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The classical Franck–Condon approximation is used together with the Monte Carlo integration technique to calculate the optical absorption band shape arising in xenon hexafluoride from the pseudo‐Jahn–Teller active t1u bending mode. The potential energy function for this mode has the Devonshire form for the hindered rotational motion of a diatomic molecule in a cubic site and is characterized by three parameters. Results are presented using values of these parameters as determined by Pitzer and Bernstein for the 1A1g electronic ground state and as estimated by us from the crystal‐field model of Wang and Lohr for the 1T1u and 3T1u electronic excited states

A theoretical study of the optical absorption band shape for xenon hexafluoride