A magnetically focused molecular beam source for deposition of spin-polarised molecular surface layers.

Separating molecular spin isomers is a challenging task, with potential applications in various fields ranging from astrochemistry to magnetic resonance imaging. A new promising method for spin-isomer separation is magnetic focusing, a method which was shown to be capable of producing a molecular beam of ortho-water. Here, we present results from a modified magnetic focusing apparatus and show that it can be used to separate the spin isomers of acetylene and methane. From the measured focused profiles of the molecular beams and a numerical simulation analysis, we provide estimations for the spin purity and the significantly improved molecular flux obtained with the new setup. Finally, we discuss the spin-relaxation conditions which will be needed to apply this new source for measuring nuclear magnetic resonance signals of a single surface layer.

Two-Dimensional Wetting of a Stepped Copper Surface.

Highly corrugated, stepped surfaces present regular 1D arrays of binding sites, creating a complex, heterogeneous environment to water. Rather than decorating the hydrophilic step sites to form 1D chains, water on stepped Cu(511) forms an extended 2D network that binds strongly to the steps but bridges across the intervening hydrophobic Cu(100) terraces. The hydrogen-bonded network contains pentamer, hexamer, and octomer water rings that leave a third of the stable Cu step sites unoccupied in order to bind water H down close to the step dipole and complete three hydrogen bonds per molecule.

How Atomic Steps Modify Diffusion and Inter-adsorbate Forces: Empirical Evidence from Hopping Dynamics in Na/Cu(115).

We followed the collective atomic-scale motion of Na atoms on a vicinal Cu(115) surface within a time scale of pico- to nanoseconds using helium spin echo spectroscopy. The well-defined stepped structure of Cu(115) allows us to study the effect that atomic steps have on the adsorption properties, the rate for motion parallel and perpendicular to the step edge, and the interaction between the Na atoms. With the support of a molecular dynamics simulation we show that the Na atoms perform strongly anisotropic 1D hopping motion parallel to the step edges. Furthermore, we observe that the spatial and temporal correlations between the Na atoms that lead to collective motion are also anisotropic, suggesting the steps efficiently screen the lateral interaction between Na atoms residing on different terraces.

Interpretation of surface diffusion data with Langevin simulations: a quantitative assessment.

Diffusion studies of adsorbates moving on a surface are often analyzed using 2D Langevin simulations. These simulations are computationally cheap and offer valuable insight into the dynamics, however, they simplify the complex interactions between the substrate and adsorbate atoms, neglecting correlations in the motion of the two species. The effect of this simplification on the accuracy of observables extracted using Langevin simulations was previously unquantified. Here we report a numerical study aimed at assessing the validity of this approach. We compared experimentally accessible observables which were calculated using a Langevin simulation with those obtained from explicit molecular dynamics simulations. Our results show that within the range of parameters we explored Langevin simulations provide a good alternative for calculating the diffusion procress, i.e. the effect of correlations is too small to be observed within the numerical accuracy of this study and most likely would not have a significant effect on the interpretation of experimental data. Our comparison of the two numerical approaches also demonstrates the effect temperature dependent friction has on the calculated observables, illustrating the importance of accounting for such a temperature dependence when interpreting experimental data.

Highly proton-ordered water structures on oxygen precovered Ru{0001}.

We present helium scattering measurements of a water ad-layer grown on a O(2 × 1)/Ru(0001) surface. The adsorbed water layer results in a well ordered helium diffraction pattern with systematic extinctions of diffraction spots due to glide line symmetries. The data reflects a well-defined surface structure that maintains proton order even at surprisingly high temperatures of 140 K. The diffraction data we measure is consistent with a structure recently derived from STM measurements performed at 6 K. Comparison with recent DFT calculation is in partial agreement, suggesting that these calculations might be underestimating the contribution of relative water molecule orientations to the binding energy.

A magnetically focused molecular beam of ortho-water.

Like dihydrogen, water exists as two spin isomers, ortho and para, with the nuclear magnetic moments of the hydrogen atoms either parallel or antiparallel. The ratio of the two spin isomers and their physical properties play an important role in a wide variety of research fields, ranging from astrophysics to nuclear magnetic resonance (NMR). Unlike ortho and para H(2), however, the two water isomers remain challenging to separate, and as a consequence, very little is currently known about their different physical properties. Here, we report the formation of a magnetically focused molecular beam of ortho-water. The beam we formed also had a particular spin projection. Thus, in the presence of holding magnetic fields, the water molecules are hyperpolarized, laying the foundation for ultrasensitive NMR experiments in the future.

Determination of the quantum contribution to the activated motion of hydrogen on a metal surface: H/Pt(111).

Measurements of the atomic-scale motion of H and D atoms on the Pt(111) surface, above the crossover temperature to deep tunneling, are presented. The results indicate that quantum effects are significant up to the highest temperature studied (250 K). The motion is shown to correspond to nearest neighbor hopping diffusion on a well defined fcc (111) lattice. The measurements provide information on the adiabatic potential of both the adsorption site and the transition state and give strong empirical support for a dissipative transition-state theory description of the quantum contribution to the motion.

Measuring surface phonons with a 3He spin echo spectrometer: a two-dimensional approach.

The helium spin echo spectrometer is a powerful apparatus for measuring surface dynamics and can be used in several different modes of operation. In this paper we present the first two-dimensional measurements of the wavelength intensity matrix, offering a new approach for studying surface phonons. The approach that we present is completely independent of the incident beam energy distribution and hence can be used to study inelastic scattering with ultra-high resolution. The additional insights obtained by using this new approach and its technical difficulties are discussed, and a comparison with other existing methods is given.

