Collisions between cold polar molecules represent a fascinating research frontier but have proven hard to probe experimentally. We report measurements of inelastic cross sections for collisions between nitric oxide (NO) and deuterated ammonia (ND3) molecules at energies between 0.1 and 580 centimeter-1, with full quantum state resolution. At energies below the ~100-centimeter-1 well depth of the interaction potential, we observed backward glories originating from peculiar U-turn trajectories. At energies below 0.2 centimeter-1, we observed a breakdown of the Langevin capture model, which we interpreted in terms of a suppressed mutual polarization during the collision, effectively switching off the molecular dipole moments. Scattering calculations based on an ab initio NO-ND3 potential energy surface revealed the crucial role of near-degenerate rotational levels with opposite parity in low-energy dipolar collisions.
We present a joint experimental and theoretical study of rotationally inelastic collisions between NO (X2Π1/2, ν = 0, j = 1/2, f) radicals and CO (X1Σ+, ν = 0, j = 0) molecules at a collision energy of 220 cm-1. State-to-state scattering images for excitation of NO radicals into various final states were measured with high resolution by combining the Stark deceleration and velocity map imaging techniques. The high image resolution afforded the observation of correlated rotational excitations of NO-CO pairs, which revealed a number of striking scattering phenomena. The so-called "parity-pair" transitions in NO are found to have similar differential cross sections, independent of the concurrent excitation of CO, extending this well-known effect for collisions between NO and rare gas atoms into the realm of bimolecular collisions. Forward scattering is found for collisions that induce a large amount of rotational energy transfer (in either NO, CO, or both), which require low impact parameters to induce sufficient energy transfer. This observation is interpreted in terms of the recently discovered hard collision glory scattering mechanism, which predicts the forward bending of initially backward receding trajectories if the energy uptake in the collision is substantial in relation to the collision energy. The experimental results are in good agreement with the predictions from coupled-channels quantum scattering calculations based on an ab initio NO-CO potential energy surface.
For molecular collisions, the deflection of a molecule's trajectory provides one of the most sensitive probes of the interaction potential and there are general rules of thumb that relate the direction of deflection to precollision conditions. Following intuition, forward scattering results from glancing collisions, whereas near head-on collisions result in back scattering. Here we present the observation of forward scattering in inelastic processes that defies this common wisdom. For deeply inelastic collisions between NO radicals and CO or HD molecules, we observed forward scattering in fully resolved pair-correlated differential cross-sections, despite the low impact parameters that are needed to induce a sufficient energy transfer. We rationalized these findings by extending the textbook model of hard-sphere scattering-taking inelastic energy transfer into account-and attribute the forward scattering to glory-type trajectories caused by attractive forces. This phenomenon, which we refer to as hard-collision glory scattering, is predicted to be ubiquitous. We derive under which conditions hard-collision glory scattering occurs and retrospectively identify such behaviour in previously studied systems.
Quantum Theory , Energy Transfer , Retrospective Studies
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.
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.
Experimental developments continue to challenge the theoretical description of molecular interactions. One key arena in which these advances have taken place is in rotationally inelastic scattering. Electric fields have been used with great success to select the initial quantum state and slow molecules for scattering studies, revealing novel stereodynamics, diffraction oscillations and scattering resonances. These have enjoyed excellent agreement with quantum scattering calculations performed on state-of-the-art coupled-cluster potential energy surfaces. To date these studies have largely employed reactants in the ground vibrational state (v = 0) and the lowest low-field-seeking quantum state. Here we describe the use of stimulated emission pumping to prepare NO molecules in arbitrary single rotational and parity states of v = 10 for inelastic scattering studies. These are employed in a near-copropagating molecular beam geometry that permits the collision energy to be tuned from above room temperature to 1 K or below, with product differential cross-sections obtained by velocity map imaging. This extremely nonequilibrium condition, not found in nature, tests current theoretical methods in a new regime.
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.
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 â j = 2) and rotational de-excitation (j = 2 â j = 0 and j = 3 â 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.
We present the first crossed beam scattering experiment using a Zeeman decelerated molecular beam. The narrow velocity spreads of Zeeman decelerated NO (X2Π3/2, j = 3/2) radicals result in high-resolution scattering images, thereby fully resolving quantum diffraction oscillations in the angular scattering distribution for inelastic NO-Ne collisions and product-pair correlations in the radial scattering distribution for inelastic NO-O2 collisions. These measurements demonstrate similar resolution and sensitivity as in experiments using Stark decelerators, opening up possibilities for controlled and low-energy scattering experiments using chemically relevant species such as H and O atoms, O2 molecules, or NH radicals.
State-to-state differential cross sections for rotationally inelastic collisions of vibrationally excited NO with Ar have been measured in a near-copropagating crossed beam experiment at collision energies of 530 and 30 cm-1. Stimulated emission pumping (SEP) to prepare NO in specific rovibrational levels is coupled with direct-current slice velocity map imaging to obtain a direct measurement of the differential cross sections. The use of nearly copropagating beams to achieve low NO-Ar collision energies and broad collision energy tuning capability are also demonstrated. The experimental differential cross sections (DCSs) for NO in v = 10 in specific rotational and parity states are compared with the corresponding DCSs predicted for NO in v = 0 obtained from quantum mechanical close coupling calculations to highlight the differences between the NO( v = 10)-Ar and NO( v = 0)-Ar interaction potentials.
