A theory for Coriolis enhanced vibrational energy transfer and its application to D2CO + rare gas collisions

Abstract

A method is described which allows Coriolis coupling and rotor asymmetry effects to be included in coupled channel calculations on collisions involving near symmetric top molecules. The method is used to investigate energy transfer between the v ₆ and v ₄ vibrational levels of D₂CO in collisions with the rare gas atoms He and Ar. Previously, this sytem has been investigated in double resonance experiments by Orr and coworkers. Our calculations indicate that vibrational relaxation in this system is greatly enhanced by Coriolis coupling, and approaches the rate of rotational relaxation.