Molecular spin echoes; multiple magnetic coherences in molecule surface scattering experiments.

In this paper we demonstrate that a molecular beam of hydrogen molecules can be magnetically manipulated to produce multiple coherences in the molecular interference pattern. Unlike spin 1/2 magnetic beam experiments, i.e., neutron and helium spin echo, the nuclear and rotational magnetic moments in a molecule are strongly coupled. We show experimentally and theoretically that this coupling leads to multiple magnetic field conditions under which the magnetic moment of molecules travelling with different speeds can be coherently refocussed. We also demonstrate that these multiple coherence signals are extremely sensitive to the scattering event, opening up new possibilities for measuring molecule-surface interactions.

Multiple echoes in beam spin-echo spectroscopy and their effect on measurements of ultra-fast dynamics.

Helium (3He) spin-echo is a powerful experimental technique used to probe ultra-fast atomic scale surface dynamics. The analysis of these measurements is typically performed assuming there is only a single spin-echo condition, expected to produce a constant signal for pure elastic scattering, a monotonically decaying signal for quasi-elastic scattering and oscillations from inelastic scattering events. In the present work, we show that there are in fact four spin-echoes which must be correctly accounted for, and that even in the case of elastic scattering these additional echoes lead to oscillations which could mistakenly be interpreted as being due to inelastic scattering. We demonstrate that it is possible to accurately simulate the experimental data by propagating the3He through the measured magnetic field profile of the apparatus and considering the geometry of the machine, allowing the effect of these additional echoes to be disentangled from inelastic scattering events in future3He spin-echo measurements.

Stopping molecular rotation using coherent ultra-low-energy magnetic manipulations.

Rotational motion lies at the heart of intermolecular, molecule-surface chemistry and cold molecule science, motivating the development of methods to excite and de-excite rotations. Existing schemes involve perturbing the molecules with photons or electrons which supply or remove energy comparable to the rotational level spacing. Here, we study the possibility of de-exciting the molecular rotation of a D2 molecule, from J = 2 to the non-rotating J = 0 state, without using an energy-matched perturbation. We show that passing the beam through a 1 m long magnetic field, which splits the rotational projection states by only 10-12 eV, can change the probability that a molecule-surface collision will stop a molecule from rotating and lose rotational energy which is 9 orders larger than that of the magnetic manipulation. Calculations confirm that different rotational orientations have different de-excitation probabilities but underestimate rotational flips (∆mJ[Formula: see text]0), highlighting the importance of the results as a sensitive benchmark for further developing theoretical models of molecule-surface interactions.

Setting benchmarks for modelling gas-surface interactions using coherent control of rotational orientation states.

The coherent evolution of a molecular quantum state during a molecule-surface collision is a detailed descriptor of the interaction potential which was so far inaccessible to measurements. Here we use a magnetically controlled molecular beam technique to study the collision of rotationally oriented ground state hydrogen molecules with a lithium fluoride surface. The coherent control nature of the technique allows us to measure the changes in the complex amplitudes of the rotational projection quantum states, and express them using a scattering matrix formalism. The quantum state-to-state transition probabilities we extract reveal a strong dependency of the molecule-surface interaction on the rotational orientation of the molecules, and a remarkably high probability of the collision flipping the rotational orientation. The scattering matrix we obtain from the experimental data delivers an ultra-sensitive benchmark for theory to reproduce, guiding the development of accurate theoretical models for the interaction of H2 with a solid surface.

A general method for controlling and resolving rotational orientation of molecules in molecule-surface collisions.

The outcome of molecule-surface collisions can be modified by pre-aligning the molecule; however, experiments accomplishing this are rare because of the difficulty of preparing molecules in aligned quantum states. Here we present a general solution to this problem based on magnetic manipulation of the rotational magnetic moment of the incident molecule. We apply the technique to the scattering of H2 from flat and stepped copper surfaces. We demonstrate control of the molecule's initial quantum state, allowing a direct comparison of differences in the stereodynamic scattering from the two surfaces. Our results show that a stepped surface exhibits a much larger dependence of the corrugation of the interaction on the alignment of the molecule than the low-index surface. We also demonstrate an extension of the technique that transforms the set-up into an interferometer, which is sensitive to molecular quantum states both before and after the scattering event.