64 research outputs found
Magnetic ordering, electronic structure and magnetic anisotropy energy in the high-spin Mn single molecule magnet
We report the electronic structure and magnetic ordering of the single
molecule magnet [MnO(2,2'-biphenoxide)Br]
based on first-principles all-electron density-functional calculations. We find
that two of the ten core Mn atoms are coupled antiferromagnetically to the
remaining eight, resulting in a ferrimagnetic ground state with total spin
S=13. The calculated magnetic anisotropy barrier is found to be 9 K in good
agreement with experiment. The presence of the Br anions impact the electronic
structure and therefore the magnetic properties of the 10 Mn atoms. However,
the electric field due to the negative charges has no significant effect on the
magnetic anisotropy.Comment: 4 pages, submitted to PR
DFT calculation of the intermolecular exchange interaction in the magnetic Mn dimer
The dimeric form of the single-molecule magnet
[MnOCl(OCEt)(py)] recently revealed interesting
phenomena: no quantum tunneling at zero field and tunneling before magnetic
field reversal. This is attributed to substantial antiferromagnetic exchange
interaction between different monomers. The intermolecular exchange
interaction, electronic structure and magnetic properties of this molecular
magnet are calculated using density-functional theory within
generalized-gradient approximation. Calculations are in good agreement with
experiment.Comment: 4 page
Coupling to haloform molecules in intercalated C60?
For field-effect-doped fullerenes it was reported that the superconducting
transition temperature Tc is markedly larger for C60.2CHX_3 (X=Cl, Br)
crystals, than for pure C60. Initially this was explained by the expansion of
the volume per C60-molecule and the corresponding increase in the density of
states at the Fermi level in the intercalated crystals. On closer examination
it has, however, turned out to be unlikely that this is the mechanism behind
the increase in Tc. An alternative explanation of the enhanced transition
temperatures assumes that the conduction electrons not only couple to the
vibrational modes of the C60-molecule, but also to the modes of the
intercalated molecules. We investigate the possibility of such a coupling. We
find that, assuming the ideal bulk structure of the intercalated crystal, both
a coupling due to hybridization of the molecular levels, and a coupling via
dipole moments should be very small. This suggests that the presence of the
gate-oxide in the field-effect-devices strongly affects the structure of the
fullerene crystal at the interface.Comment: 4 pages, 1 figure, to be published in PRB (rapid communication
Predicted Infrared and Raman Spectra for Neutral Ti_8C_12 Isomers
Using a density-functional based algorithm, the full IR and Raman spectra are
calculated for the neutral Ti_8C_12 cluster assuming geometries of Th, Td, D2d
and C3v symmetry. The Th pentagonal dodecahedron is found to be dynamically
unstable. The calculated properties of the relaxed structure having C3v
symmetry are found to be in excellent agreement with experimental gas phase
infrared results, ionization potential and electron affinity measurements.
Consequently, the results presented may be used as a reference for further
experimental characterization using vibrational spectroscopy.Comment: 6 pages, 5 figures. Physical Review A, 2002 (in press
Molecular structures and vibrations of neutral and anionic CuOx (x = 1-3,6) clusters
We report equilibrium geometric structures of CuO2, CuO3, CuO6, and CuO
clusters obtained by an all-electron linear combination of atomic orbitals
scheme within the density-functional theory with generalized gradient
approximation to describe the exchange-correlation effects. The vibrational
stability of all clusters is examined on the basis of the vibrational
frequencies. A structure with Cs symmetry is found to be the lowest-energy
structure for CuO2, while a -shaped structure with C2v symmetry is the most
stable structure for CuO3. For the larger CuO6 and CuO clusters, several
competitive structures exist with structures containing ozonide units being
higher in energy than those with O2 units. The infrared and Raman spectra are
calculated for the stable optimal geometries. ~Comment: Uses Revtex4, (Better quality figures can be obtained from authors
Occupation numbers in density-functional calculations
It is the intention of this paper to rigorously clarify the role of the
occupation numbers in the current practical applications of the density
functional formalism. In these calculations one has to decide how to distribute
a given, fixed number of electrons over a set of single-particle orbitals. The
conventional choice is to have orbitals below the Fermi level completely
occupied and the orbitals above the Fermi level empty. Although there is a
certain confusion in literature why this choice is superior to any others, the
general belief is that it can justified by treating the occupation numbers as
variational parameters and then applying Janak's theorem or similar reasoning.
