Oxygen exchange in galls of Eurosta solidaginis (Diptera: Tephritidae)

Hypoxia in plant tissue should affect animals living within. Gallmakers stimulate their plant hosts to produce the gall they inhabit and feed on, and also influence the gall phenotype for other adaptations, such as defense against predators. The potential for hypoxia in galls of Eurosta solidaginis was studied in the context of potential adaptations to gall oxygen level, using a combination of direct measurement, mathematical modelling, and respirometry on both gallmakers and hosts. Modelling results suggested mild hypoxia tolerable to the larva persists for most of the growth season, whereas more severe hypoxia may occur earlier in fully-grown young galls. Field data from one of the two years studied showed hypoxia more severe than expected, and coincided with adverse weather conditions and high larval mortality. The hypoxia may be related to host response to adverse weather. Whether hypoxia directly caused larval mortality requires further study.

Macroeconomic News and Exchange Rates: Evidence of Unstable Effect

Although the link between macroeconomic news announcements and exchange rates is well documented in recent literature, this connection may be unstable. By using a broad set of macroeconomic news announcements and high frequency forex data for the Euro/Dollar, Pound/Dollar and Yen/Dollar from Nov 1, 2004 to Mar 31, 2014, we obtain two major findings with regards to this instability. First, many macroeconomic news announcements exhibit unstable effects with certain patterns in foreign exchange rates. These news effects may change in magnitude and even in their sign over time, over business cycles and crises within distinctive contexts. This finding is robust because the results are obtained by applying a Two-Regime Smooth Transition Regression Model, a Breakpoints Regression Model, and an Efficient Test of Parameter Instability which are all consistent with each other. Second, when we explore the source of this instability, we find that global risks and the reaction by central bank monetary policy to these risks to be possible factors causing this instability.

A DYNAMIC FRAMEWORK FOR THE RELATIONS BETWEEN FOREIGN EXCHANGE RATES, SAVINGS AND INVESTMENTS

The Meese-Rogoff forecasting puzzle states that foreign exchange (FX) rates are unpredictable. Since one country’s macroeconomic conditions could affect the price of its national currency, we study the dynamic relations between the FX rates and some macroeconomic accounts. Our research tests whether the predictability of the FX rates could be improved through the advanced econometrics. Improving the predictability of the FX rates has important implications for various groups including investors, business entities and the government. The present thesis examines the dynamic relations between the FX rates, savings and investments for a sample of 25 countries from the Organization for Economic Cooperation and Development. We apply quarterly data of FX rates, macroeconomic indices and accounts including the savings and the investments over three decades. Through preliminary Augmented Dickey-Fuller unit root tests and Johansen cointegration tests, we found that the savings rate and the investment rate are cointegrated with the vector (1,-1). This result is consistent with many previous studies on the savings-investment relations and therefore confirms the validity of the Feldstein-Horioka puzzle. Because of the special cointegrating relation between the savings rate and investment rate, we introduce the savings-investment rate differential (SID). Investigating each country through a vector autoregression (VAR) model, we observe extremely insignificant coefficient estimates of the historical SIDs upon the present FX rates. We also report similar findings through the panel VAR approach. We thus conclude that the historical SIDs are useless in forecasting the FX rate. Nonetheless, the coefficients of the past FX rates upon the current SIDs for both the country-specific and the panel VAR models are statistically significant. Therefore, we conclude that the historical FX rates can conversely predict the SID to some degree. Specifically, depreciation in the domestic currency would cause the increase in the SID.

Macroeconomic News Effects and Foreign Exchange Jumps

This thesis investigates how macroeconomic news announcements affect jumps and cojumps in foreign exchange markets, especially under different business cycles. We use 5-min interval from high frequency data on Euro/Dollar, Pound/Dollar and Yen/Dollar from Nov. 1, 2004 to Feb. 28, 2015. The jump detection method was proposed by Andersen et al. (2007c), Lee & Mykland (2008) and then modified by Boudt et al. (2011a) for robustness. Then we apply the two-regime smooth transition regression model of Teräsvirta (1994) to explore news effects under different business cycles. We find that scheduled news related to employment, real activity, forward expectations, monetary policy, current account, price and consumption influences forex jumps, but only FOMC Rate Decisions has consistent effects on cojumps. Speeches given by major central bank officials near a crisis also significantly affect jumps and cojumps. However, the impacts of some macroeconomic news are not the same under different economic states.

