Experimental and theoretical investigation of resonances in low-energy NO-H2 collisions.

The experimental characterization of scattering resonances in low energy collisions has proven to be a stringent test for quantum chemistry calculations. Previous measurements on the NO-H2 system at energies down to 10 cm-1 challenged the most sophisticated calculations of potential energy surfaces available. In this report, we continue these investigations by measuring the scattering behavior of the NO-H2 system in the previously unexplored 0.4 cm-1-10 cm-1 region for the parity changing de-excitation channel of NO. We study state-specific inelastic collisions with both para- and ortho-H2 in a crossed molecular beam experiment involving Stark deceleration and velocity map imaging. We are able to resolve resonance features in the measured integral and differential cross sections. Results are compared to predictions from two previously available potential energy surfaces, and we are able to clearly discriminate between the two potentials. We furthermore identify the partial wave contributions to these resonances and investigate the nature of the differences between collisions with para- and ortho-H2. Additionally, we tune the energy spreads in the experiment to our advantage to probe scattering behavior at energies beyond our mean experimental limit.

Correlations in rotational energy transfer for NO-D2 inelastic collisions.

We present a combined experimental and theoretical study of state-to-state inelastic collisions between NO (X 2Π1/2, j = 1/2, f) radicals and D2 (j = 0, 1, 2, 3) molecules at collision energies of 100 cm-1 and 750 cm-1. Using the combination of Stark deceleration and velocity map imaging, we fully resolve pair-correlated excitations in the scattered molecules. Both spin-orbit conserving and spin-orbit changing transitions in the NO radical are measured, while the coincident rotational excitation (j = 0 → j = 2) and rotational de-excitation (j = 2 → j = 0 and j = 3 → j = 1) in D2 are observed. De-excitation of D2 shows a strong dependence on the spin-orbit excitation of NO. We observe translation-to-rotation energy transfer as well as direct rotation-to-rotation energy transfer at the lowest collision energy probed. The experimental results are in good agreement with cross sections obtained from quantum coupled-channels calculations based on recent NO-D2 potential energy surfaces. The observed trends in the correlated scattering cross sections are understood in terms of the NO-D2 quadrupole-quadrupole interaction.

Imaging diffraction oscillations for inelastic collisions of NO radicals with He and D2.

We present state-to-state differential cross sections for collisions of NO molecules (X2Π1/2,j=1/2,f) with He atoms and ortho-D2 (j = 0) molecules as a function of collision energy. A high angular resolution obtained using the combination of Stark deceleration and velocity map imaging allows for the observation of diffraction oscillations in the angular scattering distributions. Differences in the differential cross sections and, in particular, differences in the angular spacing between individual diffraction peaks are observed. Since the masses of D2 and He are almost equal and since D2(j = 0) may be considered as a pseudo-atom, these differences directly reflect the larger size of D2 as compared to He. The observations are in excellent agreement with the cross sections obtained from quantum close-coupling scattering calculations based on accurate ab initio NO-He and NO-D2 potential energy surfaces. For the latter, we calculated a new NO-D2 potential energy surface.

Mapping partial wave dynamics in scattering resonances by rotational de-excitation collisions.

One of the most important parameters in a collision is the 'miss distance' or impact parameter, which in quantum mechanics is described by quantized partial waves. Usually, the collision outcome is the result of unavoidable averaging over many partial waves. Here we present a study of low-energy NO-He collisions that enables us to probe how individual partial waves evolve during the collision. By tuning the collision energies to scattering resonances between 0.4 and 6 cm-1, the initial conditions are characterized by a limited set of partial waves. By preparing NO in a rotationally excited state before the collision and by studying rotational de-excitation collisions, we were able to add one quantum of angular momentum to the system and trace how it evolves. Distinct fingerprints in the differential cross-sections yield a comprehensive picture of the partial wave dynamics during the scattering process. Exploiting the principle of detailed balance, we show that rotational de-excitation collisions probe time-reversed excitation processes with superior energy and angular resolution.

Imaging the onset of the resonance regime in low-energy NO-He collisions.

At low energies, the quantum wave-like nature of molecular interactions results in distinctive scattering behavior, ranging from the universal Wigner laws near 0 kelvin to the occurrence of scattering resonances at higher energies. It has proven challenging to experimentally probe the individual waves underlying these phenomena. We report measurements of state-to-state integral and differential cross sections for inelastic NO-He collisions in the 0.2 to 8.5 centimeter-1 range with 0.02 centimeter-1 resolution. We studied the onset of the resonance regime by probing the lowest-lying resonance dominated by s and p waves only. The highly structured differential cross sections directly reflect the increasing number of contributing waves as the energy is increased. Only with CCSDT(Q) level of theory was it possible to reproduce our measurements.