Ab initio lattice dynamics and electron-phonon coupling of Bi(111)

We present a comprehensive ab initio study of structural, electronic, lattice dynamical and electron-phonon coupling properties of the Bi(111) surface within density functional perturbation theory. Relativistic corrections due to spin-orbit coupling are consistently taken into account. As calculations are carried out in a periodic slab geometry, special attention is given to the convergence with respect to the slab thickness. Although the electronic structure of Bi(111) thin films varies significantly with thickness, we found that the lattice dynamics of Bi(111) is quite robust and appears converged already for slabs as thin as 6 bilayers. Changes of interatomic couplings are confined mostly to the first two bilayers, resulting in super-bulk modes with frequencies higher than the optic bulk spectrum, and in an enhanced density of states at lower frequencies for atoms in the first bilayer. Electronic states of the surface band related to the outer part of the hole Fermi surfaces exhibit a moderate electron-phonon coupling of about 0.45, which is larger than the coupling constant of bulk Bi. States at the inner part of the hole surface as well as those forming the electron pocket close to the zone center show much increased couplings due to transitions into bulk projected states near Gamma_bar. For these cases, the state dependent Eliashberg functions exhibit pronounced peaks at low energy and strongly deviate in shape from a Debye-like spectrum, indicating that an extraction of the coupling strength from measured electronic self-energies based on this simple model is likely to fail.Comment: 30 pages, 11 figure

Effect of dipolar interactions on the magnetization of a cubic array of nanomagnets

We investigated the effect of intermolecular dipolar interactions on a cubic 3D ensemble of 5X5X4=100 nanomagnets, each with spin $S = 5$. We employed the Landau-Lifshitz-Gilbert equation to solve for the magnetization $M(B)$ curves for several values of the damping constant $\alpha$, the induction sweep rate, the lattice constant $a$, the temperature $T$, and the magnetic anisotropy field $H_A$. We find that the smaller the $\alpha$, the stronger the maximum induction required to produce hysteresis. The shape of the hysteresis loops also depends on the damping constant. We find further that the system magnetizes and demagnetizes at decreasing magnetic field strengths with decreasing sweep rates, resulting in smaller hysteresis loops. Variations of $a$ within realistic values (1.5 nm - 2.5 nm) show that the dipolar interaction plays an important role in the magnetic hysteresis by controlling the relaxation process. The $T$ dependencies of $\alpha$ and of $M$ are presented and discussed with regard to recent experimental data on nanomagnets. $H_A$ enhances the size of the hysteresis loops for external fields parallel to the anisotropy axis, but decreases it for perpendicular external fields. Finally, we reproduce and test an $M(B)$ curve for a 2D-system [M. Kayali and W. Saslow, Phys. Rev. B {\bf 70}, 174404 (2004)]. We show that its hysteretic behavior is only weakly dependent on the shape anisotropy field and the sweep rate, but depends sensitively upon the dipolar interactions. Although in 3D systems, dipole-dipole interactions generally diminish the hysteresis, in 2D systems, they strongly enhance it. For both square 2D and rectangular 3D lattices with ${\bm B}||(\hat{\bm x}+\hat{\bm y})$, dipole-dipole interactions can cause large jumps in the magnetization.Comment: 15 pages 14 figures, submitted to Phys. Rev.

Thermodynamic properties of Pt nanoparticles: Size, shape, support, and adsorbate effects

This study presents a systematic investigation of the thermodynamic properties of free and gamma-Al2O3-supported size-controlled Pt nanoparticles (NPs) and their evolution with decreasing NP size. A combination of in situ extended x-ray absorption fine-structure spectroscopy (EXAFS), ex situ transmission electron microscopy (TEM) measurements, and NP shape modeling revealed (i) a cross over from positive to negative thermal expansion with decreasing particle size, (ii) size- and shape-dependent changes in the mean square bond-projected bond-length fluctuations, and (iii) enhanced Debye temperatures (D-circle minus, relative to bulk Pt) with a bimodal size- dependence for NPs in the size range of similar to 0.8-5.4 nm. For large NP sizes (diameter d \u3e 1.5 nm) D-circle minus was found to decrease toward D-circle minus of bulk Pt with increasing NP size. For NPs \u3c = 1 nm, a monotonic decrease of D-circle minus was observed with decreasing NP size and increasing number of low-coordinated surface atoms. Our density functional theory calculations confirm the size- and shape-dependence of the vibrational properties of our smallest NPs and show how their behavior may be tuned by H desorption from the NPs. The experimental results can be partly attributed to thermally induced changes in the coverage of the adsorbate (H-2) used during the EXAFS measurements, bearing in mind that the interaction of the Pt NPs with the stiff, high-melting temperature gamma-Al2O3 support may also play a role. The calculations also provide good qualitative agreement with the trends in the mean square bond-projected bond-length fluctuations measured via EXAFS. Furthermore, they revealed that part of the D-circle minus enhancement observed experimentally for the smallest NPs (d \u3c = 1 nm) might be assigned to the specific sensitivity of EXAFS, which is intrinsically limited to bond-projected bond-length fluctuations

