Kerstin Hummer

Screened hybrid density functionals applied to solids

Hybrid Fock exchange/density functional theory functionals have shown to be very successful in describing a wide range of molecular properties. For periodic systems, however, the long-range nature of the Fock exchange interaction and the resultant large computational requirements present a major drawback. This is especially true for metallic systems, which require a dense Brillouin zone sampling. Recently, a new hybrid functional [HSE03, J. Heyd, G. E. Scuseria, and M. Ernzerhof, J. Chem. Phys. 118, 8207 (2003)] that addresses this problem within the context of methods that evaluate the Fock exchange in real space was introduced. We discuss the advantages the HSE03 functional brings to methods that rely on a reciprocal space description of the Fock exchange interaction, e.g., all methods that use plane wave basis sets. Furthermore, we present a detailed comparison of the performance of the HSE03 and PBE0 functionals for a set of archetypical solid state systems by calculating lattice parameters, bulk moduli, heats of formation, and band gaps. The results indicate that the hybrid functionals indeed often improve the description of these properties, but in several cases the results are not yet on par with standard gradient corrected functionals. This concerns in particular metallic systems for which the bandwidth and exchange splitting are seriously overestimated.

High pressure x-ray study on anthracene

The crystalline structure of anthracene (C14H10) under high pressure was studied performing angle dispersive x-ray diffraction experiments using synchrotron radiation in combination with Rietveld refinements and rigid body approximation. High hydrostatic pressure was applied up to 27.8 GPa using a diamond anvil cell. Full structural information (molecular orientations and lattice constants) is given up to a pressure of 20.3 GPa. At the highest pressure of 22.7 GPa the unit cell volume is decreased by 36.8%. Fourier transformation of the diffracted intensities reveals the electron density distribution within the unit cell. A pressure induced increase of the electron densities between adjacent molecules is observed. These findings are shown to be in agreement with theoretical calculations and hint towards the evolution of the anisotropic conductivity with pressure.

AB-INITIO STUDY ON THE EXCITON BINDING ENERGIES IN ORGANIC SEMICONDUCTORS

In this work, the optical properties including excitonic effects of organic semiconductors investigated within an ab-initio framework are reviewed. In particular, the imaginary part of the frequency-dependent dielectric tensor has been calculated for several organic molecular crystals consisting of short molecules and polymers, which comprise prime examples for the versatile class of organic semiconductors. The electron-hole interaction has been included by solving the Bethe–Salpeter equation for the two-particle Greens function. This approach allows for the evaluation of the exciton binding energies in such materials, which are of major interest concerning their technological application in organic opto-electronic devices. The results presented herein are compared to experimental data and surveyed together with previously reported theoretical findings, where particular emphasis is placed on analyzing the sensitivity of different approximations applied in the theoretical approaches. In this context, first the influence of the three-dimensional crystal environment versus one dimensional chains is addressed for the polymers. Second, the dependence of the exciton binding energy on the molecular size is studied by comparing the results obtained for the oligomers to those found for the polymers. As last aspect, the influence of the intermolecular interaction on the exciton binding energies is investigated by applying hydrostatic pressure.

Calculated Optical Absorption of Anthracene under High Pressure

Starting from the crystalline structure optimized with respect to the internal geometry we investigate the optical properties of anthracene up to 10.2 GPa within density functional theory. Using the random phase approximation we calculate the frequency-dependent complex dielectric tensor for several pressure values. We observe a red-shift of the absorption spectrum as a function of pressure, which is in good agreement with literature data.

Phase transition and electronic properties of fluorene: A joint experimental and theoretical high-pressure study