Macroeconomic News and LOB in Foreign Exchange ECN Market

We investigate the macroeconomic news effect on the dynamics of the limit order books (LOB) for euro-dollar ECN market in different economic states between Jan. 2006 to Dec. 2009. Using a VAR-STR model on the news surprise, pure news, aggregated good and bad news, we show that news effects on the LOB dynamics vary in different states of economy. The LOB dynamics are measured by depth, spread, slope and volatility. In contract to slope and volatility, depth and spread strongly respond to news surprise and pure news during recession and expansion. These characteristics are more affected by aggregated good and bad news during expansion. News effects are robust to alternative characteristic measures, the different sides of the LOB and the different levels in the LOB.

Systematic construction of models for the exchange hole of density functional theory.

Dans ce travail, nous étendons le nombre de conditions physiques actuellement con- nues du trou d’échange exact avec la dérivation de l’expansion de quatrième ordre du trou d’échange sphérique moyenne exacte. Nous comparons les expansions de deux- ième et de quatrième ordre avec le trou d’échange exact pour des systèmes atomiques et moléculaires. Nous avons constaté que, en général, l’expansion du quatrième ordre reproduit plus fidèlement le trou d’échange exact pour les petites valeurs de la distance interélectronique. Nous démontrons que les ensembles de base de type gaussiennes ont une influence significative sur les termes de cette nouvelle condition, en étudiant com- ment les oscillations causées par ces ensembles de bases affectent son premier terme. Aussi, nous proposons quatre modèles de trous d’échange analytiques auxquels nous imposons toutes les conditions actuellement connues du trou d’échange exact et la nou- velle présentée dans ce travail. Nous évaluons la performance des modèles en calculant des énergies d’échange et ses contributions à des énergies d’atomisation. On constate que les oscillations causeés par les bases de type gaussiennes peuvent compromettre la précision et la solution des modèles.

Exchange-correlation effects on quantum wires with spin-orbit interactions under the influence of in-plane magnetic fields.

Within the noncollinear local spin-density approximation, we have studied the ground state structure of a parabolically confined quantum wire submitted to an in-plane magnetic field, including both Rashba and Dresselhaus spin-orbit interactions. We have explored a wide range of linear electronic densities in the weak (strong) coupling regimes that appear when the ratio of spin-orbit to confining energy is small (large). These results are used to obtain the conductance of the wire. In the strong coupling limit, the interplay between the applied magnetic field¿irrespective of the in-plane direction, the exchange-correlation energy, and the spin-orbit energy-produces anomalous plateaus in the conductance vs linear density plots that are otherwise absent, or washes out plateaus that appear when the exchange-correlation energy is not taken into account.

The role of dynamical polarization of the ligand-to-metal charge transfer excitations in the ab initio determination of effective exchange parameters

The role of the bridging ligand on the effective Heisenberg coupling parameters is analyzed in detail. This analysis strongly suggests that the ligand-to-metal charge transfer excitations are responsible for a large part of the final value of the magnetic coupling constant. This permits us to suggest a variant of the difference dedicated configuration interaction (DDCI) method, presently one of the most accurate and reliable for the evaluation of magnetic effective interactions. This method treats the bridging ligand orbitals mediating the interaction at the same level than the magnetic orbitals and preserves the high quality of the DDCI results while being much less computationally demanding. The numerical accuracy of the new approach is illustrated on various systems with one or two magnetic electrons per magnetic center. The fact that accurate results can be obtained using a rather reduced configuration interaction space opens the possibility to study more complex systems with many magnetic centers and/or many electrons per center.

Electronic structure of a neutral oxygen vacancy in SrTiO3

The electronic structure of an isolated oxygen vacancy in SrTiO3 has been investigated with a variety of ab initio quantum mechanical approaches. In particular we compared pure density functional theory (DFT) approaches with the Hartree-Fock method, and with hybrid methods where the exchange term is treated in a mixed way. Both local cluster models and periodic calculations with large supercells containing up to 80 atoms have been performed. Both diamagnetic (singlet state) and paramagnetic (triplet state) solutions have been considered. We found that the formation of an O vacancy is accompanied by the transfer of two electrons to the 3d(z2) orbitals of the two Ti atoms along the Ti-Vac-Ti axis. The two electrons are spin coupled and the ground state is diamagnetic. New states associated with the defect center appear in the gap just below the conduction band edge. The formation energy computed with respect to an isolated oxygen atom in the triplet state is 9.4 eV.

