Inelastic scattering of NO(A2Σ+) + CO2: rotation-rotation pair-correlated differential cross sections.

A crossed beam velocity-map ion-imaging apparatus has been used to determine differential cross sections (DCSs) for the rotationally inelastic scattering of NO(A2Σ+, v = 0, j = 0.5) with CO2, as a function of both NO(A, v = 0, N') final state and the coincident final rotational energy of the CO2. The DCSs are dominated by forward-peaked scattering for all N', with significant rotational excitation of CO2, and a small backward scattered peak is also observed for all final N'. However, no rotational rainbow scattering is observed and there is no evidence for significant product rotational angular momentum polarization. New ab initio potential energy surface calculations at the PNO-CCSD(T)-F12b level of theory report strong attractive forces at long ranges with significant anisotropy relative to both NO and CO2. The absence of rotational rainbow scattering is consistent with removal of low-impact-parameter collisions via electronic quenching, in agreement with the literature quenching rates of NO(A) by CO2 and recent electronic structure calculations. We propose that high-impact-parameter collisions, that do not lead to quenching, experience strong anisotropic attractive forces that lead to significant rotational excitation in both NO and CO2, depolarizing product angular momentum while leading to forward and backward glory scattering.

Differential Cross Sections for Pair-Correlated Rotational Energy Transfer in NO(A2Σ+) + N2, CO, and O2: Signatures of Quenching Dynamics.

A crossed molecular beam, velocity-map ion-imaging apparatus has been used to determine differential cross sections (DCSs), as a function of collider final internal energy, for rotationally inelastic scattering of NO(A2Σ+, v = 0, j = 0.5f1) with N2, CO, and O2, at average collision energies close to 800 cm-1. DCSs are strongly forward scattered for all three colliders for all observed NO(A) final rotational states, N'. For collisions with N2 and CO, the fraction of NO(A) that is scattered sideways and backward increases with increasing N', as does the internal rotational excitation of the colliders, with N2 having the highest internal excitation. In contrast, the DCSs for collisions with O2 are essentially only forward scattered, with little rotational excitation of the O2. The sideways and backward scattering expected from low-impact-parameter collisions, and the rotational excitation expected from the orientational dependence of published van der Waals potential energy surfaces (PESs), are absent in the observed NO(A) + O2 results. This is consistent with the removal of these short-range scattering trajectories via facile electronic quenching of NO(A) by O2, in agreement with the literature determination of the coupled NO-O2 PESs and the associated conical intersections. In contrast, collisions at high-impact parameter that predominately sample the attractive van der Waals minimum do not experience quenching and are inelastically forward scattered with low rotational excitation.

Stereodynamics of rotational energy transfer in NO(A2Σ+) + Kr collisions.

A crossed molecular beam, velocity-map ion imaging apparatus has been used to determine differential cross sections (DCSs) and angle-resolved rotational angular momentum alignment moments for the state-resolved rotationally inelastic scattering of NO(A2Σ+, v = 0, j = 0.5 f1) with Kr at an average collision energy of 785 cm-1. The experimental results are compared to close-coupled quantum scattering (QS) calculations performed on a literature ab initio potential energy surface (J. Klos et al., J. Chem. Phys., 2008, 129, 244303). DCSs are very strongly forward scattered, with weaker side and backward scattered peaks becoming progressively more important at higher-N'. Good agreement is found between experimental and QS DCSs, indicating that the PES is an accurate reflection of the NO(A)-Kr interaction energies. Partial wave analysis of the QS DCSs isolates multiple scattering mechanisms contributing to the DCSs, including L-type rainbows and Fraunhofer diffraction. Measured alignment moments are not well described by a hard-shell kinematic apse scattering model, showing deviations in the forward scattering hemisphere that are in agreement with QS calculations and arise from attractive regions of the PES. These discrepancies emphasise that established scattering mechanisms for molecules such as NO with lighter noble gases cannot be extrapolated safely to heavier, more polarisable members of the series.

Non-intuitive rotational reorientation in collisions of NO(A 2Σ+) with Ne from direct measurement of a four-vector correlation.

