We present the direct far-infrared optical excitation ofNOradicals from the X-2 Pi(1/2) electronic ground state to the X-2 Pi(3/2) spin-orbit excited state. This spin-orbit forbidden transition at a photon energy near 125 cm(-1) borrows intensity by a small admixture of (2)Pi(1/2) character into the (2)Pi(3/2) wavefunction, and can be saturated using the intracavity free electron laser FELICE. In the X-2 Pi(1/2) state, the NO radical has a negligible magnetic moment, whereas the radicals have a large magnetic moment in the X-2 Pi(3/2) excited state. The direct optical excitation demonstrated here thus effectively ' switches on' the molecule's magnetic moment, and allows for the production of a sample of NO (X-2 Pi(3/2)) with almost perfect quantum state purity. These optically prepared well-defined packets of magnetic NO radicals offer interesting prospects for the use of this benchmark molecule in molecular deceleration and trapping experiments. [GRAPHICS] .

Multistage Zeeman deceleration is a technique used to reduce the velocity of neutral molecules with a magnetic dipole moment. Here we present a Zeeman decelerator that consists of 100 solenoids and 100 magnetic hexapoles, that is based on a short prototype design presented recently [Phys. Rev. A 95, 043415 (2017)]. The decelerator features a modular design with excellent thermal and vacuum properties, and is robustly operated at a 10 Hz repetition rate. This multistage Zeeman decelerator is particularly optimized to produce molecular beams for applications in crossed beam molecular scattering experiments. We characterize the decelerator using beams of atomic and molecular oxygen. For atomic oxygen, the magnetic fields produced by the solenoids are used to tune the final longitudinal velocity in the 500 - 125 m/s range, while for molecular oxygen the velocity is tunable in the 350 - 150 m/s range. This corresponds to a maximum kinetic energy reduction of 95% and 80% for atomic and molecular oxygen, respectively.

Multistage Zeeman deceleration is a technique used to reduce the velocity of neutral molecules with a magnetic dipole moment. Here we present a Zeeman decelerator that consists of 100 solenoids and 100 magnetic hexapoles, that is based on a short prototype design presented recently [Phys. Rev. A 95, 043415 (2017)]. The decelerator features a modular design with excellent thermal and vacuum properties, and is robustly operated at a 10 Hz repetition rate. We use this decelerator to demonstrate for the first time the state-selective deceleration of atomic oxygen to final mean velocities in the 500 125 m/s range. We characterize our decelerator further with molecular oxygen, which despite its heavier mass is velocity tuned in the 350 150 m/s range. This corresponds to a maximum kinetic energy reduction of 95% and 80% for atomic and molecular oxygen, respectively. The long multistage Zeeman decelerator presented here demonstrates that the concept of using alternating hexapoles and solenoids is truly phase stable. This Zeeman decelerator is ideally suited for applications in crossed beam scattering experiments; the state-selected and velocity controlled samples of O atoms and O2 molecules are particularly relevant for studies of inelastic and reactive processes.

Inelastic collisions that occur between open-shell atoms and other atoms or molecules, and that promote a spin–orbit transition, involve multiple interaction potentials. They are non-adiabatic by nature and cannot be described within the Born–Oppenheimer approximation; in particular, their theoretical modelling becomes very challenging when the collision energies have values comparable to the spin–orbit splitting. Here we study inelastic collisions between carbon in its ground state C( 3 P j =0 ) and helium atoms—at collision energies in the vicinity of spin–orbit excitation thresholds (~0.2 and 0.5 kJ mol −1 )—that result in spin–orbit excitation to C( 3 P j =1 ) and C( 3 P j =2 ). State-to-state integral cross-sections are obtained from crossed-beam experiments with a beam source that provides an almost pure beam of C( 3 P j =0 ) . We observe very good agreement between experimental and theoretical results (acquired using newly calculated potential energy curves), which validates our characterization of the quantum dynamical resonances that are observed. Rate coefficients at very low temperatures suitable for chemical modelling of the interstellar medium are also calculated.

