First-principles molecular dynamics simulation of biased electrode/solution interface

First-principles molecular dynamics simulations have been carried out for water in contact with Pt(1 1 1) surface. To apply negative bias potential to the water/Pt interface, excess electrons were added to our slab model using the recently developed computational scheme called “effective screening medium (ESM)”. Water molecules located away from the surface reoriented themselves to screen the electric field, but they responded differently near the surface. Water molecules nearest to the surface, forming a distinct layered structure with the hydrogen atom directed to the surface, increased the density with increasing field. On these bases, we discuss microscopic aspects of the electric double layer.     

Nonlinear mobility of a driven system: Temperature and disorder effects

We consider the dissipative nonlinear dynamics of a model of interacting atoms driven over a substrate potential. The substrate parameters can be suitably tuned in order to introduce disorder effects starting from two geometrically opposed ideal cases: commensurate and incommensurate interfaces. The role of temperature is also investigated through the inclusion of a stochastic force via a Langevin molecular dynamics approach. Here, we focus on the most interesting tribological case of underdamped sliding dynamics. For different values of the chain stiffness, we evaluate the static friction threshold and consider the depinning transition mechanisms as a function of the applied driving force. As experimentally observed in QCM frictional measurements of adsorbed layers, we find that disorder operates differently depending on the starting geometrical configuration. For commensurate interfaces, randomness lowers considerably the chain depinning threshold. On the contrary, for incommensurate mating contacts, disorder favors static pinning destroying the possible frictionless (superlubric) sliding states. Interestingly, thermal and disorder effects strongly influence also the occurrence of parametric resonances inside the chain, capable of converting the kinetic energy of the center-of-mass motion into internal vibrational excitations. We comment on the nature of the different dynamical states and hysteresis (due to system bi-stability) observed at different increasing and decreasing strengths of the external force.     

Methods for calculating the desorption rate of an isolated molecule from a surface: Water on MgO(0 0 1)

We present two types of Molecular Dynamics (MD) simulation for calculating the desorption rate of molecules from a surface. In the first, the molecules move freely between two surfaces, and the desorption rate is obtained either by counting the number of desorption events in a given time, or by looking at the average density of the molecules as a function of distance from the surface and then applying transition state theory (TST). In the second, the potential of mean force (PMF) for a molecule is determined as a function of distance from the surface and the desorption rate is obtained by means of TST. The methods are applied to water on the MgO(0 0 1) surface at low coverage. Classical potentials are used so that long simulations can be performed, to minimise statistical errors. The two sets of MD simulations agree well at high temperatures. The PMF method reproduces the 0 K adsorption energy of the molecule to within 5 meV, and finds that the well depth of the PMF is not linear with temperature. This implies the prefactor frequency f in the Polanyi-Wigner equation is a function of temperature, increasing at lower temperatures due to the reduction of the available configuration space associated with an adsorbed molecule compared with a free molecule.     

Investigation of the dissociative adsorption for cyclopropane on the copper surface by density functional theory and quantum chemical molecular dynamics method

The dissociative adsorption of cyclopropane on the copper surface was studied using quantum chemical molecular dynamics method with “Colors-Excite” code and density functional theory by Amsterdam Density Functional program (ADF2000). The excited state of cyclopropane was used as adsorbate to simulate the dissociated adsorption under an irradiation energy of ca. 10 eV. One of the C-C bonds in cyclopropane was broken and the two new bonds between cyclopropane and copper surface were formed. The electrons transferred from the copper atoms to cyclopropane with a value of about 0.2e. The shorter distances between the carbons and surface copper atoms showed the existence of strong interaction. Consistently, the results indicated metallacyclopentane was the most possible intermediate species in dissociative adsorption by ADF2000 and “Colors-Excite” method.     