Stereodynamic descriptions of molecular collisions concern the angular correlations that exist between vector properties of the motion of the participating species, including their velocities and rotational angular momenta. Measurements of vector correlations provide a unique view of the forces acting during collisions, and are a stringent test of electronic-structure calculations of molecular interactions. Here, we present direct measurement of the four-vector correlation between initial and final relative velocities and rotational angular momenta in a molecular collision. This property, which quantifies the extent to which a molecule retains a memory of its initial sense of rotation, or handedness, as a function of scattering angle, yields insight into the dynamics of a molecular collision. We report non-intuitive changes in the handedness for specific states and scattering angles, reproduced by classical and quantum scattering calculations. Comparison to calculations on different ab initio potential energy surfaces demonstrates this measurement's exquisite sensitivity to the underlying intermolecular forces.

Pair-correlated stereodynamics for diatom-diatom rotational energy transfer: NO(A2Σ+) + N2.

We have performed a crossed molecular beam velocity-map ion imaging study of state-to-state rotational energy transfer of NO(A2Σ+, v = 0, N = 0, j = 0.5) in collisions with N2 and have measured rotational angular momentum polarization dependent images of product NO(A) rotational levels N' = 3 and 5-11 for collisions at an average energy of 797 cm-1. We present an extension of our previously published [T. F. M. Luxford et al., J. Chem. Phys. 145, 174 304 (2016)] image analysis which includes the effect of rotational excitation of the unobserved collision partner and critically evaluate this methodology. We report differential cross sections and angle-resolved angular momentum alignment moments for NO(A) levels N' = 3 and 5-11 as a function of the rotational excitation of the coincident N2 partner. The scattering dynamics of NO(A) + N2 share similarities with those previously reported for NO(A) + Ne and Ar, although with detailed differences. We use comparison of the measurements reported here to the scattering of NO(A) with Ne, and the known NO(A)-Ne potential energy surface, to draw conclusions about the previously unknown NO(A)-N2 potential.

Experimental testing of ab initio potential energy surfaces: Stereodynamics of NO(A2Σ+) + Ne inelastic scattering at multiple collision energies.

We present a crossed molecular beam velocity-map ion imaging study of state-to-state rotational energy transfer of NO(A2Σ+, v = 0, N = 0, j = 0.5) in collisions with Ne atoms. From these measurements, we report differential cross sections and angle-resolved rotational angular momentum alignment moments for product states N' = 3 and 5-10 for collisions at an average energy of 523 cm-1, and N' = 3 and 5-14 for collisions at an average energy of 1309 cm-1, respectively. The experimental results are compared to the results of close-coupled quantum scattering calculations on two literature ab initio potential energy surfaces (PESs) [Pajón-Suárez et al., Chem. Phys. Lett. 429, 389 (2006) and Cybulski and Fernández, J. Phys. Chem. A 116, 7319 (2012)]. The differential cross sections from both experiment and theory show clear rotational rainbow structures at both collision energies, and comparison of the angles observed for the rainbow peaks leads to the conclusion that Cybulski and Fernández PES better represents the NO(A2Σ+)-Ne interaction at the collision energies used here. Sharp, forward scattered (<10°), peaks are observed in the experimental differential cross sections for a wide range of N' at both collision energies, which are not reproduced by theory on either PES. We identify these as L-type rainbows, characteristic of attractive interactions, and consistent with a shallow well in the collinear Ne-N-O geometry, similar to that calculated for the NO(A2Σ+)-Ar surface [Klos et al., J. Chem. Phys. 129, 244303 (2008)], but absent from both of the NO(A2Σ+)-Ne surfaces tested here. The angle-resolved alignment moments calculated by quantum scattering theory are generally in good agreement with the experimental results, but both experiment and quantum scattering theories are dramatically different to the predictions of a classical rigid-shell, kinematic-apse conservation model. Strong oscillations are resolved in the experimental alignment moments as a function of scattering angle, confirming and extending the preliminary report of this behavior [Steill et al., J. Phys. Chem. A 117, 8163 (2013)]. These oscillations are correlated with structure in the differential cross section, suggesting an interference effect is responsible for their appearance.

Comparative stereodynamics in molecule-atom and molecule-molecule rotational energy transfer: NO(A(2)Σ(+)) + He and D2.