We present a new concept for a multi-stage Zeeman decelerator that is optimized particularly for applications in molecular beam scattering experiments. The decelerator consists of a series of alternating hexapoles and solenoids, that effectively decouple the transverse focusing and longitudinal deceleration properties of the decelerator. It can be operated in a deceleration and acceleration mode, as well as in a hybrid mode that makes it possible to guide a particle beam through the decelerator at constant speed. The deceleration features phase stability, with a relatively large six-dimensional phase-space acceptance. The separated focusing and deceleration elements result in an unequal partitioning of this acceptance between the longitudinal and transverse directions. This is ideal in scattering experiments, which typically benefit from a large longitudinal acceptance combined with narrow transverse distributions. We demonstrate the successful experimental implementation of this concept using a Zeeman decelerator consisting of an array of 25 hexapoles and 24 solenoids. The performance of the decelerator in acceleration, deceleration and guiding modes is characterized using beams of metastable Helium (S) atoms. Up to 60% of the kinetic energy was removed for He atoms that have an initial velocity of 520 m/s. The hexapoles consist of permanent magnets, whereas the solenoids are produced from a single hollow copper capillary through which cooling liquid is passed. The solenoid design allows for excellent thermal properties, and enables the use of readily available and cheap electronics components to pulse high currents through the solenoids. The Zeeman decelerator demonstrated here is mechanically easy to build, can be operated with cost-effective electronics, and can run at repetition rates up to 10 Hz.

We demonstrate the successful experimental implementation of a multi-stage Zeeman decelerator utilizing the new concept described in the accompanying paper. The decelerator consists of an array of 25 hexapoles and 24 solenoids. The performance of the decelerator in acceleration, deceleration and guiding modes is characterized using beams of metastable Helium ($^3S$) atoms. Up to 60% of the kinetic energy was removed for He atoms that have an initial velocity of 520 m/s. The hexapoles consist of permanent magnets, whereas the solenoids are produced from a single hollow copper capillary through which cooling liquid is passed. The solenoid design allows for excellent thermal properties, and enables the use of readily available and cheap electronics components to pulse high currents through the solenoids. The Zeeman decelerator demonstrated here is mechanically easy to build, can be operated with cost-effective electronics, and can run at repetition rates up to 10 Hz.

We present a new concept for a multi-stage Zeeman decelerator that is optimized particularly for applications in molecular beam scattering experiments. The decelerator consists of a series of alternating hexapoles and solenoids, that effectively decouple the transverse focusing and longitudinal deceleration properties of the decelerator. It can be operated in a deceleration and acceleration mode, as well as in a hybrid mode that makes it possible to guide a particle beam through the decelerator at constant speed. The deceleration features phase stability, with a relatively large six-dimensional phase-space acceptance. The separated focusing and deceleration elements result in an unequal partitioning of this acceptance between the longitudinal and transverse directions. This is ideal in scattering experiments, which typically benefit from a large longitudinal acceptance combined with narrow transverse distributions. We demonstrate the successful experimental implementation of this concept using a Zeeman decelerator consisting of an array of 25 hexapoles and 24 solenoids. The performance of the decelerator in acceleration, deceleration and guiding modes is characterized using beams of metastable Helium ($^3S$) atoms. Up to 60 % of the kinetic energy was removed for He atoms that have an initial velocity of 520 m/s. The hexapoles consist of permanent magnets, whereas the solenoids are produced from a single hollow copper capillary through which cooling liquid is passed. The solenoid design allows for excellent thermal properties, and enables the use of readily available and cheap electronics components to pulse high currents through the solenoids. The Zeeman decelerator demonstrated here is mechanically easy to build, can be operated with cost-effective electronics, and can run at repetition rates up to 10 Hz