We report a high-pressure investigation of the relaxor ferroelectric lead zinc niobate PbZn{sub 1/3}Nb{sub 2/3}O{sub 3} (PZN) up to 46 GPa, which is the highest pressure yet attained in the study of relaxors. The evolution of both Raman and x-ray scattering with pressure gives evidence for important pressure instabilities, which find its expression in three successive phase transitions. The observed pressure-induced suppression of diffuse scattering above 5 GPa is similar to recent reports and supports the hypothesis that this is a general feature in relaxors at high pressures.Stable pairing states of superfluid {sup 3}He in aerogel are examined in the case with a global uniaxial anisotropy which may be created by applying a uniaxial stress to the aerogel. Due to such a global anisotropy, the stability region of an Anderson-Brinkman-Morel (ABM) pairing state becomes wider. In a uniaxially stretched aerogel, the pure polar pairing state with a horizontal line node is predicted to occur, as a three-dimensional superfluid phase, over a measurable width just below the superfluid transition at T{sub c}(P). A possible relevance of the present results to the case with no global anisotropy is also discussed.A series of Ca{sub x}CoO{sub 2} (0.15{<=}x{<=}0.40) materials have been prepared by means of an ion exchange reaction from Na{sub x}CoO{sub 2}. Transmission electron microscopy (TEM) measurements revealed a rich variety of structural phenomena resulting from cation ordering, structural distortion, and twinning. Systematic structural analysis, in combination with the experimental data of Na{sub x}CoO{sub 2} (0.15{<=}x{<=}0.8) and Sr{sub x}CoO{sub 2} (1.5{<=}x{<=}0.4) systems, suggests that there are two common well-defined cation ordered states corresponding, respectively, to the orthorhombic superstructure at around x=1/2 and the 3{sup 1/2}ax3{sup 1/2}a superstructure at around x=1/3 in this kind of system. Multiple ordered states, phase separation, and incommensurate structural modulations commonly appear in the materials with 0.33<x<0.5. The TEM observations also reveal an additional periodic structural distortion with q{sub 2}=a{sup *}/2 in materials for x{<=}0.35. This structural modulation also appears in the remarkable superconducting phase Na{sub 0.33}CoO{sub 2}{center_dot}1.3H{sub 2}O.Electrical resistance, thermoelectric power, dc magnetization, ac susceptibility, and electron spin resonance (ESR) are investigated for the polycrystalline Nd{sub 1-x}Sr{sub 1+x}CoO{sub 4} (x=0.25, 0.33, and 0.60). Powder x-ray diffraction (XRD) confirms that these compounds crystallize in K{sub 2}NiF{sub 4}-type structure with space group I4/mmm. The specimens exhibit ferromagnetic and semiconducting behaviors. With Sr doping, the lattice parameter c increases, the cusp intensity related to spin-glass states weakens, and the ferromagnetic property intensifies. The transport mechanisms in high temperature range obey Arrhenius law and might be understood by small polaron models. The magnetic properties present spin-glass states at {approx}18 K and Griffiths singularity at {approx}210 K.In this work we report on a low-energy electron diffraction (LEED) study of MnO(100) thick films grown on Ag(100) in order to determine their surface geometry. The LEED results indicate a topmost layer rumple of (4.8{+-}2.0)% with the oxygen ions moving towards the vacuum side. These results are in line with other surface structure determinations carried out on the (100) surface of different oxides having rock-salt structure but are in disagreement with MEIS results reported in the literature for the MnO(100) using a MnO single crystal.We report the observation of Co{sup 3+}/Co{sup 4+} short-range charge ordering in 10% Ho-doped SrCoO{sub 3-x} by means of high resolution neutron powder diffraction. The associated one-dimensional commensurate modulation, which can be described with the propagation vector q{sub CO}=(0 0 1/2) with respect to the cubic perovskite cell Pm3m, occurs for compositions close to x=0.20, corresponding to a 1:1 Co{sup 3+}/Co{sup 4+} ratio and extends over clusters of finite size (D{approx}250 A). The bond valence sums for the Co{sup 3+} and Co{sup 4+} sites are +3.07(7) and +3.95(11) (x=0.19), very close to their nominal values +3 and +4. We attribute this astonishing observation to the one-dimensional (1D) character of the associated distortion pattern, whose elastic stabilization is eased with respect to the 3D arrays reported for other charge-ordered perovskite oxides.The compounds RNi{sub 2}Mn (R=Tb, Dy, Ho, and Er) with a MgCu{sub 2}-type structure have been synthesized. The R to transition metal atom ratio is confirmed to be 1:3 using the energy dispersive spectroscopy. The structural and magnetic properties have been investigated by various experimental methods. The x-ray diffraction patterns (XRD) can be well indexed with a cubic Laves cell and space group Fd3m. The refinement results of the XRD patterns show the presence of vacancies in the crystallographic structure. The ordering temperatures T{sub C} have been derived to be 131, 94, 75, and 50 K for R=Tb, Dy, Ho and Er, respectively, which are much higher than those of their corresponding RNi{sub 2} and RMn{sub 2} compounds. A large difference of M-T curves between zero-field-cooling and field-cooling magnetization for all samples at a certain temperature range is observed in a low field, which can be understood in the terms of narrow-domain-wall pinning and a sensitive temperature dependence of coercivity.The structure of liquid CdTe was investigated at pressures up to 23.5 GPa