- Related item:
- Integral steric asymmetry in the inelastic scattering of NO(X)
- Description:
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The integral steric asymmetry for the inelastic scattering of NO(X) by a variety of collision partners was recorded using a crossed molecular beam apparatus. The initial state of the NO(X, v = 0, j = 1/2, Ω=1/2Ω=1/2, ϵ=−1,fϵ=−1,f) molecule was selected using a hexapole electric field, before the NO bond axis was oriented in a static electric field, allowing probing of the scattering of the collision partner at either the N- or O-end of the molecule. Scattered NO molecules were state selectively probed using (1 + 1′) resonantly enhanced multiphoton ionisation, coupled with velocity-map ion imaging. Experimental integral steric asymmetries are presented for NO(X) + Ar, for both spin-orbit manifolds, and Kr, for the spin-orbit conserving manifold. The integral steric asymmetry for spin-orbit conserving and changing transitions of the NO(X) + O2 system is also presented. Close-coupled quantum mechanical scattering calculations employing well-tested ab initio potential energy surfaces were able to reproduce the steric asymmetry observed for the NO–rare gas systems. Quantum mechanical scattering and quasi-classical trajectory calculations were further used to help interpret the integral steric asymmetry for NO + O2. Whilst the main features of the integral steric asymmetry of NO with the rare gases are also observed for the O2 collision partner, some subtle differences provide insight into the form of the underlying potentials for the more complex system.
- Related item:
- Imaging quantum stereodynamics through Fraunhofer scattering of NO radicals with rare-gas atoms
- Description:
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Stereodynamics describes how the vector properties of molecules, such as the directions in which they move and the axes about which they rotate, affect the probabilities (or cross-sections) of specific processes or transitions that occur on collision. The main aspects of stereodynamics in inelastic atom–molecule collisions can often be understood from classical considerations, in which the particles are represented by billiard-ball-like hard objects. In a quantum picture, however, the collision is described in terms of matter waves, which can also scatter into the region of the geometrical shadow of the object and reveal detailed information on the pure quantum-mechanical contribution to the stereodynamics. Here we present measurements of irregular diffraction patterns for NO radicals colliding with rare-gas atoms that can be explained by the analytical Fraunhofer model. They reveal a hitherto overlooked dependence on (or ‘propensity rule’ for) the magnetic quantum number m of the molecules, and a previously unrecognized type of quantum stereodynamics that has no classical analogue or interpretation.
- Related item:
- Stereodynamics in NO(X) + Ar inelastic collisions
- Description:
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The effect of orientation of the NO(X) bond axis prior to rotationally inelastic collisions with Ar has been investigated experimentally and theoretically. A modification to conventional velocity-map imaging ion optics is described, which allows the orientation of hexapole state-selected NO(X) using a static electric field, followed by velocity map imaging of the resonantly ionized scattered products. Bond orientation resolved differential cross sections are measured experimentally for a series of spin-orbit conserving transitions and compared with quantum mechanical calculations. The agreement between experimental results and those from quantum mechanical calculations is generally good. Parity pairs, which have previously been observed in collisions of unpolarized NO with various rare gases, are not observed due to the coherent superposition of the two j = 1/2, Ω = 1/2 Λ-doublet levels in the orienting field. The normalized difference differential cross sections are found to depend predominantly on the final rotational state, and are not very sensitive to the final Λ-doublet level. The differential steric effect has also been investigated theoretically, by means of quantum mechanical and classical calculations. Classically, the differential steric effect can be understood by considering the steric requirement for different types of trajectories that contribute to different regions of the differential cross section. However, classical effects cannot account quantitatively for the differential steric asymmetry observed in NO(X) + Ar collisions, which reflects quantum interference from scattering at either end of the molecule. This quantum interference effect is dominated by the repulsive region of the potential.
