Speed-dependent broadening and line mixing in CH4 perturbed by Ar and N2 from multispectrum fits

Speed-dependent broadenings and shifts have been determined for the P and R branches of the nu3 band of CH4 perturbed by Ar and N2 using a multispectrum fitting analysis of high-resolution tunable difference-frequency laser spectra recorded at pressures < 67 kPa. For J > 3, the tetrahedral fine structure components in each J manifold are collisionally coupled and exhibit significant interference. The coupled lines are treated using a speed-dependent first-order line-mixing profile and are compared to a speed-independent full relaxation matrix inversion procedure with off-diagonal coupling elements calculated from an atom-atom Lennard-Jones potential model.