High-dimensional quantum dynamics of adsorption and desorption of H2_2 at Cu(111)

We performed high-dimensional quantum dynamical calculations of the dissociative adsorption and associative desorption of hydrogen on Cu(111). The potential energy surface (PES) is obtained from density functional theory calculations. Two regimes of dynamics are found, at low energies sticking is determined by the minimum energy barrier, at high energies by the distribution of barrier heights. Experimental results are well-reproduced qualitatively, but some quantitative discrepancies are identified as well.Comment: 4 two column pages, revtex, 4 figures, to appear in Phys. Rev. Let

Elastic and thermodynamic properties of the shape-memory alloy AuZn

The current work reports on the elastic shear moduli, internal friction, and the specific heat of the B2 cubic ordered alloy AuZn as a function of temperature. Measurements were made on single-crystal and polycrystalline samples using Resonant Ultrasound Spectroscopy (RUS), semi-adiabatic calorimetry and stress-strain measurements. Our results confirm that this alloy exhibits the shape-memory effect and a phase transition at 64.75 K that appears to be continuous (second-order) from the specific heat data. It is argued that the combination of equiatomic composition and a low transformation temperature constrain the chemical potential and its derivatives to exhibit behavior that lies at the borderline between that of a first-order (discontinuous) and a continuous phase transition. The acoustic dissipation does not peak at the transtion temperature as expected, but shows a maximum well into the low-temperature phase. The Debye temeprature value of 219 K, obtained from the low-temperature specific heat data is in favorable agreement with that determined from the acoustic data (207 K) above the transition.Comment: 25 pages, 6 figures, submitted to Phys. Rev.

Direct observation of the formation of polar nanoregions in Pb(Mg1/3_{1/3}Nb2/3_{2/3})O3_3 using neutron pair distribution function analysis

Using neutron pair distribution function (PDF) analysis over the temperature range from 1000 K to 15 K, we demonstrate the existence of local polarization and the formation of medium-range, polar nanoregions (PNRs) with local rhombohedral order in a prototypical relaxor ferroelectric Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$. We estimate the volume fraction of the PNRs as a function of temperature and show that this fraction steadily increases from 0 % to a maximum of $\sim$ 30% as the temperature decreases from 650 K to 15 K. Below T$\sim$200 K the PNRs start to overlap as their volume fraction reaches the percolation threshold. We propose that percolating PNRs and their concomitant overlap play a significant role in the relaxor behavior of Pb(Mg$_{1/3}$Nb$_{2/3}$)O$_3$.Comment: 4 pages, 3 figure

Electrostatic Patch Effect in Cylindrical Geometry. III. Torques

We continue to study the effect of uneven voltage distribution on two close cylindrical conductors with parallel axes started in our papers [1] and [2], now to find the electrostatic torques. We calculate the electrostatic potential and energy to lowest order in the gap to cylinder radius ratio for an arbitrary relative rotation of the cylinders about their symmetry axis. By energy conservation, the axial torque, independent of the uniform voltage difference, is found as a derivative of the energy in the rotation angle. We also derive both the axial and slanting torques by the surface integration method: the torque vector is the integral over the cylinder surface of the cross product of the electrostatic force on a surface element and its position vector. The slanting torque consists of two parts: one coming from the interaction between the patch and the uniform voltages, and the other due to the patch interaction. General properties of the torques are described. A convenient model of a localized patch suggested in [2] is used to calculate the torques explicitly in terms of elementary functions. Based on this, we analyze in detail patch interaction for one pair of patches, namely, the torque dependence on the patch parameters (width and strength) and their mutual positions. The effect of the axial torque is then studied for the experimental conditions of the STEP mission.Comment: 28 pages, 6 Figures. Submitted to Classical Quantum Gravit

Ab initio Quantum and ab initio Molecular Dynamics of the Dissociative Adsorption of Hydrogen on Pd(100)

The dissociative adsorption of hydrogen on Pd(100) has been studied by ab initio quantum dynamics and ab initio molecular dynamics calculations. Treating all hydrogen degrees of freedom as dynamical coordinates implies a high dimensionality and requires statistical averages over thousands of trajectories. An efficient and accurate treatment of such extensive statistics is achieved in two steps: In a first step we evaluate the ab initio potential energy surface (PES) and determine an analytical representation. Then, in an independent second step dynamical calculations are performed on the analytical representation of the PES. Thus the dissociation dynamics is investigated without any crucial assumption except for the Born-Oppenheimer approximation which is anyhow employed when density-functional theory calculations are performed. The ab initio molecular dynamics is compared to detailed quantum dynamical calculations on exactly the same ab initio PES. The occurence of quantum oscillations in the sticking probability as a function of kinetic energy is addressed. They turn out to be very sensitive to the symmetry of the initial conditions. At low kinetic energies sticking is dominated by the steering effect which is illustrated using classical trajectories. The steering effects depends on the kinetic energy, but not on the mass of the molecules. Zero-point effects lead to strong differences between quantum and classical calculations of the sticking probability. The dependence of the sticking probability on the angle of incidence is analysed; it is found to be in good agreement with experimental data. The results show that the determination of the potential energy surface combined with high-dimensional dynamical calculations, in which all relevant degrees of freedon are taken into account, leads to a detailed understanding of the dissociation dynamics of hydrogen at a transition metal surface.Comment: 15 pages, 9 figures, subm. to Phys. Rev.