First-principles electronic theory of non-collinear magnetic order in transition-metal nanowires

The structural, electronic and magnetic properties of one-dimensional 3d transition-metal (TM) monoatomic chains having linear, zigzag and ladder geometries are investigated in the frame-work of first-principles density-functional theory. The stability of long-range magnetic order along the nanowires is determined by computing the corresponding frozen-magnon dispersion relations as a function of the 'spin-wave' vector q. First, we show that the ground-state magnetic orders of V, Mn and Fe linear chains at the equilibrium interatomic distances are non-collinear (NC) spin-density waves (SDWs) with characteristic equilibrium wave vectors q that depend on the composition and interatomic distance. The electronic and magnetic properties of these novel spin-spiral structures are discussed from a local perspective by analyzing the spin-polarized electronic densities of states, the local magnetic moments and the spin-density distributions for representative values q. Second, we investigate the stability of NC spin arrangements in Fe zigzag chains and ladders. We find that the non-collinear SDWs are remarkably stable in the biatomic chains (square ladder), whereas ferromagnetic order (q =0) dominates in zigzag chains (triangular ladders). The different magnetic structures are interpreted in terms of the corresponding effective exchange interactions J(ij) between the local magnetic moments μ(i) and μ(j) at atoms i and j. The effective couplings are derived by fitting a classical Heisenberg model to the ab initio magnon dispersion relations. In addition they are analyzed in the framework of general magnetic phase diagrams having arbitrary first, second, and third nearest-neighbor (NN) interactions J(ij). The effect of external electric fields (EFs) on the stability of NC magnetic order has been quantified for representative monoatomic free-standing and deposited chains. We find that an external EF, which is applied perpendicular to the chains, favors non-collinear order in V chains, whereas it stabilizes the ferromagnetic (FM) order in Fe chains. Moreover, our calculations reveal a change in the magnetic order of V chains deposited on the Cu(110) surface in the presence of external EFs. In this case the NC spiral order, which was unstable in the absence of EF, becomes the most favorable one when perpendicular fields of the order of 0.1 V/Å are applied. As a final application of the theory we study the magnetic interactions within monoatomic TM chains deposited on graphene sheets. One observes that even weak chain substrate hybridizations can modify the magnetic order. Mn and Fe chains show incommensurable NC spin configurations. Remarkably, V chains show a transition from a spiral magnetic order in the freestanding geometry to FM order when they are deposited on a graphene sheet. Some TM-terminated zigzag graphene-nanoribbons, for example V and Fe terminated nanoribbons, also show NC spin configurations. Finally, the magnetic anisotropy energies (MAEs) of TM chains on graphene are investigated. It is shown that Co and Fe chains exhibit significant MAEs and orbital magnetic moments with in-plane easy magnetization axis. The remarkable changes in the magnetic properties of chains on graphene are correlated to charge transfers from the TMs to NN carbon atoms. Goals and limitations of this study and the resulting perspectives of future investigations are discussed.

Financial Information Mediation: A Case Study of Standards Integration for Electronic Bill Presentment and Payment Using the COIN Mediation Technology

Each player in the financial industry, each bank, stock exchange, government agency, or insurance company operates its own financial information system or systems. By its very nature, financial information, like the money that it represents, changes hands. Therefore the interoperation of financial information systems is the cornerstone of the financial services they support. E-services frameworks such as web services are an unprecedented opportunity for the flexible interoperation of financial systems. Naturally the critical economic role and the complexity of financial information led to the development of various standards. Yet standards alone are not the panacea: different groups of players use different standards or different interpretations of the same standard. We believe that the solution lies in the convergence of flexible E-services such as web-services and semantically rich meta-data as promised by the semantic Web; then a mediation architecture can be used for the documentation, identification, and resolution of semantic conflicts arising from the interoperation of heterogeneous financial services. In this paper we illustrate the nature of the problem in the Electronic Bill Presentment and Payment (EBPP) industry and the viability of the solution we propose. We describe and analyze the integration of services using four different formats: the IFX, OFX and SWIFT standards, and an example proprietary format. To accomplish this integration we use the COntext INterchange (COIN) framework. The COIN architecture leverages a model of sources and receivers’ contexts in reference to a rich domain model or ontology for the description and resolution of semantic heterogeneity.

