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.

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 ultrasensitive benchmark for theory to reproduce, guiding the development of accurate theoretical models for the interaction of H 2 with a solid surface.

We recently presented the first attempt at using an asymmetric top molecule (para-water) to probe the superfluidity of nanoclusters (of para-hydrogen) [ Zeng , T. ; Li , H. ; Roy , P.-N. J. Phys. Chem. Lett. 2013 , 4 , 18 - 22 ]. Unfortunately, para-water could not be used to probe the para-hydrogen superfluid response. We now report a theoretical simulation of sulfur dioxide rotating in para-hydrogen clusters and show that this asymmetric top can serve as a genuine probe of superfluidity. With this probe, we predict that as few as four para-hydrogen molecules are enough to form a superfluid cluster, the smallest superfluid system to date. We also propose the concept of "exchange superfluid fraction" as a more precise measurement. New superfluid scenarios brought about by an asymmetric top dopant and potential experimental measurements are discussed.

It has become widely accepted that particles with long-range hopping do not undergo Anderson localization. However, several recent studies demonstrated localization of particles with long-range hopping. In particular, it was recently shown that the effect of long-range hopping in 1D lattices can be mitigated by cooperative shielding, which makes the system behave effectively as one with short-range hopping. Here, we show that cooperative shielding, demonstrated previously for 1D lattices, extends to 3D lattices with isotropic long-range r −α hopping, but not to 3D lattices with dipolar-like anisotropic long-range hopping. We demonstrate the presence of localization in 3D lattices with uniform (α = 0) isotropic long-range hopping and the absence of localization with uniform anisotropic long-range hopping by using the scaling behaviour of eigenstate participation ratios. We use the scaling behaviour of participation ratios and energy level statistics to show that the existence of delocalized, non-ergodic extended, or localized states in the presence of disorder depends on both the exponents α and the isotropy of the long-range hopping amplitudes.

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.

3 He beam spin-echo experiments have been used to study surface morphology, molecular and atomic surface diffusion, phonon dispersions, phason dispersions and phase transitions of ionic liquids. However, the interactions between 3 He atoms and surfaces or their adsorbates are typically isotropic and weak. To overcome these limitations, one can use molecules instead of 3 He in surface spin-echo experiments. The molecular degrees of freedom, such as rotation, may be exploited to provide additional insight into surfaces and the behaviour of their adsorbates. Indeed, a recent experiment has shown that ortho-hydrogen can be used as a probe that is sensitive to the orientation of a Cu(115) surface [Godsi et al., Nat. Comm. 8, 15357 (2017)]. However, the additional degrees of freedom offered by molecules also pose a theoretical challenge: a large manifold of molecular states and magnetic field-induced couplings between internal states. Here, we present a fully quantum mechanical approach to model molecular surface spin-echo experiments and connect the experimental signal to the elements of the time-independent molecule-surface scattering matrix. We present a one-dimensional transfer matrix method that includes the molecular hyperfine degrees of freedom and accounts for the spatial separation of the molecular wavepackets due to the magnetic control fields. We apply the method to the case of ortho-hydrogen, show that the calculated experimental signal is sensitive to the scattering matrix elements, and perform a preliminary comparison to experiment. This work sets the stage for Bayesian optimization to determine the scattering matrix elements from experimental measurements and for a framework that describes molecular surface spin-echo experiments to study dynamic surfaces.

No abstract

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 the 3He 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 future 3He spin-echo measurements.