57 research outputs found
Dissociation of O2 at Al(111): The Role of Spin Selection Rules
A most basic and puzzling enigma in surface science is the description of the
dissociative adsorption of O2 at the (111) surface of Al. Already for the
sticking curve alone, the disagreement between experiment and results of
state-of-the-art first-principles calculations can hardly be more dramatic. In
this paper we show that this is caused by hitherto unaccounted spin selection
rules, which give rise to a highly non-adiabatic behavior in the O2/Al(111)
interaction. We also discuss problems caused by the insufficient accuracy of
present-day exchange-correlation functionals.Comment: 4 pages including 3 figures; related publications can be found at
http://www.fhi-berlin.mpg.de/th/th.htm
Crystal Structures and Electronic Properties of Haloform-Intercalated C60
Using density functional methods we calculated structural and electronic
properties of bulk chloroform and bromoform intercalated C60, C60 2CHX3
(X=Cl,Br). Both compounds are narrow band insulator materials with a gap
between valence and conduction bands larger than 1 eV. The calculated widths of
the valence and conduction bands are 0.4-0.6 eV and 0.3-0.4 eV, respectively.
The orbitals of the haloform molecules overlap with the orbitals of the
fullerene molecules and the p-type orbitals of halogen atoms significantly
contribute to the valence and conduction bands of C60 2CHX3. Charging with
electrons and holes turns the systems to metals. Contrary to expectation, 10 to
20 % of the charge is on the haloform molecules and is thus not completely
localized on the fullerene molecules. Calculations on different crystal
structures of C60 2CHCl3 and C60 2CHBr3 revealed that the density of states at
the Fermi energy are sensitive to the orientation of the haloform and C60
molecules. At a charging of three holes, which corresponds to the
superconducting phase of pure C60 and C60 2CHX3, the calculated density of
states (DOS) at the Fermi energy increases in the sequence DOS(C60) < DOS(C60
2CHCl3) < DOS(C60 2CHBr3).Comment: 11 pages, 7 figures, 4 table
Non-Adiabatic Potential-Energy Surfaces by Constrained Density-Functional Theory
Non-adiabatic effects play an important role in many chemical processes. In
order to study the underlying non-adiabatic potential-energy surfaces (PESs),
we present a locally-constrained density-functional theory approach, which
enables us to confine electrons to sub-spaces of the Hilbert space, e.g. to
selected atoms or groups of atoms. This allows to calculate non-adiabatic PESs
for defined charge and spin states of the chosen subsystems. The capability of
the method is demonstrated by calculating non-adiabatic PESs for the scattering
of a sodium and a chlorine atom, for the interaction of a chlorine molecule
with a small metal cluster, and for the dissociation of an oxygen molecule at
the Al(111) surface.Comment: 11 pages including 7 figures; related publications can be found at
http://www.fhi-berlin.mpg.de/th/th.htm
Tunable Conductivity and Conduction Mechanism in a UV light activated electronic conductor
A tunable conductivity has been achieved by controllable substitution of a
novel UV light activated electronic conductor. The transparent conducting oxide
system H-doped Ca12-xMgxAl14O33 (x = 0; 0.1; 0.3; 0.5; 0.8; 1.0) presents a
conductivity that is strongly dependent on the substitution level and
temperature. Four-point dc-conductivity decreases with x from 0.26 S/cm (x = 0)
to 0.106 S/cm (x = 1) at room temperature. At each composition the conductivity
increases (reversibly with temperature) until a decomposition temperature is
reached; above this value, the conductivity drops dramatically due to hydrogen
recombination and loss. The observed conductivity behavior is consistent with
the predictions of our first principles density functional calculations for the
Mg-substituted system with x=0, 1 and 2. The Seebeck coefficient is essentially
composition- and temperature-independent, the later suggesting the existence of
an activated mobility associated with small polaron conduction. The optical gap
measured remains constant near 2.6 eV while transparency increases with the
substitution level, concomitant with a decrease in carrier content.Comment: Submitted for publicatio
Inferring the Dy-N axis orientation in adsorbed DyScN@C endofullerenes by linearly polarized x-ray absorption spectroscopy
Endofullerene DyScN@C is a single-molecule magnet with a large magnetic anisotropy and high blocking temperature, which is promising for nanomagnetic applications. As the easy axis of magnetization coincides with the Dy-N bond direction, it is important to understand the structure of the DyScN unit in the fullerene cage and to control the orientation of the molecules. Here we report on the experimental determination of Dy-N axis by x-ray absorption spectroscopy (XAS) with linear polarized light at the Dy−M white lines. DyScN@C molecules were adsorbed on a Pt(111) surface and XAS was performed as a function of temperature in the range between 35 and 300 K. The M/M branching ratio shows a clear and reversible variation with temperature which can be explained, on the basis of a thermodynamic model, by a change of average orientation of the molecules with temperature. The XAS spectra are well reproduced by ligand field multiplet calculations. It is shown that the angle between the magnetization (Dy-N) axis and the surface plane can be directly inferred from the XAS spectra with in-plane polarization by comparison with calculated spectra. It is found that the endohedral unit is randomly oriented at room temperature but tends towards orientation parallel to the surface at low temperature, indicating a weak but non-negligible interaction between the endohedral units and the metal surface
Influence of the Fermi Surface Morphology on the Magnetic Field-Driven Vortex Lattice Structure Transitions in YBaCuO0, 0.15
We report small-angle neutron scattering measurements of the vortex lattice
(VL) structure in single crystals of the lightly underdoped cuprate
superconductor YBa2Cu3O6.85. At 2 K, and for fields of up to 16 T applied
parallel to the crystal c-axis, we observe a sequence of field-driven and
first-order transitions between different VL structures. By rotating the field
away from the c-axis, we observe each structure transition to shift to either
higher or lower field dependent on whether the field is rotated towards the
[100] or [010] direction. We use this latter observation to argue that the
Fermi surface morphology must play a key role in the mechanisms that drive the
VL structure transitions. Furthermore, we show this interpretation is
compatible with analogous results obtained previously on lightly overdoped
YBa2Cu3O7. In that material, it has long-been suggested that the high field VL
structure transition is driven by the nodal gap anisotropy. In contrast, the
results and discussion presented here bring into question the role, if any, of
a nodal gap anisotropy on the VL structure transitions in both YBa2Cu3O6.85 and
YBa2Cu3O7
- …