A joint crossed beam and quantum mechanical investigation of the rotationally inelastic collisions of CO with ortho- and para-D2 molecules is reported. A new 4D potential energy surface (PES) averaged over the ground vibrational states of D2 and CO is used to calculate the rovibrational bound states of the ortho-D2-CO complexes. Close coupling calculations are then performed in the rigid rotor approximation for ortho- and para-D2 colliding with CO for the experimentally investigated transition of CO (j = 0 → 1) and for collision energies ranging from 0.1 to 25 cm-1. The agreement between theory and experiment is found to be very good for both the bound state energies of the ortho-D2-CO complexes and for the inelastic scattering cross-sections showing that the free rotation of two rigid rotors is a very good model of the D2-CO system in this low collision energy domain.

The excitation function of the S((1)D) + D2 reaction was determined in a crossed molecular beam apparatus for collision energies ranging from 1817 to 47 J mol(-1) in the near-cold regime. A very good overall agreement was found between experimental data and the theoretical results obtained using the ab initio potential energy surface built by Ho and coworkers and different methods: time-independent quantum dynamics (QM), semiclassical mean potential capture theory (sc-MPCT), and quasi-classical trajectories (QCT). The general trend of the experimental excitation function is well reproduced in most of the range by a simple capture calculation with an R(-6) dispersion potential. The present results are discussed in the light of previous studies on the isotopic variants S((1)D) + H2 and HD.

Carbon monoxide is one of the most abundant components in many interstellar media and modeling its spectra requires knowledge of rate coefficients for the rotational (de-) excitation by collision with the dominant species in molecular regions, H-2. In this Letter, we report on experimental observation of resonances in the collisional excitation of CO by para- and ortho-H-2 at low collision energies characteristic of cold molecular clouds (down to a few Kelvin). Our experimental integral cross sections are compared to the results of new quantum mechanical scattering calculations performed using the highly accurate ab initio potential energy surface of Jankowski et al. Since the scattering calculations are very sensitive to the accuracy of the potential, especially when quantum resonances are involved, the quality of the agreement between theory and experiment reinforces the confidence in the observables derived from this potential energy surface, such as collisional rate coefficients calculated in the 1-20 K range.

In molecular collisions, resonances occur at specific energies at which the colliding particles temporarily form quasibound complexes, resulting in rapid variations in the energy dependence of scattering cross sections. Experimentally, it has proven challenging to observe such scattering resonances, especially in differential cross sections. We report the observation of resonance fingerprints in the state-to-state differential cross sections for inelastic NO-He collisions in the 13 to 19 centimeter(-1) energy range with 0.3 centimeter(-1) resolution. The observed structures were in excellent agreement with quantum scattering calculations. They were analyzed by separating the resonance contributions to the differential cross sections from the background through a partitioning of the multichannel scattering matrix. This revealed the partial-wave composition of the resonances and their evolution during the collision.

An experimental study has been carried out on the reactions of state selected O(+)((4)S, (2)D, (2)P) ions with methane with the aims of characterizing the effects of both the parent ion internal energy and collision energy on the reaction dynamics and determining the fate of oxygen species in complex media, in particular the Titan ionosphere. Absolute cross sections and product velocity distributions have been determined for the reactions of (16)O(+) or (18)O(+) ions with CH4 or CD4 from thermal to 5 eV collision energies by using the guided ion beam (GIB) technique. Dissociative photoionization of O2 with vacuum ultraviolet (VUV) synchrotron radiation delivered by the DESIRS beamline at the SOLEIL storage ring and the threshold photoion photoelectron coincidence (TPEPICO) technique are used for the preparation of purely state-selected O(+)((4)S, (2)D, (2)P) ions. A complete inversion of the product branching ratio between CH4(+) and CH3(+) ions in favor of the latter is observed for excitation of O(+) ions from the (4)S ground state to either the (2)D or the (2)P metastable state. CH4(+) and CH3(+) ions, which are by far the major products for the reaction of ground state and excited states, are strongly backward scattered in the center of mass frame relative to O(+) parent ions. For the reaction of O(+)((4)S), CH3(+) production also rises with increasing collision energy but with much less efficiency than with O(+) excitation. We found that a mechanism of dissociative charge transfer, mediated by an initial charge transfer step, can account very well for all the observations, indicating that CH3(+) production is associated with the formation of H and O atoms (CH3(+) + H + O) rather than with OH formation by an hydride transfer process (CH3(+) + OH). Therefore, as the CH4(+) production by charge transfer is also associated with O atoms, the fate of oxygen species in these reactions is essentially the O production, except for the reaction of O(+)((4)S), which also produces appreciable amounts of H2O(+) ions but only at very low collision energy. The production of O atoms and the nature of the states in which they are formed are discussed for the reactions of O(+) ions with CH4 and N2.