using synchrotron x-ray diffraction. The structure factor, S(Q), and the pair distribution function, g(r), drastically change in two pressure regions, 1.8-3.0 and 7.0-9.0 GPa, accompanied with marked increase in the average coordination number. These findings suggest that there exists at least three stable liquid forms below 23.5 GPa. The pressure interval of the structural change is much smaller compared to other liquids of tetrahedrally bonded materials. Comparing the shapes of S(Q) and g(r) and other structural parameters with the respective data for the reference materials reveals that the lowest- and intermediate-pressure forms have the same local structures as the crystalline counterpart (zinc-blende-like local structure and a NaCl-like local structure), while the highest-pressure form has a different local structure from that in the crystalline form.The charge distributions of slow atomic particles that are singly scattered, multiply scattered, recoiled, and sputtered from metal surfaces are analyzed in terms of both nonadiabatic particle-substrate electron transfer and electron transfer from electronically excited substrates. The results are compared to experimental data for 50 eV Na{sup +} ions scattered from Cu(001), and Al atoms sputtered and recoiled from Al(100). The comparison allows for a quantitative determination of the role of substrate excitations in surface charge exchange. In addition, an analysis of kinetic electron emission (KEE) is carried out using similar low-energy metal projectile-metal substrate systems. Contributions to KEE from various nonadiabatic processes are quantitatively evaluated, including the same process that is responsible for charge formation in single-scattering experiments. The results are compared to experimental KEE data induced by Na{sup +} impinging on Ru(0001). The contributions of nonadiabatic one-electron processes are shown to be small when realistic particle-substrate parameters are used. Many-electron interactions are assumed to play an important role in explaining KEE and, as an illustration, a simplified hot-spot model is outlined.Neutron powder diffraction and transport measurements have been used to investigate the PrBaCo{sub 2}O{sub 5.48} compound between room temperature and 820 K. A structural phase transition, involving a rearrangement of oxygen vacancies, was found at T{sub OD}=776 K. Across the transition the perovskite structure loses its vacancy ordering, and the crystal symmetry changes from orthorhombic Pmmm to tetragonal P4/mmm. The resistivity measurements for temperatures above {approx}350 K yield high values of {rho}, indicating that the compound is rather semiconducting than metallic as usually accepted. A model in terms of thermally activated hole (polaronic) hopping is proposed.Granular films composed of well defined nanometric Co particles embedded in an insulating ZrO{sub 2} matrix were prepared by pulsed laser deposition in a wide range of Co volume concentrations (0.15<x<0.43). High-resolution transmission electron microscopy (TEM) showed very sharp interfaces between the crystalline particles and the amorphous matrix. Narrow particle size distributions were determined from TEM and by fitting the low-field magnetic susceptibility and isothermal magnetization in the paramagnetic regime to a distribution of Langevin functions. The magnetic particle size varies little for Co volume concentrations x<0.32 and increases as the percolation limit is approached. The tunneling magnetoresistance (TMR) was successfully reproduced using the Inoue-Maekawa model. The maximum value of TMR was temperature-independent within 50-300 K, and largely increased at low T, suggesting the occurrence of higher-order tunneling processes. Consequently, the tunneling conductance and TMR in clean granular metals are dominated by the Coulomb gap and the inherent particle size distribution.The five independent elastic moduli of single-crystalline hexagonal boron nitride (h-BN) are determined using inelastic x-ray scattering. At room temperature the elastic moduli are in units of GPa C{sub 11}=811, C{sub 12}=169, C{sub 13}=0, C{sub 33}=27.0, and C{sub 44}=7.7. Our experimental results are compared with predictions of ab initio calculations and previously reported incomplete datasets. These results provide solid background for further theoretical advances and quantitative input to model elasticity in boron nitride (BN) nanotubes.I argue that certain bosonic insulator-superfluid phase transitions as an interaction constant varies are driven by emergent geometric properties of insulating states. I examine the renormalized chemical potential and population of disordered bosons at different energy levels. These quantities define the geometric aspect of an effective low energy Hamiltonian which I employ to investigate various resonating states and quantum phase transitions. In a mean field approximation, I also demonstrate that the quantum phase transitions are in the universality class of a percolation problem.The electronic structure and physical properties of {gamma}-Sn{sub 3}N{sub 4} in the spinel structure are investigated by first-principles calculations. The calculated band structure, electronic bonding, and optical properties are compared with two well-studied spinel nitrides {gamma}-Si{sub 3}N{sub 4} and {gamma}-Ge{sub 3}N{sub 4}. {gamma}-Sn{sub 3}N{sub 4} is a semiconductor with a direct band gap of 1.40 eV and an attractive small electron effective mass of 0.17. Its optical properties are different from that of {gamma}-Si{sub 3}N{sub 4} and {gamma}-Ge{sub 3}N{sub 4} because of the