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Using scanning tunneling microscopy, we observe an adlayer structure that is dominated by short rows of S atoms, on unreconstructed regions of a Au(111) surface. This structure forms upon adsorption of low S coverage (less than 0.1 monolayer) on a fully reconstructed clean surface at 300 K, then cooling to 5 K for observation. The rows adopt one of three orientations that are rotated by 30 from the close-packed directions of the Au(111) substrate, and adjacent S atoms in the rows are separated by √ 3 times the surface lattice constant, a. Monte Carlo simulations are performed on lattice-gas models, derived using a limited cluster expansion based on density functional theory energetics. Models which include long-range pairwise interactions (extending to 5a), plus selected trio interactions, successfully reproduce the linear rows of S atoms at reasonable temperatures. [ABSTRACT FROM AUTHOR]

A rich menagerie of structures is identified at 5 K following adsorption of low coverages (≤0.05 monolayers) of S on Cu(111) at room temperature. This paper emphasizes the reconstructions at the steps. The A-type close-packed step has 1 row of S atoms along its lower edge, where S atoms occupy alternating pseudo-fourfold-hollow (p4fh) sites. Additionally, there are 2 rows of S atoms of equal density on the upper edge, bridging a row of extra Cu atoms, together creating an extended chain. The B-type close-packed step exhibits an even more complex reconstruction, in which triangle-shaped groups of Cu atoms shift out of their original sites and form a base for S adsorption at (mostly) 4fh sites. We propose a mechanism by which these triangles could generate Cu-S complexes and short chains like those observed on the terraces. [ABSTRACT FROM AUTHOR]

Threshold versions of Schloegl's model on a lattice, which involve autocatalytic creation and spontaneous annihilation of particles, can provide a simple prototype for discontinuous non-equilibrium phase transitions. These models are equivalent to so-called threshold contact processes. A discontinuous transition between populated and vacuum states can occur selecting a threshold of N ≥ 2 for the minimum number, N, of neighboring particles enabling autocatalytic creation at an empty site. Fundamental open questions remain given the lack of a thermodynamic framework for analysis. For a square lattice with N = 2, we show that phase coexistence occurs not at a unique value but for a finite range of particle annihilation rate (the natural control parameter). This generic two-phase coexistence also persists when perturbing the model to allow spontaneous particle creation. Such behavior contrasts both the Gibbs phase rule for thermodynamic systems and also previous analysis for this model. We find metastability near the transition corresponding to a non-zero effective line tension, also contrasting previously suggested critical behavior. Mean-field type analysis, extended to treat spatially heterogeneous states, further elucidates model behavior. [ABSTRACT FROM AUTHOR]

We explore simple lattice-gas reaction models for CO-oxidation on 1D and 2D periodic arrays of surface adsorption sites with CO adsorption and desorption, dissociative O2 adsorption and recombinative desorption (at low rate), and CO + O reaction to form CO2. Adspecies interactions are neglected, and adspecies diffusion is effectively absent. The models are motivated by studies of CO-oxidation on RuO2(110) at high-pressures. Despite the lack of adspecies interactions, negligible adspecies diffusion results in kinetically induced spatial correlations. A transition occurs from a random primarily CO-populated steady-state at high CO-partial pressure, pCO, to a strongly correlated near-O-covered steady-state for low pCO as noted by Matera et al. [J. Chem. Phys. 134, 064713 (2011)]. In addition, we identify a second transition to a random near-O-covered steady-state at very low pCO. Furthermore, we identify and analyze the slow "diffusive dynamics" for very low pCO and provide a detailed characterization of the crossover to the strongly correlated O-covered steady-state as well as of the spatial correlations in that state. [ABSTRACT FROM AUTHOR]

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 x 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 Cu2S3 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). [ABSTRACT FROM AUTHOR]

Tailored multisite lattice-gas (msLG) models are developed for CO oxidation on Pd(100) at low-pressures. These models include multiple adsorption site types and superlattice adlayer ordering due to short-range exclusion for highly mobile reactant adspecies. However, they are simplified to neglect longer-range weaker adspecies interactions, so that the key energetic parameters are the CO desorption barrier and the reaction barrier. We discuss existing density functional theory results for these energies and present additional analysis for CO adsorption. After also including an appropriate nontrivial specification of the dynamics of adsorption onto mixed reactant adlayers, we develop rate equations for the reaction kinetics. Our formulation goes beyond traditional mean-field (MF) Langmuirian treatments by accounting for multiple adsorption sites and for the strong spatial correlations associated with superlattice ordering. Specifically, we utilize factorization approximations based on appropriate site motifs, and also Padé resummation of exact low-coverage expansions for sticking coefficients. Our beyond-MF rate equations are successful in accurately predicting key aspects of reactive steady-state behavior, and thus expand the utility of rate equation formulations in surface chemistry. This is confirmed by comparison with precise kinetic Monte Carlo simulation results. Specifically, we not only assess bistability and criticality observed for CO oxidation but also find more complex multistability associated with symmetry-breaking transitions in high-coverage CO adlayers. [ABSTRACT FROM AUTHOR]

The article discusses the stochastic modeling of catalytic reaction-diffusion processes in nonporous materials and 2D surface. Topics discussed include analysis of basic irreversible first-order conversion reaction in a 1D linear nanopore, multi-site lattice gas modeling of oxidation reactions on metal catalyst surfaces at low pressure and analysis of catalytic reactions on metal oxide surfaces.

