Differential steric effects in the inelastic scattering of NO(X) + Ar: spin-orbit changing transitions.

Spin-orbit changing transitions for bond-axis oriented collisions of NO(X) with Ar have been investigated with full quantum state selection via a crossed molecular beam experiment at collision energies of 532 cm-1 and 651 cm-1. NO(X) molecules were selected in their ground rotational state (Ω = 0.5, j = 0.5, f) before being adiabatically oriented using a static electric field, such that either the N- or O-end of the molecule was directed towards the incoming Ar atom. After collision, NO(X, Ω' = 1.5, j', e) molecules were probed quantum state specifically using velocity-map ion imaging, coupled with resonantly enhanced multi-photon ionization. Differences were observed between the experimental ion images and differential cross sections for collisions occurring at the two ends of the molecule, with results that could largely be accounted for by quantum mechanical scattering calculations. The bond-axis oriented data for the spin-orbit changing collisions are compared with similar results obtained previously for spin-orbit conserving transitions, and for field free scattering of NO(X) with Ar.

Angular distributions for the inelastic scattering of NO(X2Π) with O2(X3Σg-).

The inelastic scattering of NO(X2Π) by O2(X3Σg-) was studied at a mean collision energy of 550 cm-1 using velocity-map ion imaging. The initial quantum state of the NO(X2Π, v = 0, j = 0.5, Ω=0.5, 𝜖 = -1, f) molecule was selected using a hexapole electric field, and specific Λ-doublet levels of scattered NO were probed using (1+1') resonantly enhanced multiphoton ionization. A modified "onion-peeling" algorithm was employed to extract angular scattering information from the series of "pancaked," nested Newton spheres arising as a consequence of the rotational excitation of the molecular oxygen collision partner. The extracted differential cross sections for NO(X) f→f and f→e Λ-doublet resolved, spin-orbit conserving transitions, partially resolved in the oxygen co-product rotational quantum state, are reported, along with O2 fragment pair-correlated rotational state population. The inelastic scattering of NO with O2 is shown to share many similarities with the scattering of NO(X) with the rare gases. However, subtle differences in the angular distributions between the two collision partners are observed.

Integral steric asymmetry in the inelastic scattering of NO(X2Π).

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=1/2, ϵ=-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.

Stereodynamics in NO(X) + Ar inelastic collisions.

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.

Rotational Orientation Effects in NO(X) + Ar Inelastic Collisions.

Rotational angular momentum orientation effects in the rotationally inelastic collisions of NO(X) with Ar have been investigated both experimentally and theoretically at a collision energy of 530 cm(-1). The collision-induced orientation has been determined experimentally using a hexapole electric field to select the ϵ = -1 Λ-doublet level of the NO(X) j = 1/2 initial state. Fully quantum state resolved polarization-dependent differential cross sections were recorded experimentally using a crossed molecular beam apparatus coupled with a (1 + 1') resonance-enhanced multiphoton ionization detection scheme and subsequent velocity-map imaging. To determine the NO sense of rotation, the probe radiation was circularly polarized. Experimental orientation polarization-dependent differential cross sections are compared with those obtained from quantum mechanical scattering calculations and are found to be in good agreement. The origin of the collision-induced orientation has been investigated by means of close-coupled quantum mechanical, quantum mechanical hard shell, quasi-classical trajectory (QCT), and classical hard shell calculations at the same collision energy. Although there is evidence for the operation of limiting classical mechanisms, the rotational orientation cannot be accounted for by QCT calculations and is found to be strongly influenced by quantum mechanical effects.

A new perspective: imaging the stereochemistry of molecular collisions.

The concept of the steric effect in molecular collisions is central to chemistry. In this Perspective article we review some of the progress made in studying the steric effect in inelastic and reactive collisions involving relatively small isolated atomic and molecular species. We overview the theoretical framework used to quantify the steric effect, and outline some of the key experimental approaches that can be employed to study the dynamics and mechanism of collisions involving oriented and aligned molecules. We illustrate the discussion by highlighting a few recent studies of inelastic and reactive scattering. Finally, we conclude with some reflections on possible future directions of interest.

Steric effects and quantum interference in the inelastic scattering of NO(X) + Ar.

Rotationally inelastic collisions of NO(X) with Ar are investigated in unprecedented detail using state-to-state, crossed molecular beam experiments. The NO(X) molecules are selected in the Ω = 0.5, j = 0.5, f state and then oriented such that either the 'N' or 'O' end of the molecule is directed towards the incoming Ar atom. Velocity map ion imaging is then used to probe the scattered NO molecules in well-defined quantum states. We show that the fully quantum state-resolved differential steric asymmetry, which quantifies how the relative efficiency for scattering off the 'O' and the 'N' ends of the molecule varies with scattering angle, is strongly affected by quantum interference. Significant changes in both integral and differential cross sections are found depending on whether collisions occur with the N or O ends of the molecule. The results are well accounted for by rigorous quantum mechanical calculations, in contrast to both classical trajectory calculations and more simplistic models that provide, at best, an incomplete picture of the dynamics.

Fully quantum state-resolved inelastic scattering of NO(X) + Kr: differential cross sections and product rotational alignment.

Fully quantum state selected and resolved inelastic scattering of NO(X) by krypton has been investigated. Initial Λ-doublet state selection is achieved using an inhomogeneous hexapole electric field. Differential cross sections and even-moment polarization dependent differential cross sections have been obtained at a collision energy of 514 cm(-1) for both spin-orbit and parity conserving and changing collisions. Experimental results are compared with those obtained from quantum scattering calculations and are shown to be in very good agreement. Hard shell quantum scattering calculations are also performed to determine the effects of the different parts of the potential on the scattering dynamics. Comparisons are also made with the NO(X) + Ar system.