Molecular dynamics simulation of the (0 0 0 1) α-Al2O3 and α-Cr2O3 surfaces

A simple, rigid pair-potential model is applied to investigate the dynamics of the (0 0 0 1) α-Al₂O₃ and α-Cr₂O₃ surfaces using the molecular dynamics technique. The simulations employ a two-stage equilibration process: in the first stage the simulation-cell size is determined via the constant-stress ensemble, and in the second stage the equilibration of the size-corrected simulation cell is continued in the canonical ensemble. The thermal expansion coefficients of bulk alumina and chromia are evaluated as a function of temperature. Furthermore, the surface relaxation and mean-square displacement of the atoms versus depth into the slab are calculated, and their behaviour in the surface region analysed in detail. The calculations show that even moderate temperatures (∼400 °C) give rise to displacements of the atoms at the surface which are similar to the lattice mismatch between α-alumina and chromia. This will help in the initial nucleation stage during thin film growth, and thus facilitate the deposition of α-Al₂O₃ on (0 0 0 1) α-Cr₂O₃ templates.     

Dissociative adsorption of N2 on W(1 1 0): Theoretical study of the dependence on the incidence angle

The dissociative adsorption of N₂ on W(1 1 0) is studied using classical dynamics on a six-dimensional potential energy surface obtained from density functional theory calculations. Two distinct channels are identified in the dissociation process: a direct one and an indirect one. It is shown that the direct channel is inhibited for low energy molecules (E_i < 400 meV) and low incidence angles. The indirect channel includes long-lasting dynamic trapping of the molecule at the surface before dissociation. The dependence of the sticking coefficient on the initial incidence angle is analyzed. The theoretical results compare well with values measured using molecular beam techniques.     

Structural and electronic properties of V, Nb and Ta nanoclusters by tight-binding molecular dynamics simulations

We present tight-binding molecular dynamics (TBMD) calculations on V, Nb and Ta nanoclusters with N = 15, 65, 175 and 369 atoms. We found that rhombic dodecahedra are energetically favoured over rhombic hexahedra and icosahedra, with V forming the most compact cluster with the gyration radius increasing with the cluster size. In addition, from the calculated electronic density of states we found that the cluster size plays an important role in the HOMO-LUMO gap and that an increase in cluster size results in enhancement of the electronic density around the Fermi level. Furthermore, we found that the small clusters (N = 15, 65) exhibit energy gap that persists even at 900 K. These findings originate from charge transfer occurring between the inner and outer cluster atoms; interestingly, we found that in the small N = 15, 65 clusters electronic charge accumulates at each surface site at the expense of the inner cluster atoms, while in the larger clusters, N = 175 and 369, charge is gathered on the central particles of the cluster, suggesting different sub-surface character of the clusters. These findings are in agreement with available experimental and theoretical data and promise to offer important information for creating nanostructured materials with improved properties suitable for multiple technological applications.     

Molecular dynamics simulation of CH3 interaction with Si(1 0 0) surface

Molecular dynamics simulations of the CH₃ interaction with Si(1 0 0) were performed using the Tersoff-Brenner potential. The H/C ratio obtained from the simulations is in agreement with available experimental data. The results show that H atoms preferentially react with Si. SiH is the dominant form of SiH_x generated. The amount of hydrogen that reacts with silicon is essentially energy-independent. H atoms do not react with adsorbed carbon atoms. The presence of C-H bonds on the surface is due to molecular adsorption.     

Scattering of a Light Particle by a System of Harmonic Oscillators

We discuss the asymptotic wave function of a quantum system in ?³ composed by heavy and light particles, in the case where the light particles are in scattering states and no interaction is assumed among particles of the same kind. We first review a recent result concerning the case of K heavy and N light particles, where the one-particle potential acting on each heavy particle decays at infinity. Then we consider the case of one light particle interacting with a system of harmonic oscillators and prove the same kind of result following, with some modification, the proof of the previous case. A possible application to the analysis of the scattering of a light particle from condensed matter is also outlined.     

Mechanisms of the pancake vortex and vortex line movement in the high Tc superconductors Bi2Sr2CaCu2O8+δand La1.93Sr0.07CuO4+δ

In the strict sense, it is not very clear why with magnetic field increasing, the normal-superconductive (NS) transition becomes broad for Bi2Sr2CaCu2O8+δ(Bi2212) while the NS transitions are almost parallel for La1.93Sr0.07CuO4+δ(La214). In this paper, R-T relations are measured by the six-probe method. We propose a moving mechanism of the pancake vortex and vortex line for Bi2212. The theoretical curves fit the experiment data well.