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Chemisorbed species can enhance the fluxional dynamics of nanostructured metal surfaces which has implications for applications such as catalysis. Scanning tunneling microscopy studies at room temperature reveal that the presence of adsorbed sulfur (S) greatly enhances the decay rate of 2D Au islands in the vicinity of extended step edges on Au(111). This enhancement is already significant at S coverages, θ S , of a few hundredths of a monolayer (ML), and is most pronounced for 0.1-0.3 ML where the decay rate is increased by a factor of around 30. For θ S close to saturation at about 0.6 ML, sulfur induces pitting and reconstruction of the entire surface, and Au islands are stabilized. Enhanced coarsening at lower θ S is attributed to the formation and diffusion across terraces of Au-S complexes, particularly AuS 2 and Au 4 S 4 , with some lesser contribution from Au 3 S 4 . This picture is supported by density functional theory analysis of complex formation energies and diffusion barriers., (© 2020 Wiley-VCH GmbH.)

Ordering of different chalcogens, S, Se, and Te, on Au(111) exhibit broad similarities but also some distinct features, which must reflect subtle differences in relative values of the long-range pair and many-body lateral interactions between adatoms. We develop lattice-gas (LG) models within a cluster expansion framework, which includes about 50 interaction parameters. These LG models are developed based on density functional theory (DFT) analysis of the energetics of key adlayer configurations in combination with the Monte Carlo (MC) simulation of the LG models to identify statistically relevant adlayer motifs, i.e., model development is based entirely on theoretical considerations. The MC simulation guides additional DFT analysis and iterative model refinement. Given their complexity, development of optimal models is also aided by strategies from supervised machine learning. The model for S successfully captures ordering motifs over a broader range of coverage than achieved by previous models, and models for Se and Te capture the features of ordering, which are distinct from those for S. More specifically, the modeling for all three chalcogens successfully explains the linear adatom rows (also subtle differences between them) observed at low coverages of ∼0.1 monolayer. The model for S also leads to a new possible explanation for the experimentally observed phase with a (5 × 5)-type low energy electron diffraction (LEED) pattern at 0.28 ML and to predictions for LEED patterns that would be observed with Se and Te at this coverage.

Adsorbed sulfur has been investigated on the Ag(110) surface at two different coverages, 0.02 and 0.25 monolayers. At the lower coverage, only sulfur adatoms are present. At the higher coverage, there are additional bright features which we identify as linear, independent AgS 2 complexes. This identification is based upon density functional theory (DFT) and its comparison with experimental observations including bias dependence and separation between complexes. DFT also predicts the absence of AgS 2 complexes at low coverage, and the development of AgS 2 complexes around a coverage of 0.25 monolayers of sulfur, as is experimentally observed. To our knowledge, this is the first example of an isolated linear sulfur-metal-sulfur complex.

Experimental data from low-temperature Scanning Tunneling Microscopy (LTSTM) studies on coinage metal surfaces with very low coverages of S is providing new insights into metal-S interactions. A previous LTSTM study for Cu(100), and a new analysis reported here for Ag(100), both indicate no metal-sulfur complex formation, but an Au4S5 complex was observed previously on Au(100). In marked contrast, various complexes have been proposed and/or observed on Ag(111) and Cu(111), but not on Au(111). Also, exposure to trace amounts of S appears to enhance mass transport far more dramatically on (111) than on (100) surfaces for Cu and Ag, a feature tied to the propensity for complex formation. Motivated by these observations, we present a comprehensive assessment at the level of DFT to assess the existence and stability of complexes on (100) surfaces, and compare results with previous analyses for (111) surfaces. Consistent with experiment, our DFT analysis finds no stable complexes on Ag(100) and Cu(100), but several exist for Au(100). In addition, we systematically relate stability for adsorbed and gas-phase species within the framework of Hess's law. We thereby provide key insight into the various energetic contributions to stability which in turn elucidates the difference in behavior between (100) and (111) surfaces.

In this paper, we report that S atoms on Ag(100) and Ag(110) exhibit a distinctive range of appearances in scanning tunneling microscopy (STM) images, depending on the sample bias voltage, V S . Progressing from negative to positive V S , the atomic shape can be described as a round protrusion surrounded by a dark halo (sombrero) in which the central protrusion shrinks, leaving only a round depression. This progression resembles that reported previously for S atoms on Cu(100). We test whether DFT can reproduce these shapes and the transition between them, using a modified version of the Lang-Tersoff-Hamann method to simulate STM images. The sombrero shape is easily reproduced, but the sombrero-depression transition appears only for relatively low tunneling current and correspondingly realistic tip-sample separation, d T , of 0.5-0.8 nm. Achieving these conditions in the calculations requires sufficiently large separation (vacuum) between slabs, together with high energy cutoff, to ensure appropriate exponential decay of electron density into vacuum. From DFT, we also predict that an analogous transition is not expected for S atoms on Ag(111) surfaces. The results are explained in terms of the through-surface conductance, which defines the background level in STM, and through-adsorbate conductance, which defines the apparent height at the point directly above the adsorbate. With increasing V S , for Ag(100) and Ag(110), we show that through-surface conductance increases much more rapidly than through-adsorbate conductance, so the apparent adsorbate height drops below background. In contrast, for Ag(111) the two contributions increase at more comparable rates, so the adsorbate level always remains above background and no transition is seen.

Strong hydrogen bonds such as F···H···F offer new strategies to fabricate molecular architectures exhibiting novel structures and properties. Along these lines and, to potentially realize hydrogen-bond mediated superexchange interactions in a frustrated material, we synthesized [H 2 F] 2 [Ni 3 F 6 (Fpy) 12 ][SbF 6 ] 2 (Fpy = 3-fluoropyridine). It was found that positionally-disordered H 2 F + ions link neutral NiF 2 (Fpy) 4 moieties into a kagome lattice with perfect 3-fold rotational symmetry. Detailed magnetic investigations combined with density-functional theory (DFT) revealed weak antiferromagnetic interactions (J ~ 0.4 K) and a large positive-D of 8.3 K with m s = 0 lying below m s = ±1. The observed weak magnetic coupling is attributed to bond-disorder of the H 2 F + ions which leads to disrupted Ni-F···H-F-H···F-Ni exchange pathways. Despite this result, we argue that networks such as this may be a way forward in designing tunable materials with varying degrees of frustration.

Using scanning tunneling microscopy, we characterize the size and bias-dependent shape of sulfur atoms on Cu(100) at low coverage (below 0.1 monolayers) and low temperature (quenched from 300 to 5 K). Sulfur atoms populate the Cu(100) terraces more heavily than steps at low coverage, but as coverage approaches 0.1 monolayers, close-packed step edges become fully populated, with sulfur atoms occupying sites on top of the step. Density functional theory (DFT) corroborates the preferential population of terraces at low coverage as well as the step adsorption site. In experiment, small regions with p(2 × 2)-like atomic arrangements emerge on the terraces as sulfur coverage approaches 0.1 monolayer. Using DFT, a lattice gas model has been developed, and Monte Carlo simulations based on this model have been compared with the observed terrace configurations. A model containing eight pairwise interaction energies, all repulsive, gives qualitative agreement. Experiment shows that atomic adsorbed sulfur is the only species on Cu(100) up to a coverage of 0.09 monolayers. There are no Cu-S complexes. In contrast, prior work has shown that a Cu 2 S 3 complex forms on Cu(111) under comparable conditions. On the basis of DFT, this difference can be attributed mainly to stronger adsorption of sulfur on Cu(100) as compared with Cu(111).