Effects of Side-Chain and Electron Exchange Correlation on the Band Structure of Perylene Diimide Liquid Crystals: A Density Functional Study

The structural and electronic properties of perylene diimide liquid crystal PPEEB are studied using ab initio methods based on the density functional theory (I)FT). Using available experimental crystallographic data as a guide, we propose a detailed structural model for the packing of solid PPEEB. We find that due to the localized nature of the band edge wave function, theoretical approaches beyond the standard method, such as hybrid functional (PBE0), are required to correctly characterize the band structure of this material. Moreover, unlike previous assumptions, we observe the formation of hydrogen bonds between the side chains of different molecules, which leads to a dispersion of the energy levels. This result indicates that the side chains of the molecular crystal not only are responsible for its structural conformation but also can be used for tuning the electronic and optical properties of these materials.

On the lower bound on the exchange-correlation energy in two dimensions

We study the properties of the lower bound on the exchange-correlation energy in two dimensions. First we review the derivation of the bound and show how it can be written in a simple density-functional form. This form allows an explicit determination of the prefactor of the bound and testing its tightness. Next we focus on finite two-dimensional systems and examine how their distance from the bound depends on the system geometry. The results for the high-density limit suggest that a finite system that comes as close as possible to the ultimate bound on the exchange-correlation energy has circular geometry and a weak confining potential with a negative curvature. (c) 2009 Elsevier B.V. All rights reserved.

On the generalized eigenvalue method for energies and matrix elements in lattice field theory

We discuss the generalized eigenvalue problem for computing energies and matrix elements in lattice gauge theory, including effective theories such as HQET. It is analyzed how the extracted effective energies and matrix elements converge when the time separations are made large. This suggests a particularly efficient application of the method for which we can prove that corrections vanish asymptotically as exp(-(E(N+1) - E(n))t). The gap E(N+1) - E(n) can be made large by increasing the number N of interpolating fields in the correlation matrix. We also show how excited state matrix elements can be extracted such that contaminations from all other states disappear exponentially in time. As a demonstration we present numerical results for the extraction of ground state and excited B-meson masses and decay constants in static approximation and to order 1/m(b) in HQET.

Orbital-polarization terms: From a phenomenological to a first-principles description of orbital magnetism in density-functional theory

Phenomenological orbital-polarizition (OP) terms have been repeatedly introduced in the single-particle equations of spin-density-functional theory, in order to improve the description of orbital magnetic moments in systems containing transition metal ions. Here we show that these ad hoc corrections can be interpreted as approximations to the exchange-correlation vector potential A(xc) of current-density functional theory (CDFT). This connection provides additional information on both approaches: phenomenological OP terms are connected to first-principles theory, leading to a rationale for their empirical success and a reassessment of their limitations and the approximations made in their derivation. Conversely, the connection of OP terms with CDFT leads to a set of simple approximations to the CDFT potential A(xc), with a number of desirable features that are absent from electron-gas-based functionals. (C) 2008 Wiley Periodicals, Inc.

Isolated capital cities and misgovernance: theory and evidence

Motivated by a novel stylized fact { countries with isolated capital cities display worse quality of governance { we provide a framework of endogenous institutional choice based on the idea that elites are constrained by the threat of rebellion, and that this threat is rendered less e ective by distance from the seat of political power. In established democracies, the threat of insurgencies is not a binding constraint, and the model predicts no correlation between isolated capitals and misgovernance. In contrast, a correlation emerges in equilibrium in the case of autocracies. Causality runs both ways: broader power sharing (associated with better governance) means that any rents have to be shared more broadly, hence the elite has less of an incentive to protect its position by isolating the capital city; conversely, a more isolated capital city allows the elite to appropriate a larger share of output, so the costs of better governance for the elite, in terms of rents that would have to be shared, are larger. We show evidence that this pattern holds true robustly in the data. We also show that isolated capitals are associated with less power sharing, a larger income premium enjoyed by capital city inhabitants, and lower levels of military spending by ruling elites, as predicted by the theory.

Workplace diversity and incentive contracts : theory and evidence

This paper presents a simple theory of the provision of incentives in firms in which the principal optimally chooses both compensation contracts and the composition of the work force. Assuming that individuals display group loyalty, a less diverse (more homogeneous) work force will be more cooperative. Simple comparative statics provide some testable implications relating risk, diversity and incentive pay. I also analyze the case in which workers’ characteristics cannot be readily observed ex ante. The theory then predicts that firms are more likely to prevent workers from interacting with each other when workers are expected to have similar characteristics. This shows a surprising effect of diversity in the workplace: more diverse firms will promote more interactions between workers of different types, i.e. they will be less segregated. I test the main predictions of the model using a cross-sectional sample of corporate boards. I use the proportion of women on boards as a measure of diversity. There are three main empirical findings: (1) a significant negative correlation between firm risk and diversity, (2) a significant positive relationship between performance-based compensation and diversity and (3) a significant positive correlation between the number of board meetings (a measure of interactions among directors) and diversity. The evidence is broadly consistent with the implications of the theory.

Effect of electron correlation on positronium formation in positron-helium scattering

A three-parameter correlated wave function for the helium ground state is used to study the scattering reaction e(+) + He --> He+ + Ps, where Ps stands for positronium atom. An exact analytical expression is constructed for the first Born scattering amplitude for Ps formation from helium. Based on this numerical results are presented for both differential and total cross-sections. It is demonstrated that the inner electronic correlation of the target atom plays a crucial role in explaining the discrepency between theory and experiment.

