Non-Marcus energy gap dependence of electron transfer rate in contact ion pairs. Novel interplay between relaxation and reaction in solution

Electron transfer reactions between donor-acceptor pairs in solution and in organized media exhibit diverse behaviour. Recent experiments have indicated an interesting breakdown of the Marcus parabolic energy gap dependence in the normal regime for back electron transfer from contact ion pairs. A novel explanation of this breakdown has recently been proposed (M. Tachiya and S. Murata, J. Am. Chem. Sec., 116(1994) 2434) which attributes the breakdown to the interplay between the relaxation in the reactant well and the reaction. A particularly interesting aspect of the model is that it envisages the electron transfer in the normal regime to take place from a completely non-equilibrium condition. In this article a time dependent solution of the model is presented for the first time, after generalizing it to include a realistic initial population distribution. The decay of the contact ion pair population is completely non-exponential. This can be used to check the validity of the Tachiya-Murata model. The dynamics of electron transfer from the solvent separated ion pair, which seem to obey the Marcus relation, is exponential.

Interplay of spin and lattice degrees of freedom in the frustrated antiferromagnet CdCr2O4: High-field and temperature-induced anomalies of the elastic constants

Temperature and magnetic field studies of the elastic constants of the chromium spinel CdCr2O4 show pronounced anomalies related to strong spin-phonon coupling in this frustrated antiferromagnet. A detailed comparison of the longitudinal acoustic mode propagating along the 111] direction with a theory based on an exchange-striction mechanism leads to an estimate of the strength of the magnetoelastic interaction. The derived spin-phonon coupling constant is in good agreement with previous determinations based on infrared absorption. Further insight is gained from intermediate and high magnetic field experiments in the field regime of the magnetization plateau. The role of the antisymmetric Dzyaloshinskii-Moriya interaction is discussed.

Crystallographic texture and microstructure evolution during hot compression of Ti-6Al-4V-0.1B alloy in the (alpha plus beta)-regime

Microstructure and texture are known to undergo drastic modifications due to trace hypoeutectic boron addition (similar to 0.1wt.%) for various titanium alloys e.g. Ti-6Al-4V. The deformation behaviour of such an alloy Ti-6Al-4V-0.1B is investigated in the (+) phase field and compared against that of the base alloy Ti-6Al-4V studied under selfsame conditions. The deformation microstructures for the two alloys display bending and kinking of lamellae in near and softening via globularization of lamella in near phase regimes, respectively. The transition temperature at which pure slip based deformation changes to softening is lower for the boron added alloy. The presence of TiB particles is largely held attributable for the early softening of Ti-6Al-4V-0.1B alloy. The compression texture of both the alloys carry signature of pure phase defamation at lower temperature and phase transformation near the transus temperature. Texture is influenced by a complex interplay of the deformation and transformation processes in the intermediate temperature range. The contribution from phase transformation is prominent for Ti-6Al-4V-0.1B alloy at comparatively lower temperature.

The interplay of localization and interactions in quantum many-body systems

Disorder and interactions both play crucial roles in quantum transport. Decades ago, Mott showed that electron-electron interactions can lead to insulating behavior in materials that conventional band theory predicts to be conducting. Soon thereafter, Anderson demonstrated that disorder can localize a quantum particle through the wave interference phenomenon of Anderson localization. Although interactions and disorder both separately induce insulating behavior, the interplay of these two ingredients is subtle and often leads to surprising behavior at the periphery of our current understanding. Modern experiments probe these phenomena in a variety of contexts (e.g. disordered superconductors, cold atoms, photonic waveguides, etc.); thus, theoretical and numerical advancements are urgently needed. In this thesis, we report progress on understanding two contexts in which the interplay of disorder and interactions is especially important.

The first is the so-called “dirty” or random boson problem. In the past decade, a strong-disorder renormalization group (SDRG) treatment by Altman, Kafri, Polkovnikov, and Refael has raised the possibility of a new unstable fixed point governing the superfluid-insulator transition in the one-dimensional dirty boson problem. This new critical behavior may take over from the weak-disorder criticality of Giamarchi and Schulz when disorder is sufficiently strong. We analytically determine the scaling of the superfluid susceptibility at the strong-disorder fixed point and connect our analysis to recent Monte Carlo simulations by Hrahsheh and Vojta. We then shift our attention to two dimensions and use a numerical implementation of the SDRG to locate the fixed point governing the superfluid-insulator transition there. We identify several universal properties of this transition, which are fully independent of the microscopic features of the disorder.

