NMR shielding tensors for density fitted local second-order Mo̸ller-Plesset perturbation theory using gauge including atomic orbitals

An efficient method for the calculation of nuclear magnetic resonance (NMR) shielding tensors is presented, which treats electron correlation at the level of second-order Mo?ller-Plesset perturbation theory. It uses spatially localized functions to span occupied and virtual molecular orbital spaces, respectively, which are expanded in a basis of gauge including atomic orbitals (GIAOs or London atomic orbitals). Doubly excited determinants are restricted to local subsets of the virtual space and pair energies with an interorbital distance beyond a certain threshold are omitted. Furthermore, density fitting is employed to factorize the electron repulsion integrals. Ordinary Gaussians are employed as fitting functions. It is shown that the errors in the resulting NMR shielding constant, introduced (i) by the local approximation and (ii) by density fitting, are very small or even negligible. The capabilities of the new program are demonstrated by calculations on some extended molecular systems, such as the cyclobutane pyrimidine dimer photolesion with adjacent nucleobases in the native intrahelical DNA double strand (ATTA sequence). Systems of that size were not accessible to correlated ab initio calculations of NMR spectra before. The presented method thus opens the door to new and interesting applications in this area.     

Investigation of superconductivity effects in single-phase and multiphase Bi2Sr2CaCu2O8 single-crystals at 2-MM wavelengths

Experimental investigations of superconductivity effects in single-phase and multiphase Bi₂Sr₂CaCu₂O₈ single-crystals have been carried out at 142 GHz frequency by means of the standing wave profile method [1]. Josephson harmonic generation has been observed to be responsible for the appearence of additional peaks on the standing wave profile of the open dielectric resonator loaded with a properly orientated multiphase high-T_c superconductor specimen. This leads to the conclusion that most of the Josephson junctions in multiphase crystals are located in certain crystallographic planes. The investigations of temperature dependencies showed that sharp resonant peaks of conductivity observed earlier [2] at 60 GHz could also be observed at 142 GHz.     

The blogosphere as an excitable social medium: Richter’s and Omori’s Law in media coverage

We study the dynamics of public media attention by monitoring the content of online blogs. Social and media events can be traced by the propagation of word frequencies of related keywords. Media events are classified as exogenous–where blogging activity is triggered by an external news item–or endogenous where word frequencies build up within a blogging community without external influences. We show that word occurrences exhibit statistical similarities to earthquakes. Moreover the size distribution of events scales with a similar exponent as found in the Gutenberg–Richter law. The dynamics of media events before and after the main event can be satisfactorily modeled as a type of process which has been used to understand fore–and aftershock rate distributions in earthquakes–the Omori law. We present empirical evidence that for media events of endogenous origin the overall public reception of the event is correlated with the behavior of word frequencies at the beginning of the event, and is to a certain degree predictable. These results imply that the process of opinion formation in a human society might be related to effects known from excitable media.     

Assemblies from metallic and semiconducting nanocrystals

Optical properties of nanomaterials such as semiconductor and metal quantum dots are important for sensors and photovoltaic applications. We report on optical, microscopic, and AFM investigations on bulk and single nanoobjects such as metal and semiconducting nanoparticles. Firstly, of special interest is the investigation of Ag metal nanoaggregates formed in zeolites. Here, the defined structure of the zeolite serves both as size directing and a stabilizing agent. The size selected Ag aggregates fluoresce in the zeolite cages even after storage under ambient conditions for almost one year. In addition, single Ag particles escape the cages and can be investigated by fluorescence microscopy also with respect to sensor applications. Secondly, with respect to photovoltaic applications, energy transfer among organic dye molecules and semiconductor quantum dots is of great importance. We report on the extension of the optical absorption of ZnSe quantum dots into the UV regime and investigate excitation energy transfer within self-assembled nanoaggregates of surface functionalized QDs and fluorescent styrylpyridine dyes.     

Equation of state of CaMnO3: a combined experimental and computational study

Elastic properties of CaMnO₃ are of primary importance in the science and technology of CaMnO₃-based perovskites. From X-ray diffraction experiments performed at pressures up to 100 kbar using a diamond-anvil cell to hydrostatically compress our sample, a bulk modulus, K ₀, of 1734(96) kbar was obtained after fitting parameters to the third-order Birch–Murnaghan equation of state. Mean field, semiclassical simulations predict, for the first time, the third-order equation-of-state parameters and show how the bulk modulus increases with pressure (the zero pressure value being 2062.1 kbar) and decreases with the extent of nonstoichiometry caused by the formation of oxygen vacancies. These trends are amplified for the shear modulus. A more accurate model that allows for the explicit reduction of Mn ions, or localization of excess electrons, yields qualitatively similar results. The experimental and calculated axial ratios show the same trends in their variation with rising pressure.     

Full vectorial band structure computation of photonic crystals with hexagonal lattice and a staircase approximation of the slanted unit cells

This paper describes band structure computations of photonic crystals with a hexagonal lattice. Particularly, the full vectorial three-dimensional case is considered. The unit cells are approximated with a staircase approximation. Due to their periodicity, fields inside the computational window can be related to those outside of this area. Numerical results are compared with those from the literature and show a very good agreement.     

Semiclassical Approximations for Hamiltonians with Operator-Valued Symbols

We consider the semiclassical limit of quantum systems with a Hamiltonian given by the Weyl quantization of an operator valued symbol. Systems composed of slow and fast degrees of freedom are of this form. Typically a small dimensionless parameter ${\varepsilon \ll 1}$ controls the separation of time scales and the limit ${\varepsilon\to 0}$ corresponds to an adiabatic limit, in which the slow and fast degrees of freedom decouple. At the same time ${\varepsilon\to 0}$ is the semiclassical limit for the slow degrees of freedom. In this paper we show that the ${\varepsilon}$ -dependent classical flow for the slow degrees of freedom first discovered by Littlejohn and Flynn (Phys Rev A (3) 44(8):5239–5256, 1991), coming from an ${\varepsilon}$ -dependent classical Hamilton function and an ${\varepsilon}$ -dependent symplectic form, has a concrete mathematical and physical meaning: Based on this flow we prove a formula for equilibrium expectations, an Egorov theorem and transport of Wigner functions, thereby approximating properties of the quantum system up to errors of order ${\varepsilon^2}$ . In the context of Bloch electrons formal use of this classical system has triggered considerable progress in solid state physics (Xiao et al. in Rev Mod Phys 82(3):1959–2007, 2010). Hence we discuss in some detail the application of the general results to the Hofstadter model, which describes a two-dimensional gas of non-interacting electrons in a constant magnetic field in the tight-binding approximation.     

Drag reduction in bubbly Taylor-Couette turbulence

In Taylor-Couette flow the total energy dissipation rate and therefore the drag can be determined by measuring the torque on the system. We do so for Reynolds numbers between Re=7 x 10(4) and Re=10(6) after having injected (i) small bubbles (R=1 mm) up to a volume concentration of alpha=5% and (ii) buoyant particles (rhop/rhol=0.14) of comparable volume concentration. In case (i) we observe a crossover from little drag reduction at smaller Re to strong drag reduction up to 20% at Re=10(6). In case (ii) we observe at most little drag reduction throughout. Several theoretical models for bubbly drag reduction are discussed in view of our findings.