We demonstrate that there is a serious flaw in those arguments,mainly the
kinetic energy and therefore the exchange-correlation potential are not
differentiable with respect to density for arbitrary occupation numbers. It is
rigorously shown that in the present context of the density functional
calculations there is no freedom to vary the occupation numbers. The occupation
numbers cannot be considered as variational parameters.Comment: 10 pages, Revtex, accepted for publication by Phys.Rev.
Investigation of the Jahn-Teller Transition in TiF3 using Density Functional Theory
We use first principles density functional theory to calculate electronic and
magnetic properties of TiF3 using the full potential linearized augmented plane
wave method. The LDA approximation predicts a fully saturated ferromagnetic
metal and finds degenerate energy minima for high and low symmetry structures.
The experimentally observed Jahn-Teller phase transition at Tc=370K can not be
driven by the electron-phonon interaction alone, which is usually described
accurately by LDA.
Electron correlations beyond LDA are essential to lift the degeneracy of the
singly occupied Ti t2g orbital. Although the on-site Coulomb correlations are
important, the direction of the t2g-level splitting is determined by the
dipole-dipole interactions. The LDA+U functional predicts an aniferromagnetic
insulator with an orbitally ordered ground state. The input parameters U=8.1 eV
and J=0.9 eV for the Ti 3d orbital were found by varying the total charge on
the TiF ion using the molecular NRLMOL code. We estimate the
Heisenberg exchange constant for spin-1/2 on a cubic lattice to be
approximately 24 K. The symmetry lowering energy in LDA+U is about 900 K per
TiF3 formula unit.Comment: 7 pages, 9 figures, to appear in Phys. Rev.
Superdiffusion in a Model for Diffusion in a Molecularly Crowded Environment
We present a model for diffusion in a molecularly crowded environment. The
model consists of random barriers in percolation network. Random walks in the
presence of slowly moving barriers show normal diffusion for long times, but
anomalous diffusion at intermediate times. The effective exponents for square
distance versus time usually are below one at these intermediate times, but can
be also larger than one for high barrier concentrations. Thus we observe sub-
as well as super-diffusion in a crowded environment.Comment: 8 pages including 4 figure
Direct Minimization Generating Electronic States with Proper Occupation Numbers
We carry out the direct minimization of the energy functional proposed by
Mauri, Galli and Car to derive the correct self-consistent ground state with
fractional occupation numbers for a system degenerating at the Fermi level. As
a consequence, this approach enables us to determine the electronic structure
of metallic systems to a high degree of accuracy without the aid of level
broadening of the Fermi-distribution function. The efficiency of the method is
illustrated by calculating the ground-state energy of C and Si
molecules and the W(110) surface to which a tungsten adatom is adsorbed.Comment: 4 pages, 4 figure
Stability, Electronic Structure and Vibrational Modes of Ti_8C_12 Dimer
We present our density functional results of the geometry, electronic
structure and dissociation energy of Ti_8C_12 dimer. We show that as opposed to
the currently held view that Ti_8C_12 are highly stable monodispersed clusters,
the neutral Ti_8C_12 clusters form covalent bonds and form stable dimers. We
determine that the Ti atoms bond weakly (0.9 eV/bond) to organic ligands such
as ammonia. Alternatively the Met-Car dimer has a cohesive energy of 4.84 eV or
approximately 1.2 eV per bond. While Met-Car dimers are stable, formation of
these dimers may be quenched in an environment that contains a significant
population of organic ligands. The ionization and dissociation energies of the
dimer are of same order which prevents the observation of the dimer in the ion
mass spectroscopy. The analysis of the vibrational frequencies show the
lowest-energy structure to be dynamically stable. We also present infrared
absorption and Raman scattering spectra of the Ti_8C_12 dimer.Comment: 5 pages, 3 figures (Better quality figures available on request).
Physical Review B (Rapid Communication) (2002, in press
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