We present a crossed molecular beam scattering study, using velocity-map ion-imaging detection, of state-to-state rotational energy transfer for NO(A(2)Σ(+)) in collisions with the kinematically identical colliders He and D2. We report differential cross sections and angle-resolved rotational angular momentum polarization moments for transfer of NO(A, v = 0, N = 0, j = 0.5) to NO(A, v = 0, N' = 3, 5-12) in collisions with He and D2 at respective average collision energies of 670 cm(-1) and 663 cm(-1). Quantum scattering calculations on a literature ab initio potential energy surface for NO(A)-He [J. Klos et al., J. Chem. Phys. 129, 244303 (2008)] yield near-quantitative agreement with the experimental differential scattering cross sections and good agreement with the rotational polarization moments. This confirms that the Klos et al. potential is accurate within the experimental collisional energy range. Comparison of the experimental results for NO(A) + D2 and He collisions provides information on the hitherto unknown NO(A)-D2 potential energy surface. The similarities in the measured scattering dynamics of NO(A) imply that the general form of the NO(A)-D2 potential must be similar to that calculated for NO(A)-He. A consistent trend for the rotational rainbow maximum in the differential cross sections for NO(A) + D2 to peak at more forward angles than those for NO(A) + He is consistent with the NO(A)-D2 potential being more anisotropic with respect to NO(A) orientation. No evidence is found in the experimental measurements for coincident rotational excitation of the D2, consistent with the potential having low anisotropy with respect to D2. The NO(A) + He polarization moments deviate systematically from the predictions of a hard-shell, kinematic-apse scattering model, with larger deviations as N' increases, which we attribute to the shallow gradient of the anisotropic repulsive NO(A)-He potential energy surface.

Rotationally inelastic scattering of NO(A(2)Σ(+)) + Ar: Differential cross sections and rotational angular momentum polarization.

We present the implementation of a new crossed-molecular beam, velocity-map ion-imaging apparatus, optimized for collisions of electronically excited molecules. We have applied this apparatus to rotational energy transfer in NO(A(2)Σ(+), v = 0, N = 0, j = 0.5) + Ar collisions, at an average energy of 525 cm(-1). We report differential cross sections for scattering into NO(A(2)Σ(+), v = 0, N' = 3, 5, 6, 7, 8, and 9), together with quantum scattering calculations of the differential cross sections and angle dependent rotational alignment. The differential cross sections show dramatic forward scattered peaks, together with oscillatory behavior at larger scattering angles, while the rotational alignment moments are also found to oscillate as a function of scattering angle. In general, the quantum scattering calculations are found to agree well with experiment, reproducing the forward scattering and oscillatory behavior at larger scattering angles. Analysis of the quantum scattering calculations as a function of total rotational angular momentum indicates that the forward scattering peak originates from the attractive minimum in the potential energy surface at the N-end of the NO. Deviations in the quantum scattering predictions from the experimental results, for scattering at angles greater than 10°, are observed to be more significant for scattering to odd final N'. We suggest that this represents inaccuracies in the potential energy surface, and in particular in its representation of the difference between the N- and O-ends of the molecule, as given by the odd-order Legendre moments of the surface.

Rotational alignment of NO (A2Σ+) from collisions with Ne.

We report the direct angle-resolved measurement of collision-induced alignment of short-lived electronically excited molecules using crossed atomic and molecular beams. Utilizing velocity-mapped ion imaging, we measure the alignment of NO in its first electronically excited state (A(2)Σ(+)) following single collisions with Ne atoms. We prepare A(2)Σ(+) (v = 0, N = 0, j = 0.5) and by comparing images obtained using orthogonal linear probe laser polarizations, we experimentally determine the degree of alignment induced by collisional rotational excitation for the final rotational states N' = 4, 5, 7, and 9. The experimental results are compared to theoretical predictions using both a simple classical hard-shell model and quantum scattering calculations on an ab initio potential energy surface (PES). The experimental results show overall trends in the scattering-angle dependent polarization sensitivity that are accounted for by the simple classical model, but structure in the scattering-angle dependence that is not. The quantum scattering calculations qualitatively reproduce this structure, and we demonstrate that the experimental measurements have the sensitivity to critique the best available potential surfaces. This sensitivity to the PES is in contrast to that predicted for ground-state NO(X) alignment.