Electronic and vibrational contributions to first hyperpolarizability of donor-acceptor-substituted azobenzene

In this study we report on the electronic and vibrational (hyper)polarizabilities of donor–acceptorsubstituted azobenzene. It is observed that both electronic and vibrational contributions to the electric dipole first hyperpolarizability of investigated photoactive molecule substantially depend on the conformation. The contributions to the nuclear relaxation first hyperpolarizability are found to be quite important in the case of two considered isomers (cis and trans). Although the double-harmonic term is found to be the largest in terms of magnitude, it is shown that the total value of the nuclear relaxation contribution to vibrational first hyperpolarizability is a result of subtle interplay of higher-order contributions. As a part of the study, we also assess the performance of long-range-corrected density functional theory in determining vibrational contributions to electric dipole (hyper)polarizabilities. In most cases, the applied long-range-corrected exchange correlation potentials amend the drawbacks of their conventional counterparts

Electronic properties, redox behavior, and interactions with H2O2 of pH-sensitive hydroxyphenyl-1,2,4-triazole-based oxovanadium(V)complexes

The syntheses and spectroscopic characterization of two 1,2,4-triazole-based oxovanadium(V) complexes are reported: 1(-)[VO(2)L1](-) and 2 [(VOL2)(2)(OMe)(2)] (where H(2)L1 = 3-(2'-hydroxyphenyl)-5-(pyridin-2"-yl)-H-1-1,2,4-triazole, H3L2 = bis-3,5-(2'-hydroxyphenyl)-1H-1,2,4-triazole). The ligand environment (N,N,O vs O,N,O) is found to have a profound influence on the properties and reactivity of the complexes formed. The presence of the triazolato ligand allows for pH tuning of the spectroscopic and electrochemical properties, as well as the interaction and stability of the complexes in the presence of hydrogen peroxide. The vanadium(IV) oxidation states were generated electrochemically and characterized by UV-vis and EPR spectroscopies, For 2, under acidic conditions, rapid exchange of the methoxide ligands with solvent [in particular, in the vanadium(IV) redox state] was observed.

Solvent-dependent modulation of metal–metal electronic interactions in a dinuclear cyanoruthenate complex: a detailed electrochemical, spectroscopic and computational study

The dinuclear complex [{Ru(CN)4}2(μ-bppz)]4− shows a strongly solvent-dependent metal–metal electronic interaction which allows the mixed-valence state to be switched from class 2 to class 3 by changing solvent from water to CH2Cl2. In CH2Cl2 the separation between the successive Ru(II)/Ru(III) redox couples is 350 mVand the IVCT band (from the UV/Vis/NIR spectroelectrochemistry) is characteristic of a borderline class II/III or class III mixed valence state. In water, the redox separation is only 110 mVand the much broader IVCT transition is characteristic of a class II mixed-valence state. This is consistent with the observation that raising and lowering the energy of the d(π) orbitals in CH2Cl2 or water, respectively, will decrease or increase the energy gap to the LUMO of the bppz bridging ligand, which provides the delocalisation pathway via electron-transfer. IR spectroelectrochemistry could only be carried out successfully in CH2Cl2 and revealed class III mixed-valence behaviour on the fast IR timescale. In contrast to this, time-resolved IR spectroscopy showed that the MLCTexcited state, which is formulated as RuIII(bppz˙−)RuII and can therefore be considered as a mixed-valence Ru(II)/Ru(III) complex with an intermediate bridging radical anion ligand, is localised on the IR timescale with spectroscopically distinct Ru(II) and Ru(III) termini. This is because the necessary electron-transfer via the bppz ligand is more difficult because of the additional electron on bppz˙− which raises the orbital through which electron exchange occurs in energy. DFT calculations reproduce the electronic spectra of the complex in all three Ru(II)/Ru(II), Ru(II)/Ru(III) and Ru(III)/Ru(III) calculations in both water and CH2Cl2 well as long as an explicit allowance is made for the presence of water molecules hydrogen-bonded to the cyanides in the model used. They also reproduce the excited-state IR spectra of both [Ru(CN)4(μ-bppz)]2– and [{Ru(CN)4}2(μ-bppz)]4− very well in both solvents. The reorganization of the water solvent shell indicates a possible dynamical reason for the longer life time of the triplet state in water compared to CH2Cl2.

Shubnikov de Haas oscillations in double wells with opposite signs of the electronic g-factor

We report on the measurements of the Shubnikov de Haas oscillations (SdH) in symmetrically doped AlxGa1-xAs double wells with different Al compositions in wells, which lead to the opposite signs of the electronic g-factor in each layer. Surprisingly, the spin splitting appears and collapses several times with increase in the magnetic field, We attribute such behaviour to the oscillations of the exchange-correlation term with Landau filling factor. (C) 2007 Elsevier B.V. All rights reserved.