Collisional line widths of autoperturbed N 2: Measurements and quantum calculations

Abstract

In this work we present new experimental and theoretical values for the line broadening coefficients of the Q-branch Raman lines of autoperturbed N 2. For the experimental determination of the coefficients, high resolution stimulated Raman spectra of the Q-branch of N 2 at different pressures were obtained at 77, 194 and 298 K. Simultaneously, quantum dynamical calculations, performed on two potential energy surfaces, were carried out for the system between 77 and 298 K, rendering a set of theoretical line broadening coefficients that could be directly compared to those obtained from the present measurements and the previous ones. Within the limit of considering the colliding molecules distinguishable we discuss the ortho and para contributions to the pressure broadening cross-sections. Because such calculations are time consuming we indicate routes to circumvent this difficulty. We observe a reasonable agreement between theoretical and experimental values of the collisional line broadening coefficients at all the studied temperatures.