Vibrational dependence of pressure induced spectral linewidths and line shifts - Application of the infinite order sudden scattering approximation

The infinite order sudden (IOS) approximation to molecular rotation is applied to simplify the theory of linewidths and shifts in vibration–rotation spectra. This approximation is expected to be most accurate for hard, short‐range collisions and is therefore complementary to Anderson theory which is best for weak, glancing collisions. The IOS approximation predicts identical linewidths and shifts for P‐ and R‐branch transitions with the same line number. It also predicts zero line shifts for pure rotational spectra. The dependence of linewidths and shifts on vibrational band is seen to be due mainly to variation in diagonal vibrational matrix elements of the intermolecular potential. Calculations are performed for the 0–0, 0–1, and 0–2 bands of CO perturbed by He, using a theoretical interaction potential with no semiempirical or adjustable parameters; results are in satisfactory accord with experimental data.

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