Studying the microscopic nature of diffusion with helium-3 spin-echo.

Helium-3 spin-echo (3HeSE) is a powerful, new experimental technique for studying dynamical phenomena at surfaces with ultra-high energy resolution. Resolution is achieved by using the 3He nuclear spin as an internal timer, to enable measurement of the energy changes of individual atoms as they scatter. The technique yields a measurement of surface correlation in reciprocal space and real time, and probes the nanometre length scales and picosecond to nanosecond timescales that are characteristic of many important atomistic processes. In this article we provide an introductory description of the 3HeSE technique for quasi-elastic scattering measurements and explain how it can be used to obtain unique insights into the motion of adsorbates. We illustrate the technique by reviewing recent measurements, starting with simple hopping and then showing how correlations, arising from adsorbate interactions, can be observed. The final measurements demonstrate how the absence of such correlations, when expected, are used to question the conventional description that attributes the coverage dependence of surface processes entirely to pairwise forces between adsorbates. The emphasis throughout is on the characteristic signatures of adsorbate motion that can be seen in the data, without recourse to a detailed theoretical analysis. Numerical simulations using the Langevin equation are used to illustrate generic behaviour and to provide a quantitative analysis of the experiment.

Linewidths in bound state resonances for helium scattering from Si(111)-(1 × 1)H.

Helium-3 spin-echo measurements of resonant scattering from the Si(111)-(1 × 1)H surface, in the energy range 4-14 meV, are presented. The measurements have high energy resolution yet they reveal bound state resonance features with uniformly broad linewidths. We show that exact quantum mechanical calculations of the elastic scattering, using the existing potential for the helium/Si(111)-(1 × 1)H interaction, cannot reproduce the linewidths seen in the experiment. Further calculations rule out inelastic and other mechanisms that might give rise to losses from the elastic scattering channels. We show that corrugation in the attractive part of the atom-surface potential is the most likely origin of the experimental lineshapes.

Analysis and refinement of the Cu(001) c(2 x 2)CO-He potential using (3)He selective adsorption resonances.

Measurements of (3)He scattering from the Cu(001)c(2 x 2)CO surface using (3)He spin-echo spectroscopy show a number of selective adsorption resonance features. The features cannot be reproduced by close coupled scattering calculations based on the existing Cu(001)c(2 x 2)CO-He interaction potential. An empirical potential is created by adjusting the shape, depth, and width of the existing potential to improve agreement with the experimental data.

A refined He-LiF(001) potential from selective adsorption resonances measured with high-resolution helium spin-echo spectroscopy.

The authors have developed a new experimental approach for measuring gas-surface selective adsorption resonances with much higher energy resolution and over a wider range of kinematic conditions than has previously been possible. The technique involves using a 3He spin-echo spectrometer as a Fourier transform helium atom scattering apparatus. The authors applied the technique to the He-LiF(001) system. They developed a new empirical potential for the He-LiF(001) system by analyzing and refining the best existing potentials in the light of the new data set. Following an initial free-particle model analysis, the authors used exact close coupling scattering calculations to compare the existing potentials with the new experimental data set. Systematic differences are observed between the two. The existing potentials are modified by simple transformations to give a refined potential that is consistent with and fully reproduces the experimental data. Their technique represents a new approach for developing very high precision empirical potentials in order to test first principles theory.

Onset of 3D collective surface diffusion in the presence of lateral interactions: Na/Cu(001).

3He spin-echo measurements are used to follow the picosecond motion of sodium atoms on a copper (001) substrate. 2D correlated motion arising from repulsive adsorbate interactions is observed for coverages as low as 0.04 ML. At coverages greater than 0.05 ML there is a pronounced onset of motion perpendicular to the surface. The perpendicular motion is thermally activated and seems related to the basic translational hopping diffusion process. The correlated motion is modeled successfully using a molecular dynamics simulation and a dipolelike lateral interaction. A simple model which relates the apparent height of the atom with its local coverage is shown to reproduce the experimental observations.

Observation of microscopic CO dynamics on Cu(001) using 3He spin-echo spectroscopy.

We present momentum resolved measurements of quasielastic helium atom scattering made using a new 3He spin-echo spectrometer. Our data for the dynamics of CO on Cu(001) indicates an activated jump mechanism which we analyze in detail using molecular dynamics simulations. A nearly isotropic potential energy surface is found with an average barrier height of approximately 125 meV, yielding comparable hopping rates along both the <110> and <100> directions. The measurements provide the first rigorous experimental test of state-of-the-art first-principles calculations previously made on this system.

Spatial mapping of mobility and density of the conduction electrons in (FA)2PF6

Novel implementation of the Fourier imaging technique on conduction electron spins in the one-dimensional organic conductors (FA)2PF6 (FA: fluoranthene) is reported. Two-dimensional spatial imaging of resolution 30 &mgr;m(2) is combined with the pulsed-gradient spin-echo technique, to derive maps revealing the local properties of the electron spin density and mobility. The maps generally show pronounced inhomogeneity of both density and mobility on the scale of approximately 30-300 &mgr;m. Highly mobile regions were identified to exist, and the mobility in these was quantitatively evaluated by a basic theoretical model of restricted diffusion.

Three-dimensional pulsed ESR Fourier imaging.

Three-dimensional pulsed ESR imaging was performed on a (FA)(2)PF(6) crystal using a three-dimensional Fourier imaging sequence. The best resolution achieved was of 20 microm(3). Comparison with images obtained using the filtered back-projection method shows the superiority of this method under the given conditions.