, have been made. The results show that the formalism improved in this way leads to rather accurate predictions.