Sulfur-metal complexes, containing only a few atoms, can open new, highly efficient pathways for transport of metal atoms on surfaces. For example, they can accelerate changes in the shape and size of morphological features, such as two-dimensional nanoclusters, over time. In this study we perform STM under conditions that are designed to specifically isolate such complexes. We find a new, unexpected S-Cu complex on the Cu(111) surface, which we identify as Cu2S3. We propose that Cu2S3 enhances mass transport in this system, which contradicts a previous proposal based on Cu3S3. We analyze bonding within these Cu-S complexes, identifying a principle for stabilization of sulfur complexes on coinage metal surfaces. [ABSTRACT FROM AUTHOR]

The dynamics of nanoscale clusters can be distinct from macroscale behavior described by continuum formalisms. For diffusion of 2D clusters of N atoms in homoepitaxial systems mediated by edge atom hopping, macroscale theory predicts simple monotonic size scaling of the diffusion coefficient, DN - Nβ , with β = 3/2. However, modeling for nanoclusters on metal(100) surfaces reveals that slow nucleation-mediated diffusion displaying weak size scaling β < 1 occurs for "perfect" sizes Np = L2 and L(L+1) for integer L = 3,4,. . . (with unique square or near-square ground state shapes) and also for Np+3, Np+4,. . . . In contrast, fast facile nucleation-free diffusion displaying strong size scaling β≈2.5 occurs for sizesNp+1 andNp+2.DN versusNoscillates strongly between the slowest branch (for Np+3) and the fastest branch (for Np+1). All branches merge for N = O(102), but macroscale behavior is only achieved for much larger N = O(103). This analysis reveals the unprecedented diversity of behavior on the nanoscale. [ABSTRACT FROM AUTHOR]

We consider Schloegl models (or contact processes) where particles on a square grid annihilate at a rate p and are created at a rate of kn=n(n-1)/[N(N-1)] at empty sites with n particles in a neighborhood ΩN of size N. Simulation reveals a discontinuous transition between populated and vacuum states, but equistable p=peq determined by the stationarity of planar interfaces between these states depends on the interface orientation and on ΩN. The behavior for large ΩN follows from continuum equations. These also depend on the interface orientation and on ΩN shape, but a unique peq=0.211 376 320 4 emerges imposing a Gibbs phase rule. [ABSTRACT FROM AUTHOR]

For diffusion of two-dimensional homoepitaxial clusters of N atoms on metal (100) surfaces mediated by edge atom hopping, macroscale continuum theory suggests that the diffusion coefficient scales like DN ~N -β with β = 3/2. However, we find quite different and diverse behavior in multiple size regimes. These include: (i) facile diffusion for small sizes N < 9 ; (ii) slow nucleation-mediated diffusion with small β < 1 for "perfect" sizes N = Np = L2 or L(L+1), for L = 3, 4, ... having unique ground-state shapes, for moderate sizes 9 ≤ N ≤ O (102); the same also applies for N = Np+3,Np+4, ... (iii) facile diffusion but with large β > 2 for N = Np+1 andNp+ 2 also for moderate sizes 9 ≤ N ≤ O (102); (iv) merging of the above distinct branches and subsequent anomalous scaling with 1 ≲ β < 3/2, reflecting the quasifacetted structure of clusters, for larger N = O (102) to N = O (103) ; (v) classic scaling with β = 3/2 for very large N = O (103) and above. The specified size ranges apply for typical model parameters. We focus on the moderate size regime where we show that diffusivity cycles quasiperiodically from the slowest branch forNp+ 3 (notNp) to the fastest branch forNp+ 1. Behavior is quantified by kinetic Monte Carlo simulation of an appropriate stochastic lattice-gas model. However, precise analysis must account for a strong enhancement of diffusivity for short time increments due to back correlation in the cluster motion. Further understanding of this enhancement, of anomalous size scaling behavior, and of the merging of various branches, is facilitated by combinatorial analysis of the number of the ground-state and low-lying excited state cluster configurations, and also of kink populations. [ABSTRACT FROM AUTHOR]

In order to gain insight into the nature of chemical bonding of sulfur atoms on coinage metal surfaces, we compare the adsorption energy and structural parameters for sulfur at four-fold hollow (4fh) sites on (100) facets and at three-fold hollow (3fh) sites on (111) facets of Cu nanoclusters. Consistent results are obtained from localized atomic orbital and plane-wave based density functional theory using the same functionals. PBE and its hybrid counterpart (PBE0 or HSE06) also give similar results. 4fh sites are preferred over 3fh sites with stronger bonding by ~0.6 eV for nanocluster sizes above ~280 atoms. However, for smaller sizes there are strong variations in the binding strength and the extent of the binding site preference. We show that suitable averaging over clusters of different sizes, or smearing the occupancy of orbitals, provide useful strategies to aid assessment of the behavior in extended surface systems. From site-projected density of states analysis using the smearing technique, we show that S adsorbed on a 4fh site has similar bonding interactions with the substrate as that on a 3fh site, but with much weaker antibonding interactions. [ABSTRACT FROM AUTHOR]