difference in the conduction band minimum. The Sn K, Sn L{sub 3}, Sn M{sub 5}, and N K edges of the x-ray-absorption near-edge structure spectra in {gamma}-Sn{sub 3}N{sub 4} are calculated using a supercell approach and are found to be rich in structures. These spectra are discussed in the context of the electronic structure of the unoccupied conduction band in the presence of the electron core-hole interaction. These calculated spectra can be used for the characterization of this novel compound.The structure of the incommensurate phase of Rb{sub 2}ZnCl{sub 4} has been determined at 194 K (2 K above the lock-in transition) within the soliton regime using satellites up to fifth order. The rather anharmonic modulation functions agree with the expected steplike functions supported by theoretical arguments. In addition, the constancy of the ratio between the amplitudes of the fifth-order and first-order harmonics, a relation predicted by theory, indicate the correctness of the model and imply a value of 0.4 for the soliton density n{sub s}. A symmetry mode analysis shows that the incommensurate structure is consistent with the one of the lock-in phase in the sense that the displacement pattern of every symmetry mode remains unaltered in the transition except for a global change in the amplitudes.X-ray diffraction of SnO{sub 2} (cassiterite) at high pressures and temperatures demonstrates the existence of four phase transitions to 117 GPa. The observed sequence of phases for SnO{sub 2} is rutile-type (P4{sub 2}/mnm){yields}CaCl{sub 2}-type(Pnnm){yields}pyrite-type(Pa3){yields}ZrO{sub 2} orthorhombic phase I (Pbca){yields}cotunnite-type (Pnam). Our observations of the first three phases are generally in agreement with earlier studies. The orthorhombic phase I and cotunnite-type structure (orthorhombic phase II) were observed in SnO{sub 2} for the first time. The Pbca phase is found at 50-74 GPa during room-temperature compression. The cotunnite-type structure was synthesized when SnO{sub 2} was compressed to 74 GPa and heated at 1200 K. The cotunnite-type form was observed during compression between 54-117 GPa with additional laser heating carried out at 91 and 111 GPa. Fitting the pressure-volume data for the high-pressure phases to the second-order Birch-Murnaghan equation of state yields a bulk modulus of 259(26) GPa for the Pbca phase and 417(7) GPa for the cotunnite-type phase.We report x-ray photoelectron spectroscopy (XPS) study of Na and K adlayers on icosahedral Al{sub 70.5}Pd{sub 21}Mn{sub 8.5} (i-Al-Pd-Mn) quasicrystal. The Na 1s core-level exhibits a continuous linear shift of 0.8 eV towards lower binding energies (BE) with increasing coverage up to one monolayer (ML) saturation coverage. In the case of K/i-Al-Pd-Mn, a similar linear shift in the K 2p spectra towards lower BE is observed. In both cases, the plasmon related loss features are observed only above 1 ML. The substrate core-level peaks, such as Al 2p, do not exhibit any shift with the adlayer deposition up to the highest coverage. Based on these experimental observations and previous studies of alkali metal growth on metals, we conclude that below 1 ML, both Na and K form a dispersed phase on i-Al-Pd-Mn and there is hardly any charge transfer to the substrate. The variation of the adlayer and substrate core-level intensities with coverage indicates layer by layer growth.We report the magnetic properties of the ZnL{sub 2}S{sub 4} (L=Er,Tm,Yb) olivines, in which the magnetic lanthanide ions are in a potentially frustrated geometry consisting of sawtooth chains of corner-sharing triangles. Fits to the high-temperature magnetic susceptibility yielded Curie-Weiss temperatures of {theta}{sub W}{approx_equal}-4, -13, and -75 K for the Er, Tm, and Yb compounds, respectively. None of the compounds displayed magnetic long-range order above T=1.8 K. The lack of ordering at temperatures near {theta}{sub W} may be attributed to either the low dimensionality of the structure or the frustrating effect of the triangular geometry.

X-ray diffraction study of anthracene under high pressure

The aim of this study is to investigate the structural changes of molecular crystals based on aromatic molecules under high pressure. For this purpose we carried out angle dispersive X-ray diffraction experiments under pressure up to 25 GPa in combination with Rietveld refinement methods. Furthermore density functional calculations based on the experimentally obtained lattice parameters were carried out. We discuss the structural change of anthracene as a function of pressure and find very good agreement between experiment and theory.

The Crystal Sructure of Anthracene up to 22 GPa: a X-ray Diffraction Study

The aim of this study is to investigate the crystalline structure of anthracene C14H10 under high pressure performing angle dispersive x-ray diffraction experiments using synchrotron radiation in combination with Rietveld refinements and rigid body approximation. High hydrostatic pressure was applied up to 27.8 GPa using a diamond anvil cell. Full structural information (molecular orientations and lattice constants) is given up to a pressure of 20.3 GPa. At the highest pressure of 22.7 GPa the unit cell volume is decreased by 36.8%. Fourier transformation of the diffracted intensities reveals the electron density distribution within the unit cell. A pressure induced increase of the electron densities between adjacent molecules is observed. These findings are shown to be in agreement with theoretical calculations and hint towards the evolution of the anisotropic conductivity with pressure.