Local-strain mapping on Ag(111) islands on Nb(110)

The local in-plane strain of Ag(111) islands on the Nb(110) surface has been derived from the lateral variation of the electronic density of states measured by scanning tunneling spectroscopy. The onset energy E-ss of the Shockley-type surface-state band is shifted to higher energies compared to the bulk due to thermal strain arising from the difference in thermal expansion between Nb and Ag and cooling by 565K. A quantitative dependence of E-ss from the strain is obtained by density-functional theory calculations. This allows a mapping of the local strain of individual Ag islands on the nanometer scale

Thermodynamic properties of Pt nanoparticles: Size, shape, support, and adsorbate effects

This study presents a systematic investigation of the thermodynamic properties of free and γ -Al 2 O 3 -supported size-controlled Pt nanoparticles (NPs) and their evolution with decreasing NP size. A combination of in situ extended x-ray absorption fine-structure spectroscopy (EXAFS), ex situ transmission electron microscopy (TEM) measurements, and NP shape modeling revealed (i) a cross over from positive to negative thermal expansion with decreasing particle size, (ii) size-and shape-dependent changes in the mean square bond-projected bond-length fluctuations, and (iii) enhanced Debye temperatures ( D , relative to bulk Pt) with a bimodal size-dependence for NPs in the size range of ∼0.8-5.4 nm. For large NP sizes (diameter d >1.5 nm) D was found to decrease toward D of bulk Pt with increasing NP size. For NPs 1 nm, a monotonic decrease of D was observed with decreasing NP size and increasing number of low-coordinated surface atoms. Our density functional theory calculations confirm the size-and shape-dependence of the vibrational properties of our smallest NPs and show how their behavior may be tuned by H desorption from the NPs. The experimental results can be partly attributed to thermally induced changes in the coverage of the adsorbate (H 2 ) used during the EXAFS measurements, bearing in mind that the interaction of the Pt NPs with the stiff, high-melting temperature γ -Al 2 O 3 support may also play a role. The calculations also provide good qualitative agreement with the trends in the mean square bond-projected bond-length fluctuations measured via EXAFS. Furthermore, they revealed that part of the D enhancement observed experimentally for the smallest NPs (d 1 nm) might be assigned to the specific sensitivity of EXAFS, which is intrinsically limited to bond-projected bond-length fluctuations

Anomalously Soft and Stiff Modes of Transition-Metal Nanoparticles

We propose an explanation for the enhanced low- and high-energy tails of the vibrational density of states (VDOS) of nanoparticles (NPs) with respect to their bulk counterparts. Density functional theory calculations of the frequency and eigenvector of each mode allow us to identify radial breathing/multipolar and nonradial tidal/shear/torsional vibrations as the modes that populate such tails. These modes have long been obtained from elasticity theory and are thus analogous to the widely studied and observed pulsations in variable stars. The features particular to the VDOS of NPs are rationalized in terms of the charge density distribution around low-coordinated atoms, the quasi-radial geometric distribution of NPs, force constant variations, degree of symmetry of the nanoparticle, discreteness of the spectrum, and the confinement of the eigenmodes. Our results indicate that the high- and low-energy tails of the VDOS may be a powerful tool to reveal information about the chemical composition and geometric structure of small NPs. In particular, the size of the confinement gap at the low-frequency end of the VDOS and the extent by which the high-frequency end surpasses the bulk limit signal whether a NP is bulk-like or non-bulk-like and the extent to which it is disordered. © 2014 American Chemical Society

Rational Design of Competitive Electrocatalysts for Hydrogen Fuel Cells

We report a mechanism-based screening technique to rapidly identify eukaryotic topoisomerase I targeting agents. The method is based on genetic tagging of topoisomerase I to immobilize the enzyme on a solid surface in a microtiter well format. DNA is added to the wells, and retained DNA is detected by Pico Green fluorescence. Compounds that result in an increase in Pico Green staining represent potential topoisomerase interfacial poisons, whereas those that reduce fluorescence report catalytic inhibitors; therefore, the solid phase assay represents a bimodal readout that reveals mechanisms of action. The method has been demonstrated to work with known interfacial poisons and catalytic inhibitors. This method is rapid, robust, economical, and scalable for large library screens. © 2011 Elsevier Inc. All rights reserved