Polarization of emission from asymmetric rotors. II. Vector reorientation through intramolecular coupling and inelastic collisions

Abstract

We report measurements of the linear and circular polarization ratios from fully resolved rotational levels of the asymmetric rotor NH2 populated by collisions with H atoms. The results compare well with a theoretical model that includes the depolarizing effects of intramolecular coupling of rotational angular momentum N to nuclear and to electron spin. These have a very significant influence on fluorescence polarization. The model also incorporates the tilting of the N vector in the molecule frame that occurs when inter-k stack transitions take place. Changes in N vector orientation are described with the aid of the angular momentum sphere, a classical representation of the motion of the N vector in a molecule fixed frame. The theoretical treatment assumes the classically impulsive limit for the collisional interaction with conservation of the m quantum number along the kinematic apse. This description of the fate of the N vector under the influence of intra- and intermolecular interactions allows stereodynamical conclusions to be drawn from experimental observations of fluorescence polarization.