Structure and electronic structure of Metal-Organic Frameworks within the Density-Functional based Tight-Binding method

Density-functional based tight-binding is a powerful method to describe large molecules and materials. Metal-Organic Frameworks (MOFs), materials with interesting catalytic properties and with very large surface areas have been developed and have become commercially available. Unit cells of MOFs typically include hundreds of atoms, which make the application of standard Density-Functional methods computationally very expensive, sometimes even unfeasible. The aim of this paper is to prepare and to validate the Self-Consistent Charge Density-Functional based Tight Binding (SCC-DFTB) method for MOFs containing Cu, Zn and Al metal centers. The method has been validated against full hybrid density-functional calculations for model clusters, against gradient corrected density-functional calculations for supercells, and against experiment. Moreover, the modular concept of MOF chemistry has been discussed on the basis of their electronic properties. We concentrate on MOFs comprising three common connector units: copper paddlewheels (HKUST-1), zinc oxide Zn4O tetrahedron (MOF-5, MOF-177, DUT-6 (MOF-205)) and aluminium oxide AlO4(OH)2 octahedron (MIL-53). We show that SCC-DFTB predicts structural parameters with a very good accuracy (with less than 5% deviation, even for adsorbed CO and H2O on HKUST-1), while adsorption energies differ by 12 kJ mol-1 or less for CO and water compared to DFT benchmark calculations.Comment: Submitted to Phys. Status Solidi

Average ground-state energy of finite Fermi systems

Semiclassical theories like the Thomas-Fermi and Wigner-Kirkwood methods give a good description of the smooth average part of the total energy of a Fermi gas in some external potential when the chemical potential is varied. However, in systems with a fixed number of particles N, these methods overbind the actual average of the quantum energy as N is varied. We describe a theory that accounts for this effect. Numerical illustrations are discussed for fermions trapped in a harmonic oscillator potential and in a hard wall cavity, and for self-consistent calculations of atomic nuclei. In the latter case, the influence of deformations on the average behavior of the energy is also considered.Comment: 10 pages, 8 figure

Trace formula for dielectric cavities II: Regular, pseudo-integrable, and chaotic examples

Dielectric resonators are open systems particularly interesting due to their wide range of applications in optics and photonics. In a recent paper [PRE, vol. 78, 056202 (2008)] the trace formula for both the smooth and the oscillating parts of the resonance density was proposed and checked for the circular cavity. The present paper deals with numerous shapes which would be integrable (square, rectangle, and ellipse), pseudo-integrable (pentagon) and chaotic (stadium), if the cavities were closed (billiard case). A good agreement is found between the theoretical predictions, the numerical simulations, and experiments based on organic micro-lasers.Comment: 18 pages, 32 figure

Local structure study of In_xGa_(1-x)As semiconductor alloys using High Energy Synchrotron X-ray Diffraction

Nearest and higher neighbor distances as well as bond length distributions (static and thermal) of the In_xGa_(1-x)As (0<x<1) semiconductor alloys have been obtained from high real-space resolution atomic pair distribution functions (PDFs). Using this structural information, we modeled the local atomic displacements in In_xGa_(1-x)As alloys. From a supercell model based on the Kirkwood potential, we obtained 3-D As and (In,Ga) ensemble averaged probability distributions. This clearly shows that As atom displacements are highly directional and can be represented as a combination of and displacements. Examination of the Kirkwood model indicates that the standard deviation (sigma) of the static disorder on the (In,Ga) sublattice is around 60% of the value on the As sublattice and the (In,Ga) atomic displacements are much more isotropic than those on the As sublattice. The single crystal diffuse scattering calculated from the Kirkwood model shows that atomic displacements are most strongly correlated along directions.Comment: 10 pages, 12 figure

First measurement of the Head-Tail directional nuclear recoil signature at energies relevant to WIMP dark matter searches

We present first evidence for the so-called Head-Tail asymmetry signature of neutron-induced nuclear recoil tracks at energies down to 1.5 keV/amu using the 1m^3 DRIFT-IIc dark matter detector. This regime is appropriate for recoils induced by Weakly Interacting Massive Particle (WIMPs) but one where the differential ionization is poorly understood. We show that the distribution of recoil energies and directions induced here by Cf-252 neutrons matches well that expected from massive WIMPs. The results open a powerful new means of searching for a galactic signature from WIMPs.Comment: 4 pages, 6 figures, 1 tabl

Observation of isotonic symmetry for enhanced quadrupole collectivity in neutron-rich 62,64,66Fe isotopes at N=40

The transition rates for the 2_{1}^{+} states in 62,64,66Fe were studied using the Recoil Distance Doppler-Shift technique applied to projectile Coulomb excitation reactions. The deduced E2 strengths illustrate the enhanced collectivity of the neutron-rich Fe isotopes up to N=40. The results are interpreted by the generalized concept of valence proton symmetry which describes the evolution of nuclear structure around N=40 as governed by the number of valence protons with respect to Z~30. The deformation suggested by the experimental data is reproduced by state-of-the-art shell calculations with a new effective interaction developed for the fpgd valence space.Comment: 4 pages, 2 figure