The role of higher-multipolar and repulsive forces in the calculation of collision-broadened line-widths of linear molecules

Collision-broadened line widths in CO-CO2 and CO-O2 collisions have been calculated by incorporating interactions due to octopoles and hexadecapoles and short-range repulsive interactions into Anderson's (1949) theory. It is shown how these higher-order interactions can be manipulated to yield good agreement with experimental data. A critical evaluation of this totally empirical manipulation suggests that a thorough revision of the theory is required for all but simple dipole-dipole interactions. In the process of the evaluation, the values of the multipole moments are discussed.