Diels–Alder cycloadditions are efficient routes for the synthesis of cyclic organic compounds. There has been a long-standing discussion whether these reactions proceed via stepwise or concerted mechanisms. Here, we adopt an experimental approach to explore the mechanism of the model polar cycloaddition of 2,3-dibromo-1,3-butadiene with propene ions by probing its conformational specificities in the entrance channel under single-collision conditions in the gas phase. Combining a conformationally controlled molecular beam with trapped ions, we find that both conformers of the diene, gauche and s-trans, are reactive with capture-limited reaction rates. Aided by quantum-chemical and quantum-capture calculations, this finding is rationalised by a simultaneous competition of concerted and stepwise reaction pathways, revealing an interesting mechanistic borderline case.

The structure and quantum state of the reactants have a profound impact on the kinetics and dynamics of chemical reactions. Over the past years, significant advances have been made in the control and manipulation of molecules with external electric and magnetic fields in molecular-beam experiments for investigations of their state-, structure-and energy-specific chemical reactivity. Whereas studies for neutrals have so far mainly focused on weak-field-seeking species, we report here progress towards investigating reactions of strong-field-seeking molecules by introducing a novel crossed-molecular-beam experiment featuring an electrostatic deflector. The new setup enables the characterisation of state-and geometry-specific effects in reactions under single-collision conditions. As a proof of principle, we present results on the chemi-ionisation reaction of metastable neon atoms with rotationally state-selected carbonyl sulfide (OCS) molecules and show that the branching ratio between the Penning and dissociative ionisation pathways strongly depends on the initial rotational state of OCS.

We present and compare two high-pressure, high-frequency electric-discharge sources for the generation of supersonic beams of fluorine radicals. The sources are based on dielectric-barrier-discharge (DBD) and plate-discharge units attached to a pulsed solenoid valve. The corrosion-resistant discharge sources were operated with fluorine gas seeded in helium up to backing pressures as high as 30 bar. We employed a (3+1) resonance-enhanced multiphoton ionization combined with velocity-map imaging for the optimization, characterization and comparison of the fluorine beams. Additionally, universal femtosecond-laser-ionization detection was used for the characterization of the discharge sources at experimental repetition rates up to 200 Hz. Our results show that the plate discharge is more efficient in F 2 dissociation than the DBD by a factor of 8-9, whereas the DBD produces internally colder fluorine radicals.

Substrates comprising heteroepitaxially grown single-crystalline diamond epilayers were used to fabricate pseudovertical Schottky diodes. These consisted of Ti/Pt/Au contacts on p− Boron-doped diamond (BDD) layers (1015–1016 cm−3) with varying thicknesses countered by ohmic contacts on underlying p+ layers (1019–1020 cm−3) on the quasi-intrinsic diamond starting substrate. Whereas the forward current exhibited a low-voltage shunt conductance and, for higher voltages, thermionic emission behavior with systematic dependence on the p− film thickness, the reverse leakage current appeared to be space-charge-limited depending on the existence of local channels and thus local defects, and depending less on the thickness. For the Schottky barriers ϕSB, a systematic correlation to the ideality factors n was observed, with an “ideal” n = 1 Schottky barrier of ϕSB = 1.43 eV. For the best diodes, the breakdown field reached 1.5 MV/cm.

Recent advances in experimental methodology enabled studies of the quantum-state- and conforma- tional dependence of chemical reactions under precisely controlled conditions in the gas phase. Here, we generated samples of...