146 research outputs found
Theoretical calculations of magnetic order and anisotropy energies in molecular magnets
We present theoretical electronic structure calculations on the nature of electronic states and the magnetic coupling in the Mn12O12 free cluster and the Mn12O12(RCOO)16(H2O)4 molecular magnetic crystal. The calculations have been performed with the all-electron full-potential NRLMOL code. We find that the free Mn12O12cluster relaxes to an antiferromagneticcluster with no net moment. However, when coordinated by sixteen HCOO ligands and four H2O groups, as it is in the molecular crystal, we find that the ferrimagnetic ordering and geometrical and magnetic structure observed in the experiments is restored. Local Mn moments for the free and ligandated molecular magnets are presented and compared to experiment. We identify the occupied and unoccupied electronic states that are most responsible for the formation of the large anisotropy barrier and use a recently developed full-space and full-potential method for calculating the spinâorbit coupling interaction and anisotropy energies. Our calculated second-order anisotropy energy is in excellent agreement with experiment
Theory of Threading Edge and Screw Dislocations in GaN
The atomic structures, electrical properties, and line energies for threading screw and threading edge dislocations of wurtzite GaN are calculated within the local-density approximation. Both dislocations are electrically inactive with a band gap free from deep levels. These results are understood to arise from relaxed core structures which are similar to (1010) surfaces
Vibrational signatures for low-energy intermediate-sized Si clusters
We report low-energy locally stable structures for the clusters Si20 and Si21. The structures were obtained by performing geometry optimizations within the local density approximation. Our calculated binding energies for these clusters are larger than any previously reported for this size regime. To aid in the experimental identification of the structures, we have computed the full vibrational spectra of the clusters, along with the Raman and IR activities of the various modes using a recently developed first-principles technique. These represent, to our knowledge, the first calculations of Raman and IR spectra for Si clusters of this size
Density-functional-based predictions of Raman and IR spectra for small Si clusters
We have used a density-functional-based approach to study the response of silicon clusters to applied electric fields. For the dynamical response, we have calculated the Raman activities and infrared (IR) intensities for all of the vibrational modes of several clusters (SiN with N=3-8, 10, 13, 20, and 21) using the local density approximation (LDA). For the smaller clusters (N=3-8) our results are in good agreement with previous quantum-chemical calculations and experimental measurements, establishing that LDA-based IR and Raman data can be used in conjunction with measured spectra to determine the structure of clusters observed in experiment. To illustrate the potential of the method for larger clusters, we present calculated IR and Raman data for two low-energy isomers of Si10 and for the lowest-energy structure of Si13 found to date. For the static response, we compare our calculated polarizabilities for N=10, 13, 20, and 21 to recent experimental measurements. The calculated results are in rough agreement with experiment, but show less variation with cluster size than the measurements. Taken together, our results show that LDA calculations can offer a powerful means for establishing the structures of experimentally fabricated clusters and nanoscale systems
van der Waals interaction in nanotube bundles : consequences on vibrational modes
We have developed a pair-potential approach for the evaluation of van der
Waals interaction between carbon nanotubes in bundles.