Context. Oxygen molecules (O2) are of particular interest because of their crucial role in astrochemisty. Modelling of O2 molecular emission spectra from interstellar clouds requires the calculation of rate coefficients for excitation by collisions with the most abundant species. Aims. Rotational excitation of O2(X 3 Σ − )b y H 2 is investigated theoretically and experimentally and we check the validity of the local thermodynamic equilibrium (LTE) approach for interpreting O2 observations. Methods. Using a new ab initio potential energy surface, collisional excitation of O2 is studied using a full close-coupling approach. The theoretical calculations are validated by comparison with crossed beam scattering experiments. We also performed calculations for the excitation of O2 from a large velocity gradient (LVG) radiative transfer code using the new rate coefficients. Results. State-to-state rate coefficients between the 27 lowest levels of O2 were calculated for temperatures ranging from 5 K to 150 K. The critical densities of the O2 lines are found to be at >10 4 cm −3 for temperatures higher than 50 K. This value is slightly larger than the one previously determined using previous He rate coefficients. Conclusions. The new rate coefficients will help in interpreting O2 emission lines observed where LTE conditions are not fully fulfilled and enable an accurate determination of the O2 abundance in the interstellar medium.

Les calculs theoriques prevoient que la dynamique d’excitation rotationnelle desmolecules CO et O2, induite par collision avec H2, est dominee par des resonancesquantiques aux tres basses energies. Leur mise en evidence experimentale estrendue difficile par la necessite d’obtenir des energies de collision tres faibles et unegrande resolution en energie. Les experiences menees grâce a un montage defaisceaux moleculaires croises a angle d’intersection variable, nous permettent ainsid’observer le seuil des transitions j = 0  1 de CO a 3,85 cm-1 et Nj = 10  11 de O2a 3,96 cm-1. Ces energies correspondent a l’energie cinetique moyenne d’un gaz aune temperature inferieure a 4 K. Les pics dans le trace des sections efficacesintegrales en fonction de l’energie de collision, constituent la premiere observationexperimentale de resonances pour des processus inelastiques. Le bon accord avecles calculs theoriques permet de valider les potentiels d’interaction et ainsi dededuire les constantes de vitesse pour la modelisation du milieu interstellaire. Nosresultats experimentaux mettent en relief la nature quantique des interactionsmoleculaires aux tres basses energies.

Partial wave resonances predicted to occur in bimolecular collision processes have proven challenging to observe experimentally. Here, we report crossed-beam experiments and quantum-scattering calculations on inelastic collisions between ground-state O-2 and H-2 molecules that provide state-to-state cross sections for rotational excitation of O-2 (rotational state N = 1, j = 0) to O-2 (N = 1, j = 1) in the vicinity of the thermodynamic threshold at 3.96 centimeter(-1). The close agreement between experimental and theoretical results confirms the classically forbidden character of this collision-induced transition, which occurs exclusively in a purely quantum mechanical regime via shape and Feshbach resonances arising from partial waves with total angular momentum (J) = 2 to 4.