Journal of the American Chemical Society, Vol.128, No.27, 8777-8789, 2006
Quantum interference as the source of steric asymmetry and parity propensity rules in NO-rare gas inelastic scattering
Rotationally inelastic scattering of rare gas atoms and oriented NO molecules exhibits a remarkable alternation in the sign of steric asymmetry between even and odd changes in rotational quantum number. This effect has also been found in full quantum-mechanical scattering calculations. However, until now no physical picture has been given for the alternation. In this work, a newly developed quasi-quantum treatment (QQT) provides the first demonstration that quantum interferences between different orientations of the repulsive potential ( that are present in the oriented wave function) are the source of this alternation. Further, from application of the treatment to collisions of nonoriented molecules, a previously unrecognized propensity rule is derived. The angular dependence of the cross sections for excitation to neighboring rotational states with the same parity is shown to be similar, except for a prefactor. Experimental results are presented to support this rule. Unlike conventional quantum-mechanical (or semiclassical) treatments, QQT requires no summation over the orbital angular momentum quantum number l or integration over the impact parameter b. This eliminates the need to solve large sets of coupled differential equations that couple l and rotational state channels among which interference can occur. The QQT provides a physical interpretation of the scattering amplitude that can be represented by a Legendre moment. Application of the QQT on a simple hard-shell potential leads to near-quantitative agreement with experimental observations.