The second focus of this thesis is the interplay of localization and interactions in systems with high energy density (i.e., far from the usual low energy limit of condensed matter physics). Recent theoretical and numerical work indicates that localization can survive in this regime, provided that interactions are sufficiently weak. Stronger interactions can destroy localization, leading to a so-called many-body localization transition. This dynamical phase transition is relevant to questions of thermalization in isolated quantum systems: it separates a many-body localized phase, in which localization prevents transport and thermalization, from a conducting (“ergodic”) phase in which the usual assumptions of quantum statistical mechanics hold. Here, we present evidence that many-body localization also occurs in quasiperiodic systems that lack true disorder.

Archives information publishing new design in post-custodial regime: The National Archives Experience Digital Vaults

The uses of Information and Communication Technologies (ICT) and Web environments for creation, treatment and availability of information have supported the emergence of new social-cultural patterns represented by convergences in textual, image and audio languages. This paper describes and analyzes the National Archives Experience Digital Vaults as a digital publishing web environment and as a cultural heritage. It is a complex system - synthesizer of information design options at information setting, provides new aesthetic aspects, but specially enlarges the cognition of the subjects who interact with the environment. It also enlarges the institutional spaces that guard the collective memory beyond its role of keeping the physical patrimony collected there. Digital Vaults lies as a mix of guide and interactive catalogue to be dealt in a ludic way. The publishing design of the information held on the Archives is meant to facilitate access to knowledge. The documents are organized in a dynamic and not chronological way. They are not divided in fonds or distinct categories, but in controlled interaction of documents previously indexed and linked by the software. The software creates information design and view of documental content that can be considered a new paradigm in Information Science and are part of post-custodial regime, independent from physical spaces and institutions. Information professionals must be prepared to understand and work with the paradigmatic changes described and represented by the new hybrid digital environments; hence the importance of this paper. Cyberspace interactivity between user and the content provided by the environment design provide cooperation, collaboration and sharing knowledge actions, all features of networks, transforming culture globally.

Archives information publishing new design in post-custodial regime: the national archives experience digital vaults

The uses of Information and Communication Technologies (ICT) and Web environments for creation, treatment and availability of information have supported the emergence of new social-cultural patterns represented by convergences in textual, image and audio languages. This paper describes and analyzes the National Archives Experience Digital Vaults as a digital publishing web environment and as a cultural heritage. It is a complex system - synthesizer of information design options at information setting, provides new aesthetic aspects, but specially enlarges the cognition of the subjects who interact with the environment. It also enlarges the institutional spaces that guard the collective memory beyond its role of keeping the physical patrimony collected there. Digital Vaults lies as a mix of guide and interactive catalogue to be dealt in a ludic way. The publishing design of the information held on the Archives is meant to facilitate access to knowledge. The documents are organized in a dynamic and not chronological way. They are not divided in fonds or distinct categories, but in controlled interaction of documents previously indexed and linked by the software. The software creates information design and view of documental content that can be considered a new paradigm in Information Science and are part of post-custodial regime, independent from physical spaces and institutions. Information professionals must be prepared to understand and work with the paradigmatic changes described and represented by the new hybrid digital environments; hence the importance of this paper. Cyberspace interactivity between user and the content provided by the environment design provide cooperation, collaboration and sharing knowledge actions, all features of networks, transforming culture globally.

Recoupled separated-local-field experiments and applications to study intermediate-regime molecular motions

A specific separated-local-field NMR experiment, dubbed Dipolar-Chemical-Shift Correlation (DIPSHIFT) is frequently used to study molecular motions by probing reorientations through the changes in XH dipolar coupling and T-2. In systems where the coupling is weak or the reorientation angle is small, a recoupled variant of the DIPSHIFT experiment is applied, where the effective dipolar coupling is amplified by a REDOR-like pi-pulse train. However, a previously described constant-time variant of this experiment is not sensitive to the motion-induced T-2 effect, which precludes the observation of motions over a large range of rates ranging from hundreds of Hz to around a MHz. We present a DIPSHIFT implementation which amplifies the dipolar couplings and is still sensitive to T-2 effects. Spin dynamics simulations, analytical calculations and experiments demonstrate the sensitivity of the technique to molecular motions, and suggest the best experimental conditions to avoid imperfections. Furthermore, an in-depth theoretical analysis of the interplay of REDOR-like recoupling and proton decoupling based on Average-Hamiltonian Theory was performed, which allowed explaining the origin of many artifacts found in literature data. (C) 2012 Elsevier Inc. All rights reserved.

