Based on the fact that the underpotential electrochemical deposition of Ag atoms on the $Au(100)$ surface exhibits sharp first-order phase transitions at well-defined values of the (coexistence) chemical potential ($μ_{coex}$), we performed extensive simulations aimed at investigating the hysteretic dynamic behavior of the system close to coexistence upon the application of a periodic signal of the form $μ(t) = μ_{coex} + μ_{o}sin(2Πt/τ) $, where $μ_{o}$ and $τ$ are the amplitude and the period of the sweep, respectively. For relatively short periods and small enough amplitudes the system becomes trapped either at low or high Ag coverage states, as evidenced by recording hysteresis loops. This scenario is identified as dynamically ordered states (DOS), such that the relaxation time $(τ_{relax})$ of the corresponding metastable state obeys $τ_{relax} > τ$. On the other hand, by properly increasing $μ_{o}$ or/and $τ$, one finds that the $Ag$ coverage gently follows the external drive (here $τ_{relax} < τ$) and the system is said to enter into dynamically disordered states (DDS), where hysteresis loops show almost symmetric limiting cycles. This symmetry breaking between limiting cycles driven by an external signal is discussed in terms of the concept of (out-of-equilibrium) Dynamic Phase Transitions between DOS and DDS, similar to those encountered when a magnetic system is placed in the presence of a variable external magnetic field. However, a careful finite-size scaling study reveals that, at least at $T = 300K$, the $Ag/Au(100)$ system does not exhibit true second-order phase transitions but rather a crossover behavior between states. A diagram showing the location of the ordered and disordered states in the $μ$ versus $τ$ plane is obtained and discussed.
We overview recent results on intrinsic frictional properties of adsorbed monolayers, composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of a dynamical master equation approach we determine the velocity of a biased impure molecule - the tracer particle (TP), constrained to move inside the adsorbed monolayer probing its frictional properties, define the frictional forces exerted by the monolayer on the TP, as well as the particles density distribution in the monolayer.
We study the response of an adsorbed monolayer under a driving force as a model of sliding friction phenomena between two crystalline surfaces with a boundary lubrication layer. Using Langevin-dynamics simulation, we determine the nonlinear response in the direction transverse to a high symmetry direction along which the layer is already sliding. We find that below a finite transition temperature, there exist a critical depinning force and hysteresis effects in the transverse response in the dynamical state when the adlayer is sliding smoothly along the longitudinal direction.
Simulation evidence of an incipient triple point is reported for xenon submonolayers adsorbed on the (111) surface of platinum. This is in stark contrast to the "normal" triple point found in simulations and experiments for xenon on the basal plane surface of graphite. The motions of the atoms in the surface plane are treated with standard 2D "NVE" molecular dynamics simulations using modern interactions. The simulation evidence strongly suggests an incipient triple point in the 120-150 K range for adsorption on the Pt (111) surface while the adsorption on graphite shows a normal triple point …
We comment and discuss the findings and conclusions of a recent theoretical study of the diffraction of He atoms from a monolayer of Xe atoms adsorbed on the graphite (0001) surface [Khokonov et al., Surf. Sci. 496(2002)L13]. By revisiting the problem we demonstrate that all main conclusions of Khokonov et al. that pertain to the studied system are at variance with the available experimental and theoretical evidence and the results of multiple scattering calculations presented in this comment.
We present the first large-scale molecular dynamics simulations of hexane on graphite that completely reproduces all experimental features of the melting transition. The canonical ensemble simulations required and used the most realistic model of the system: (i) fully atomistic representation of hexane; (ii) explicit site-by-site interaction with carbon atoms in graphite; (iii) CHARMM force field with carefully chosen adjustable parameters of non-bonded interaction; (iv) numerous $\ge$ 100 ns runs, requiring a total computation time of ca. 10 CPU-years. This has allowed us to determine correct…
We examine the hydrodynamic phonon spectrum of a monolayer film adsorbed on the wall of a spherical pore. Due to the boundary conditions, the monolayer film exhibits a discrete phonon spectrum. The corresponding density of states per unit frequency is thus a set of delta functions and the heat capacity exhibits Arrhenius behavior at low temperatures. At high temperatures, the heat capacity approaches the C ~ T^2 behavior of a two-dimensional monolayer film. Our results for the spherical surface film are compared to previous calculations for films confined to a cylindrical surface.