Starting from a continuum model, we show that the intertube modes range from
to . Using a non-orthogonal tight-binding approximation
for describing the covalent intra-tube bonding in addition, we confirme a
slight chiral dependance of the breathing mode frequency and we found that this
breathing mode frequency increase by 10 % if the nanotube lie inside a
bundle as compared to the isolated tube.Comment: 5 pages, 2 figure
Theoretical investigation of carbon defects and diffusion in α-quartz
The geometries, formation energies, and diffusion barriers of carbon point defects in silica (α-quartz) have been calculated using a charge-self-consistent density-functional based nonorthogonal tight-binding method. It is found that bonded interstitial carbon configurations have significantly lower formation energies (on the order of 5 eV) than substitutionals. The activation energy of atomic C diffusion via trapping and detrapping in interstitial positions is about 2.7 eV. Extraction of a CO molecule requires an activation energy <3.1âeV but the CO molecule can diffuse with an activation energy <0.4âeV. Retrapping in oxygen vacancies is hinderedâunlike for O2âby a barrier of about 2 eV
Conductance of Distorted Carbon Nanotubes
We have calculated the effects of structural distortions of armchair carbon
nanotubes on their electrical transport properties. We found that the bending
of the nanotubes decreases their transmission function in certain energy ranges
and leads to an increased electrical resistance. Electronic structure
calculations show that these energy ranges contain localized states with
significant - hybridization resulting from the increased curvature
produced by bending. Our calculations of the contact resistance show that the
large contact resistances observed for SWNTs are likely due to the weak
coupling of the NT to the metal in side bonded NT-metal configurations.Comment: 5 pages RevTeX including 4 figures, submitted to PR
Evidence for Quantum Interference in SAMs of Arylethynylene Thiolates in Tunneling Junctions with Eutectic Ga-In (EGaIn) Top-Contacts
This paper compares the current density (J) versus applied bias (V) of self-assembled monolayers (SAMs) of three different ethynylthiophenol-functionalized anthracene derivatives of approximately the same thickness with linear-conjugation (AC), cross-conjugation (AQ), and broken-conjugation (AH) using liquid eutectic Ga-In (EGaIn) supporting a native skin (~1 nm thick) of Ga2O3 as a nondamaging, conformal top-contact. This skin imparts non-Newtonian rheological properties that distinguish EGaIn from other top-contacts; however, it may also have limited the maximum values of J observed for AC. The measured values of J for AH and AQ are not significantly different (J â 10-1 A/cm2 at V = 0.4 V). For AC, however, J is 1 (using log averages) or 2 (using Gaussian fits) orders of magnitude higher than for AH and AQ. These values are in good qualitative agreement with gDFTB calculations on single AC, AQ, and AH molecules chemisorbed between Au contacts that predict currents, I, that are 2 orders of magnitude higher for AC than for AH at 0 < |V| < 0.4 V. The calculations predict a higher value of I for AQ than for AH; however, the magnitude is highly dependent on the position of the Fermi energy, which cannot be calculated precisely. In this sense, the theoretical predictions and experimental conclusions agree that linearly conjugated AC is significantly more conductive than either cross-conjugated AQ or broken conjugate AH and that AQ and AH cannot necessarily be easily differentiated from each other. These observations are ascribed to quantum interference effects. The agreement between the theoretical predictions on single molecules and the measurements on SAMs suggest that molecule-molecule interactions do not play a significant role in the transport properties of AC, AQ, and AH.
Modeling the series of (n x 2) Si-rich reconstructions of beta-SiC(001): a prospective atomic wire?
We perform ab initio plane wave supercell density functional calculations on
three candidate models of the (3 x 2) reconstruction of the beta-SiC(001)
surface. We find that the two-adlayer asymmetric-dimer model (TAADM) is
unambiguously favored for all reasonable values of Si chemical potential. We
then use structures derived from the TAADM parent to model the silicon lines
that are observed when the (3 x 2) reconstruction is annealed (the (n x 2)
series of reconstructions), using a tight-binding method. We find that as we
increase n, and so separate the lines, a structural transition occurs in which
the top addimer of the line flattens. We also find that associated with the
separation of the lines is a large decrease in the HOMO-LUMO gap, and that the
HOMO state becomes quasi-one-dimensional. These properties are qualititatively
and quantitatively different from the electronic properties of the original (3
x 2) reconstruction.Comment: 22 pages, including 6 EPS figure
Pseudopotential study of binding properties of solids within generalized gradient approximations: The role of core-valence exchange-correlation
In ab initio pseudopotential calculations within density-functional theory
the nonlinear exchange-correlation interaction between valence and core
electrons is often treated linearly through the pseudopotential. We discuss the
accuracy and limitations of this approximation regarding a comparison of the
local density approximation (LDA) and generalized gradient approximations
(GGA), which we find to describe core-valence exchange-correlation markedly
different. (1) Evaluating the binding properties of a number of typical solids
we demonstrate that the pseudopotential approach and namely the linearization
of core-valence exchange-correlation are both accurate and limited in the same
way in GGA as in LDA. (2) Examining the practice to carry out GGA calculations
using pseudopotentials derived within LDA we show that the ensuing results
differ significantly from those obtained using pseudopotentials derived within
GGA. As principal source of these differences we identify the distinct behavior
of core-valence exchange-correlation in LDA and GGA which, accordingly,
contributes substantially to the GGA induced changes of calculated binding
properties.Comment: 13 pages, 6 figures, submitted to Phys. Rev. B, other related
publications can be found at http://www.rz-berlin.mpg.de/th/paper.htm
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