Overlapping effects and motional narrowing in molecular band shapes: Application to the Q branch of HDa)

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Abstract
A new formulation of the theory of strong overlapping effects in molecular line broadening is presented in terms of the intermolecular potential. This formulation takes into account the vibrational degrees of freedom and includes in an acceptable form the close collisions. A detailed analysis of such effects is carried out for the motional narrowing arising in the Q branch of HD at sufficiently high densities. A very good consistency is obtained between the experimental data and the present calculation at room and low temperatures. The nonadditivity effects in infrared absorption and anisotropic Raman overlapping lines treated in the general frame of this paper may also be easily calculated when required.