In the present paper we overview our recent results on intrinsic frictional properties of adsorbed monolayers, composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. Within the framework of a dynamical master equation approach, describing the time evolution of the system, we determine in the most general form the terminal velocity of some biased impure molecule - the tracer particle (TP), constrained to move inside the adsorbed monolayer probing its frictional properties, define the frictional forces as well as the particles density distribution in the monol…
We study dynamics of a probe particle, which performs biased diffusive motion in a one-dimensional adsorbed monolayer of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of a mean-field-type approach, based on the decoupling of the third-order correlation functions into a product of the pairwise correlations, we determine analytically the density profiles of the monolayer particles, as seen from the stationary moving probe, and calculate the terminal velocity, mobility and the self-diffusion coefficient of the probe. Our analytical results are confirmed b…
We study the intrinsic friction of monolayers adsorbed on solid surfaces from a gas phase or vapor. Within the framework of the Langmuir model of delocalized adsorption, we calculate the resistance offered by the mobile adsorbate's particles to some impure tracer molecule, whose diffusive random motion is biased by a constant external force. We find that for sufficiently small driving forces the force exerted on the tracer shows viscous-like behavior. We derive then the analog of the Stokes formula for two-dimensional adsorbates, calculate the corresponding friction coefficient and determine t…
Quantum Monte Carlo simulations at zero temperature of a $^3$He monolayer adsorbed on graphite, either clean or preplated with $^4$He, unexpectedly point to a gas-liquid phase transition at a very low areal density of the order of 0.01Å$^{-2}$. This result stems from an essentially unbiased calculation of the ground state energy for an infinite, defect-free substrate which interacts with He atoms via a realistic potential, whereas the interaction between two He atoms includes two- and three-body terms. The sensitivity of the gas-liquid coexistence region on the model Hamiltonian employed is di…
We consider a deposition model in which balls rain down at random towards a 2-dimensional surface, roll downwards over existing adsorbed balls, are adsorbed if they reach the surface, and discarded if not. We prove a spatial law of large numbers and central limit theorem for the ultimate number of balls adsorbed onto a large toroidal surface, and also for the number of balls adsorbed on the restriction to a large region of an infinite surface.
In this paper, which completes our earlier short publication [Phys. Rev. Lett. 84, 511 (2000)], we study dynamics of a hard-core tracer particle (TP) performing a biased random walk in an adsorbed monolayer, composed of mobile hard-core particles undergoing continuous exchanges with a vapor phase. In terms of an approximate approach, based on the decoupling of the third-order correlation functions, we obtain the density profiles of the monolayer particles around the TP and derive the force-velocity relation, determining the TP terminal velocity, V_{tr}, as the function of the magnitude of exte…
The interplay between the torsional potential energy and the scaling of the 1-4 van der Waals and Coulomb interactions determines the stiffness of flexible molecules. In molecular simulations often ad-hoc values for the scaling factor (SF) are adopted without adequate justification. In this letter we demonstrate for the first time that the precise value of the SF has direct consequences on the critical properties and mechanisms of systems undergoing a phase transition. By analyzing the melting of n-alkanes (hexane C6, dodecane C12, tetracosane C24) on graphite, we show that the SF is not a uni…
We discuss Molecular Dynamics (MD) computer simulations of tetracosane (C24H50) monolayer physisorbed onto a graphite surface. The alkane molecules are simulated with explicit hydrogens, and the graphite substrate is represented as an all-atom struc-ture having six graphene layers. The tetracosane dynamics modeled in the fully ato-mistic manner agree well with experiment. The low-temperature ordered solid orga-nizes in rectangular centered structure, incommensurate with underlying graphite. Above T = 200 K, as the molecules start to lose their translational and orientational order via gauche d…
We study the response of an adsorbed monolayer on a disordered substrate under a driving force using Brownian molecular-dynamics simulation. We find that the sharp longitudinal and transverse depinning transitions with hysteresis still persist in the presence of weak disorder. However, the transitions are smeared out in the strong disorder limit. The theoretical results here provide a natural explanation for the recent data for the depinning transition of Kr films on gold substrate.