Planet formation models: the interplay with the planetesimal disc

Context. According to the sequential accretion model (or core-nucleated accretion model), giant planet formation is based first on the formation of a solid core which, when massive enough, can gravitationally bind gas from the nebula to form the envelope. The most critical part of the model is the formation time of the core: to trigger the accretion of gas, the core has to grow up to several Earth masses before the gas component of the protoplanetary disc dissipates. Aims: We calculate planetary formation models including a detailed description of the dynamics of the planetesimal disc, taking into account both gas drag and excitation of forming planets. Methods: We computed the formation of planets, considering the oligarchic regime for the growth of the solid core. Embryos growing in the disc stir their neighbour planetesimals, exciting their relative velocities, which makes accretion more difficult. Here we introduce a more realistic treatment for the evolution of planetesimals' relative velocities, which directly impact on the formation timescale. For this, we computed the excitation state of planetesimals, as a result of stirring by forming planets, and gas-solid interactions. Results: We find that the formation of giant planets is favoured by the accretion of small planetesimals, as their random velocities are more easily damped by the gas drag of the nebula. Moreover, the capture radius of a protoplanet with a (tiny) envelope is also larger for small planetesimals. However, planets migrate as a result of disc-planet angular momentum exchange, with important consequences for their survival: due to the slow growth of a protoplanet in the oligarchic regime, rapid inward type I migration has important implications on intermediate-mass planets that have not yet started their runaway accretion phase of gas. Most of these planets are lost in the central star. Surviving planets have masses either below 10 M⊕ or above several Jupiter masses. Conclusions: To form giant planets before the dissipation of the disc, small planetesimals (~0.1 km) have to be the major contributors of the solid accretion process. However, the combination of oligarchic growth and fast inward migration leads to the absence of intermediate-mass planets. Other processes must therefore be at work to explain the population of extrasolar planets that are presently known.

The function of property in creating an effective legal regime for trade in environmental offsets

Market-based environmental regulation is becoming increasingly common within international and national frameworks. Environmental offset and trading regimes are part of the market-based instrument revolution. This paper proposes that environmental market mechanisms could be used to introduce an ethic of land holder responsibility. In order for market based regimes to attract sufficient levels of stakeholder engagement, participants within such scheme require an incentive to participate and furthermore need to feel a sense of security about investing in such processes. A sense of security is often associated with property based interests. This paper explores the property related issues connected with environmental offset and trading scheme initiatives. Relevant property-related considerations include land tenure considerations, public versus private management of land choices, characteristics and powers associated with property interests, theories defining property and the recognition of legal proprietal interests. The Biodiversity Banking Scheme in New South Wales is then examined as a case study followed by a critique on the role of environmental markets.

Business model construction : the importance of regime of appropriability strategies

To date, most theories of business models have theorized value capture assuming that appropriability regimes were exogenous and that the firm would face a unique, ideal-typical appropriability regime. This has led theory contributions to focus on governance structures to minimize transaction costs, to downplay the interdepencies between value capture and value creation, and to ignore revenue generation strategies. We propose a reconceptualization of business models value capture mechanisms that rely on assumptions of endogeneity and multiplicity of appropriability regimes. This new approach to business model construction highlights the interdependencies and trade-offs between value creation and value capture offered by different types and combinations of appropriability regimes. The theory is illustrated by the analysis of three cases of open source software business models

Australian media ethics regime and ethical risk management

Media organizations are simultaneously key elements of an effective democracy and, for the most part, commercial entities seeking success in the market. They play an essential role in the formation of public opinion and the influence on personal choices. Yet most of them are commercial enterprises seeking readers or viewers, advertising, favorable regulatory decisions for their media, and other assets. This creates some intrinsic difficulties and produces some sharp tensions within media ethics. In this article, we examine such tensions—in theory and practice. We then consider the feasibility of introducing an ethics regime to the media industry—a regime that would be effective in a deregulated environment in protecting public interest and social responsibility. In the article, we also outline a rationale and a methodology for the institutionalization of an acceptable and workable media ethics regime that aims to protect the integrity of the industry in a future of undoubtedly increasing commercial pressure.