Comparison of quantum, semiclassical and classical methods in hydrogen broadening of nitrogen lines

We use an accurate N2-H2ab initio potential energy surface (PES) in order to inter-compare various methods commonly employed to calculate pressure broadening coefficients. Close-coupling (CC) calculations of the collisional linewidths of the isotropic Raman lines of N2 perturbed by H2 are performed for temperatures between 77 and 2000 K. The CC results compare well with available experimental values. Three less exact methods of calculation are also used: the full classical (FC) model of Gordon, the semiclassical (SC) formalism of Robert and Bonamy and the quantum dynamical coupled states (CS) method. The CS method provides good agreement with CC calculations for all studied temperatures, FC calculations can be considered as accurate above room temperature while the SC method gives overestimated values by about 20-30% in all cases. The temperature dependences of pressure broadening coefficients provided by each method are very similar at elevated (above room) temperatures.

► Pressure broadening coefficients N2-H2. ► Isotropic Raman Q lines. ► Comparison between various theoretical methods. ► High temperatures. ► The temperature dependence of these pressure broadening coefficients is provided.