We study the dynamics of a tracer particle, which performs a totally directed random walk in an adsorbed monolayer composed of mobile hard-core particles undergoing continuous exchanges with a vapour phase. In terms of a mean-field-type approach, based on the decoupling of the tracer-particle-particle correlation functions into the product of pairwise, tracer-particle correlations, we determine the density profiles of the monolayer particles, as seen from the stationary moving tracer, and calculate its terminal velocity, V_{tr}. In the general case the latter is determined implicitly, as the s…
X-ray reflectivity measurements of the binary liquid Ga-Bi alloy reveal a dramatically different surface structure above and below the monotectic temperature $T_{mono}=222^{\circ}$ C. A Gibbs-adsorbed Bi monolayer resides at the surface at both regimes. However, a 30 Å thick, Bi-rich wetting film intrudes between the Bi monolayer and the Ga-rich bulk for $T > T_{mono}$. The internal structure of the wetting film is determined with Å resolution, showing a theoretically unexpected concentration gradient and a highly diffuse interface with the bulk phase.
Monolayers of the halomethane CF$_3$Br adsorbed on graphite have been investigated by x-ray diffraction. The layers crystallize in a commensurate triangular lattice. On cooling they approach a three-sublattice antiferroelectric pattern of the in-plane components of the dipole moments. The ordering is not consistent with a conventional phase transition, but points to Kosterlitz-Thouless behavior. It is argued that the transition is described by a 6-state clock model on a triangular lattice with antiferromagnetic nearest neighbor interactions which is studied with Monte-Carlo simulations. A fini…
The superfluid transition of $^3$He-$^4$He mixture films adsorbed on alumina powder is studied, with a $^4$He superfluid coverage near one layer. With up to 1.3 layers of $^3$He added, the transition becomes strongly broadened, indicating a linear increase in the vortex core size for $^3$He coverages below one layer. Annealing of the sample mixture at 4.2 K is found to be critically important in ensuring a homogeneous film across the porous substrate.
We investigate the first layer of helium adsorbed on graphite with path-integral Monte Carlo, examining the role of substrate corrugations on the phase diagram. When no corrugations are present, the equilibrium state of the system is a liquid phase, with solidification occurring only under compression but before layer promotion. We determine the solid-liquid coexistence region and compare our results to recent Green's function Monte Carlo calculations on the same system. When substrate corrugations are included, we find that the equilibrium phase is the $\sqrt 3 \times \sqrt3$ commensurate sol…
The phase behaviour and structural properties of a monolayer of hard particles is examined in such a confinement, where the adsorbed particles are constrained to the surface of a narrow hard cylindrical pore. The diameter of the pore is chosen such that only first and second neighbour interactions occur between the hard particles. The transfer operator method of Percus and Zhang [Mol. Phys., 69, 347 (1990)] is reformulated to obtain information about the structure of the monolayer. We have found that a true phase transition is not possible in the examined range of pore diameters. The monolayer…
Graphene-based nanostructured systems and van-der-Waals heterostructures comprise a material class of growing technological and scientific importance. Joining materials with vastly different properties, polymer-graphene heterosystems promise diverse applications in surface- and nanotechnology, including photovoltaics or nanotribology. Fundamentally, molecular adsorbates are prototypical systems to study confinement-induced phase transitions exhibiting intricate dynamics, which require a comprehensive understanding of the dynamical and static properties on molecular time and length scales. Here…
