Role of Rotations on Surface Diffusion of Water Trimers on Pd\{111\}

Diffusion barriers for a cluster of three water molecules on Pd(111) have been estimated from ab-initio Density Functional Theory. A model for the diffusion of the trimer based in rotations yields a simple explanation of why the cluster can diffuse faster than a single water molecule by a factor $\approx 10^{2}$. This model is based on the differences between the adsorption geometry for the three monomers forming the cluster. One member interacts strongly with the surface and sits closer to the surface (d) while the other two interact weakly and stay at a larger separation from the surface (u). The trimer rotates nearly freely around the axis determined by the d monomer. Translations of the whole trimer imply breaking the strong interaction of the d monomer with the surface. Alternatively, thermal fluctuations exchange the actual monomer sitting closer to the surface with a lower energetic cost. Rotations around different axis introduce a diffusion mechanism where a strong interaction is kept along the diffusion path between the water molecule defining the axis of rotation and the Pd underneath.Comment: water ; monomer ; trimer ; water clusters ; diffusion ; rotation assisted ; Pd\{111\} ; ab-initio ; density functional theor

Crystal structure and electronic states of tripotassium picene

The crystal structure of potassium doped picene with an exact stoichiometry (K3C22H14, K3picene from here onwards) has been theoretically determined within Density Functional Theory allowing complete variational freedom of the crystal structure parameters and the molecular atomic positions. A modified herringbone lattice is obtained in which potassium atoms are intercalated between two paired picene molecules displaying the two possible orientations in the crystal.Along the c-axis, organic molecules alternate with chains formed by three potassium atoms. The electronic structureof the doped material resembles pristine picene, except that now the bottom of the conduction band is occupied by six electrons coming from the ionized K atoms (six per unit cell). Wavefunctions remain based mainly on picene molecular orbitals getting their dispersion from intralayer edge to face CH/pi bonding, while eigenenergies have been modified by the change in the electrostatic potential. The small dispersion along the c-axis is assigned to small H-H overlap. From the calculated electronic density of states we expect metallic behavior for potassium doped picene.Comment: Published version: 8 twocolumn pages, 7 color figures, 2 structural .cif files include

China in Latin America: lessons for South-South cooperation and sustainable development

This repository item contains a report from the Boston University Global Economic Governance Initiative. The Global Economic Governance Initiative (GEGI) is a research program of the Center for Finance, Law & Policy, the Frederick S. Pardee Center for the Study of the Longer-Range Future, and the Frederick S. Pardee School of Global Studies. It was founded in 2008 to advance policy-relevant knowledge about governance for financial stability, human development, and the environment

Trapping of electrons near chemisorbed hydrogen on graphene

Chemical adsorption of atomic hydrogen on a negatively charged single layer graphene sheet has been analyzed with ab-initio Density Functional Theory calculations. We have simulated both finite clusters and infinite periodic systems to investigate the effect of different ingredients of the theory, e.g. exchange and correlation potentials, basis sets, etc. Hydrogen's electron affinity dominates the energetic balance in the charged systems and the extra electron is predominantly attracted to a region nearby the chemisorbed atom. The main consequences are: (i) the cancellation of the unpaired spin resulting in a singlet ground-state, and (ii) a stronger interaction between hydrogen and the graphene sheet.Comment: 11 pages, 8 figures, to be published in PR

Ab-initio calculation of the effect of stress on the chemical activity of graphene

Graphene layers are stable, hard, and relatively inert. We study how tensile stress affects $\sigma$ and $\pi$ bonds and the resulting change in the chemical activity. Stress affects more strongly $\pi$ bonds that can become chemically active and bind to adsorbed species more strongly. Upon stretch, single C bonds are activated in a geometry mixing $120^{o}$ and $90^{o}$; an intermediate state between $sp^{2}$ and $sp^{3}$ bonding. We use ab-initio density functional theory to study the adsorption of hydrogen on large clusters and 2D periodic models for graphene. The influence of the exchange-correlation functional on the adsorption energy is discussed

Patterson Function from Low-Energy Electron Diffraction Measured Intensities and Structural Discrimination

Surface Patterson Functions have been derived by direct inversion of experimental Low-Energy Electron Diffraction I-V spectra measured at multiple incident angles. The direct inversion is computationally simple and can be used to discriminate between different structural models. 1x1 YSi_2 epitaxial layers grown on Si(111) have been used to illustrate the analysis. We introduce a suitable R-factor for the Patterson Function to make the structural discrimination as objective as possible. From six competing models needed to complete the geometrical search, four could easily be discarded, achieving a very significant and useful reduction in the parameter space to be explored by standard dynamical LEED methods. The amount and quality of data needed for this analysis is discussed.Comment: 5 pages, 4 figure

Two-fluid behavior of the Kondo lattice in the 1/N slave boson approach

It has been recently shown by Nakatsuji, Pines, and Fisk [S. Nakatsuji, D. Pines, and Z. Fisk, Phys. Rev. Lett. 92, 016401 (2004)] from the phenomenological analysis of experiments in Ce1-xLaxCoIn5 and CeIrIn5 that thermodynamic and transport properties of Kondo lattices below coherence temperature can be very successfully described in terms of a two-fluid model, with Kondo impurity and heavy electron Fermi liquid contributions. We analyze thermodynamic properties of Kondo lattices using 1/N slave boson treatment of the periodic Anderson model and show that these two contributions indeed arise below the coherence temperature. We find that the Kondo impurity contribution to thermodynamics corresponds to thermal excitations into the flat portion of the energy spectrum.Comment: 7 pages, 2 figure