Exciting discussions on the impact of quantum effects in small molecular systems took place in the historical city of Edinburgh this fall 2018 in the unique conference format of the Faraday Discussions. During this three day conference meeting close to Holyrood Park, 65 leading experts from all over the world came together to discuss the developments, advances and challenges in the wide field of quantum effects in small molecular systems, either isolated or embedded into clusters, clathrates or cold matrices. The meeting clearly reflected the importance of the accurate description, characterization and prediction of quantum effects in isolated, solvated and complexed molecular systems, while allowing the community to crystallize future perspectives and directions in the field, as well as applications in chemistry, physics, biology, environmental sciences and industry.
Over the last 25 years, the formalism known as coupled-cluster (CC) theory has emerged as the method of choice for the ab initio calculation of intermolecular interaction potentials. The implementation known as CCSD(T) is often referred to as the gold standard in quantum chemistry. It gives excellent agreement with experimental observations for a variety of energy-transfer processes in molecular collisions, and it is used to calibrate density functional theory. Here, we present measurements of low-energy collisions between NO radicals and H2 molecules with a resolution that challenges the most sophisticated quantum chemistry calculations at the CCSD(T) level. Using hitherto-unexplored anti-seeding techniques to reduce the collision energy in a crossed-beam inelastic-scattering experiment, a resonance structure near 14 cm-1 is clearly resolved in the state-to-state integral cross-section, and a unique resonance fingerprint is observed in the corresponding differential cross-section. This resonance structure discriminates between two NO-H2 potentials calculated at the CCSD(T) level and pushes the required accuracy beyond the gold standard.
Although collisions between atoms and molecules are largely understood, collisions between two molecules have proven much harder to study. In both experiment and theory, our ability to determine quantum-state-resolved bimolecular cross-sections lags behind their atom-molecule counterparts by decades. For many bimolecular systems, even rules of thumb-much less intuitive understanding-of scattering cross sections are lacking. Here, we report the measurement of state-to-state differential cross sections on the collision of state-selected and velocity-controlled nitric oxide (NO) radicals and oxygen (O2) molecules. Using velocity map imaging of the scattered NO radicals, the full product-pair correlations of rotational excitation that occurs in both collision partners from individual encounters are revealed. The correlated cross sections show surprisingly good agreement with quantum scattering calculations using ab initio NO-O2 potential energy surfaces. The observations show that the well-known energy-gap law that governs atom-molecule collisions does not generally apply to bimolecular excitation processes, and reveal a propensity rule for the vector correlation of product angular momenta.
We present state-to-state differential cross sections for collisions of NO molecules (X2Π1/2, j = 1/2f) with para-H2 and ortho-D2 molecules, at a collision energy of 510 and 450 cm-1, respectively. The angular scattering distributions for various final states of the NO radical are measured with high resolution using a crossed molecular beam apparatus that employs the combination of Stark deceleration and velocity map imaging. Rotational rainbows as well as diffraction oscillations are fully resolved in the scattering images. The observed angular scattering distributions are in excellent agreement with the cross sections obtained from quantum close-coupling scattering calculations based on recently computed NO-H2 potential energy surfaces, except for excitation of NO into the j = 7/2f channel. For this particular inelastic channel, a significant discrepancy with theory is observed, despite various additional measurements and calculations, at present, not understood.
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.
The influence of aqueous electrolytes on the water bending vibration was studied with Raman spectroscopy. For all salts investigated (NaI, NaBr, NaCl, and NaSCN), we observed a nonlinear intensity increase of the water bending vibration with increasing concentration. Different lasers and a tunable frequency-doubled optical parametric oscillator system were used to achieve excitation wavelengths between 785 and 374 nm. Focusing on NaI solutions, the relative enhancement of the water bending vibration was found to increase strongly with excitation photon energy, in line with a preresonance effect from the iodide-water charge-transfer transition. We used multivariate curve resolution (MCR) to decompose the measured Raman spectra of NaI solutions into three interconverting spectral components assigned to bulk water and water molecules interacting with one (X···H-O-H···O) and two (X···H-O-H···X) iodide ions (X = I(-)). The Raman spectrum of solid sodium iodide dihydrate supports the assignment of the latter. Using the MCR results, relative Raman scattering cross sections of 4.0 ± 0.6 and 14.0 ± 0.1 were calculated for the mono- and di-iodide species, respectively (compared to that of bulk water set to unity). In addition, it was found that at relatively low concentrations each iodide ion affects the Raman spectrum of roughly 22 surrounding water molecules, indicating that the influence of iodide extends beyond the first solvation shell. Our results demonstrate that the Raman bending vibration of water is a sensitive probe, providing new insights into anion solvation in aqueous environments.
