239 research outputs found
Density-functional theory study on the arrangement of adsorbed formate molecules on Cu(110)
The interaction of formate molecules with the Cu(110) surface is investigated using density-functional theory calculations. We find that in the most stable structures for low and high coverage, the formate molecules are sitting perpendicular to the Cu(110) surface, and they are adsorbed in a bridge position, i.e., the O-C-O group forms a bridge between two Cu atoms. Other tested configurations are less stable by at least 0.45 eV per formate molecule. In the case of an oxygen-precovered Cu(110) surface with high formate coverage [two molecules in a (2x2) unit cell] we find a very similar adsorption geometry. We find an attractive interaction between adsorbed formate molecules on the copper surface. Our results are consistent with experimental results by scanning tunneling microscopy and photoelectron diffraction
Role of the van der Waals interactions on the bonding mechanism of pyridine on Cu(110) and Ag(110) surfaces: A first-principles study
We performed density-functional calculations aimed to investigate the adsorption mechanism of a single pyridine (C5H5N) molecule on Cu(110) and Ag(110) surfaces. Our ab initio simulations show that, in the ground state, the pyridine molecule adsorbs with its molecular plane perpendicular to these substrates and is oriented along the [001] direction. In this case, the bonding mechanism involves a sigma bond through the lone-pair electrons of the nitrogen atom. When the heterocyclic ring is parallel to the surface, the bonding takes place via pi-like molecular orbitals. However, depending on the position of the N atom on the surface, the planar adsorption configuration can relax to a perpendicular geometry. The role of the long-range van der Waals interactions on the adsorption geometries and energies was analyzed in the framework of the semiempirical method proposed by Grimme [J. Comput. Chem. 27, 1787 (2006)]. We demonstrate that these dispersion effects are very important for geometry and electronic structure of flat adsorption configurations
Cd-vacancy and Cd-interstitial complexes in Si and Ge
The electrical field gradient (EFG), measured e.g. in perturbed angular
correlation (PAC) experiments, gives particularly useful information about the
interaction of probe atoms like 111In / 111Cd with other defects. The
interpretation of the EFG is, however, a difficult task. This paper aims at
understanding the interaction of Cd impurities with vacancies and interstitials
in Si and Ge, which represents a controversial issue. We apply two
complementary ab initio methods in the framework of density functional theory
(DFT), (i) the all electron Korringa-Kohn-Rostoker (KKR) Greenfunction method
and (ii) the Pseudopotential-Plane-Wave (PPW) method, to search for the correct
local geometry. Surprisingly we find that both in Si and Ge the substitutional
Cd-vacancy complex is unstable and relaxes to a split-vacancy complex with the
Cd on the bond-center site. This complex has a very small EFG, allowing a
unique assignment of the small measured EFGs of 54MHz in Ge and 28MHz in Si.
Also, for the Cd-selfinterstitial complex we obtain a highly symmetrical split
configuration with large EFGs, being in reasonable agreement with experiments
Vacancy complexes with oversized impurities in Si and Ge
In this paper we examine the electronic and geometrical structure of
impurity-vacancy complexes in Si and Ge. Already Watkins suggested that in Si
the pairing of Sn with the vacancy produces a complex with the Sn-atom at the
bond center and the vacancy split into two half vacancies on the neighboring
sites. Within the framework of density-functional theory we use two
complementary ab initio methods, the pseudopotential plane wave (PPW) method
and the all-electron Kohn-Korringa-Rostoker (KKR) method, to investigate the
structure of vacancy complexes with 11 different sp-impurities. For the case of
Sn in Si, we confirm the split configuration and obtain good agreement with EPR
data of Watkins. In general we find that all impurities of the 5sp and 6sp
series in Si and Ge prefer the split-vacancy configuration, with an energy gain
of 0.5 to 1 eV compared to the substitutional complex. On the other hand,
impurities of the 3sp and 4sp series form a (slightly distorted) substitutional
complex. Al impurities show an exception from this rule, forming a split
complex in Si and a strongly distorted substitutional complex in Ge. We find a
strong correlation of these data with the size of the isolated impurities,
being defined via the lattice relaxations of the nearest neighbors.Comment: 8 pages, 4 bw figure
Interplay of structure and spin-orbit strength in magnetism of metal-benzene sandwiches: from single molecules to infinite wires
Based on first-principles density functional theory calculations we explore
electronic and magnetic properties of experimentally producible sandwiches and
infinite wires made of repeating benzene molecules and transition-metal atoms
of V, Nb, and Ta. We describe the bonding mechanism in the molecules and in
particular concentrate on the origin of magnetism in these structures. We find
that all the considered systems have sizable magnetic moments and ferromagnetic
spin-ordering, with the single exception of the V3-Bz4 molecule. By including
the spin-orbit coupling into our calculations we determine the easy and hard
axes of the magnetic moment, the strength of the uniaxial magnetic anisotropy
energy (MAE), relevant for the thermal stability of magnetic orientation, and
the change of the electronic structure with respect to the direction of the
magnetic moment, important for spin-transport properties. While for the V-based
compounds the values of the MAE are only of the order of 0.05-0.5 meV per metal
atom, increasing the spin-orbit strength by substituting V with heavier Nb and
Ta allows to achieve an increase in anisotropy values by one to two orders of
magnitude. The rigid stability of magnetism in these compounds together with
the strong ferromagnetic ordering makes them attractive candidates for
spin-polarized transport applications. For a Nb-benzene infinite wire the
occurrence of ballistic anisotropic magnetoresistance is demonstrated.Comment: 23 pages, 8 figure
The mechanism of caesium intercalation of graphene
Properties of many layered materials, including copper- and iron-based
superconductors, topological insulators, graphite and epitaxial graphene can be
manipulated by inclusion of different atomic and molecular species between the
layers via a process known as intercalation. For example, intercalation in
graphite can lead to superconductivity and is crucial in the working cycle of
modern batteries and supercapacitors. Intercalation involves complex diffusion
processes along and across the layers, but the microscopic mechanisms and
dynamics of these processes are not well understood. Here we report on a novel
mechanism for intercalation and entrapment of alkali-atoms under epitaxial
graphene. We find that the intercalation is adjusted by the van der Waals
interaction, with the dynamics governed by defects anchored to graphene
wrinkles. Our findings are relevant for the future design and application of
graphene-based nano-structures. Similar mechanisms can also play a role for
intercalation of layered materials.Comment: 8 pages, 7 figures in published form, supplementary information
availabl
- …