On the coupling of the self-dual field to dynamical U(1) matter and its dual theory

We consider arbitrary U (1) charged matter non-minimally coupled to the self-dual field in d = 2 + 1. The coupling includes a linear and a rather general quadratic term in the self-dual field. By using both Lagragian gauge embedding and master action approaches we derive the dual Maxwell Chern-Simons-type model and show the classical equivalence between the two theories. At the quantum level the master action approach in general requires the addition of an awkward extra term to the Maxwell Chern-Simons-type theory. Only in the case of a linear coupling in the self-dual field can the extra term be dropped and we are able to establish the quantum equivalence of gauge invariant correlation functions in both theories.

Perturbative bosonization from two-point correlation functions

Here we address the problem of bosonizing massive fermions without making expansions in the fermion masses in both massive QED(2) and QED(3) with N fermion flavors including also a Thirring coupling. We start from two-point correlators involving the U(1) fermionic current and the gauge field. From the tensor structure of those correlators we prove that the U(1) current must be identically conserved (topological) in the corresponding bosonized theory in both D=2 and D=3 dimensions. We find an effective generating functional in terms of bosonic fields which reproduces these two-point correlators and from that we obtain a map of the Lagrangian density (ψ) over bar (r)(ipartial derivative-m)psi(r) into a bosonic one in both dimensions. This map is nonlocal but it is independent of the electromagnetic and Thirring couplings, at least in the quadratic approximation for the fermionic determinant.

Intense and broad photoluminescence at room temperature in structurally disordered Ba[Zr0.25Ti0.75]O-3 powders: An experimental/theoretical correlation

Intense and broad photoluminescence (PL) emission at room temperature was observed on structurally disordered Ba[Zr0.25Ti0.75]O-3 (BZT) powders synthesized by the polymeric precursor method. BZT powders were annealed at 573 K for different times and at 973 K for 2 h in oxygen atmosphere. The single-phase cubic perovskite structure of the powder annealed at 973 K for 2 It was identified by X-ray diffraction and Fourier transform Raman techniques. PL emission increased with the increase of annealing time, which reached its maximum value in the powder annealed at 573 K for 192 h. First principles quantum mechanical calculations based on density functional theory (B3LYP level) were employed to study the electronic structure of ordered and disordered models. The theoretical calculations and experimental measurements of Ultraviolet-visible absorption spectroscopy indicate that the presence of intermediary energy levels in the band gap is favorable for the intense and broad PL emission at room temperature in disordered BZT powders. The PL behavior is probably due the existence of a charge gradient on the disordered structure, denoted by means of a charge transfer process from [TiO5]-[ZrO6] or [TiO6]-[ZrO5] clusters to [TiO6]-[ZrO6] clusters. (C) 2008 Elsevier Ltd. All rights reserved.

A heuristic approach for accessing and employing the infrared behavior of Yang-Mills correlation functions

This work analyses a hypothetically improved perturbative approach taking a dressed massive-like gluon propagator and an effective coupling into account. As an early step, corrections were calculated to the ghost and gluon propagators, and the ghost-gluon vertex in the Landau gauge, pure SU(3) Yang-Mills theory. Results were satisfactorily compared with lattice data. © 2013 American Institute of Physics.

Comments on correlation functions of large spin operators and null polygonal Wilson loops

We discuss the relation between correlation functions of twist-two large spin operators and expectation values of Wilson loops along light-like trajectories. After presenting some heuristic field theoretical arguments suggesting this relation, we compute the divergent part of the correlator in the limit of large 't Hooft coupling and large spins, using a semi-classical world-sheet which asymptotically looks like a GKP rotating string. We show this diverges as expected from the expectation value of a null Wilson loop, namely, as (ln mu(-2))(2). mu being a cut-off of the theory. (C) 2012 Elsevier B.V. All rights reserved.

Release of Cyanopyridine from a Ruthenium Complex Adsorbed on Gold: Surface-Enhanced Raman Scattering, Electrochemistry, and Density Functional Theory Analyses

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Correlation between structural and electronic order-disorder effects and optical properties in ZnO nanocrystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

On soft limits of large-scale structure correlation functions

We study soft limits of correlation functions for the density and velocity fields in the theory of structure formation. First, we re-derive the (resummed) consistency conditions at unequal times using the eikonal approximation. These are solely based on symmetry arguments and are therefore universal. Then, we explore the existence of equal-time relations in the soft limit which, on the other hand, depend on the interplay between soft and hard modes. We scrutinize two approaches in the literature: the time-flow formalism, and a background method where the soft mode is absorbed into a locally curved cosmology. The latter has been recently used to set up (angular averaged) 'equal-time consistency relations'. We explicitly demonstrate that the time-flow relations and 'equal-time consistency conditions'are only fulfilled at the linear level, and fail at next-to-leading order for an Einstein de-Sitter universe. While applied to the velocities both proposals break down beyond leading order, we find that the 'equal-time consistency conditions'quantitatively approximates the perturbative results for the density contrast. Thus, we generalize the background method to properly incorporate the effect of curvature in the density and velocity fluctuations on short scales, and discuss the reasons behind this discrepancy. We conclude with a few comments on practical implementations and future directions.