Autonomy and Control of State Agencies:Comparing States and Agencies

Do public organizations with similar tasks or structures differ across states with respect to their autonomy and control? If so, why? By comparing the autonomy, control and internal management of state agencies, this book shows how New Public Management doctrines actually work in three small European states with different politico-administrative regimes. Using a unique set of similar survey data on 226 state agencies in Norway, Ireland and Flanders, this study explains differences in agency autonomy, control and management by referring to international isomorphic pressures, state-specific politico-administrative regimes and characteristics of agencies. Therefore, organization theory and neo-institutional schools are used to formulate four competing theoretical perspectives and hypotheses are tested through simple and advanced statistical techniques. By comparing practices between states and between types of agencies, this study substantially enhances scientific knowledge about why public organizations are granted autonomy, why they are controlled in specific ways, and how autonomy affects internal management.

Density Functional Theory Study on the Cleavage Mechanism of the Carbonyl Bond in Amides on Flat and Stepped Ru Surfaces: Hydrogen-Induced or Direct C-O Bond Breaking?

We have performed density functional theory (DFT) calculations to investigate the reaction mechanism of the cleavage of the carbonyl bond in amides on both flat and stepped Ru surfaces. The simplest amide molecule, N,N-dimethylacetamide (DMA), was used as the exemplar model molecule. Through the calculations, the most stable transition states (TSs) in all the pathways on both flat and stepped Ru surfaces are identified. Comparing the energy profiles of different reaction pathways, we find that a direct cleavage mechanism is always energetically favored as compared with an alternative hydrogen-induced mechanism on either the flat or stepped Ru surface. It is easier for the dissociation process to occur on the stepped surface than on the flat surface. However, as compared with the terrace, the superiority of step sites boosting the C-O bond dissociation is not as evident as that on CO dissociation.

Electronic properties of interfaces and defects from many-body perturbation theory: Recent developments and applications

We review some recent developments in many body perturbation theory (MBPT) calculations that have enabled the study of interfaces and defects. Starting from the theoretical basis of MBPT, Hedin's equations are presented, leading to the CW and CWI' approximations. We introduce the perturbative approach, that is the one most commonly used for obtaining quasiparticle (QP) energies. The practical strategy presented for dealing with the frequency dependence of the self energy operator is based on either plasmon-pole models (PPM) or the contour deformation technique, with the latter being more accurate. We also discuss the extrapolar method for reducing the number of unoccupied states which need to be included explicity in the calculations. The use of the PAW method in the framework of MBPT is also described. Finally, results which have been obtained using, MBPT for band offsets a interfaces and for defects presented, with companies on the main difficulties and cancels.

Schematic representation of the QP corrections (marked with ) to the band edges (E and E-v) and a defect level (F) for a Si/SiO2 interface (Si and O atoms are represented in blue and red, respectively, in the ball and stick model) with an oxygen vacancy leading to a Si-Si bond (the Si atoms involved in this bond are colored light blue).

Macroscopic limit of time-dependent density-functional theory for adiabatic local approximations of the exchange-correlation kernel

Time-dependent density-functional theory is a rather accurate and efficient way to compute electronic excitations for finite systems. However, in the macroscopic limit (systems of increasing size), for the usual adiabatic random-phase, local-density, or generalized-gradient approximations, one recovers the Kohn-Sham independent-particle picture, and thus the incorrect band gap. To clarify this trend, we investigate the macroscopic limit of the exchange-correlation kernel in such approximations by means of an algebraical analysis complemented with numerical studies of a one-dimensional tight-binding model. We link the failure to shift the Kohn-Sham spectrum of these approximate kernels to the fact that the corresponding operators in the transition space act only on a finite subspace.

Density functionals from many-body perturbation theory: The band gap for semiconductors and insulators

Theoretically the Kohn-Sham band gap differs from the exact quasiparticle energy gap by the derivative discontinuity of the exchange-correlation functional. In practice for semiconductors and insulators the band gap calculated within any local or semilocal density approximations underestimates severely the experimental energy gap. On the other hand, calculations with an "exact" exchange potential derived from many-body perturbation theory via the optimized effective potential suggest that improving the exchange-correlation potential approximation can yield a reasonable agreement between the Kohn-Sham band gap and the experimental gap. The results in this work show that this is not the case. In fact, we add to the exact exchange the correlation that corresponds to the dynamical (random phase approximation) screening in the GW approximation. This accurate exchange-correlation potential provides band structures similar to the local density approximation with the corresponding derivative discontinuity that contributes 30%-50% to the energy gap. Our self-consistent results confirm substantially the results for Si and other semiconductors obtained perturbatively [R. W. Godby , Phys. Rev. B 36, 6497 (1987)] and extend the conclusion to LiF and Ar, a wide-gap insulator and a noble-gas solid. (c) 2006 American Institute of Physics.

Almost all quantum states have nonclassical correlations

Quantum discord quantifies nonclassical correlations in a quantum system including those not captured by entanglement. Thus, only states with zero discord exhibit strictly classical correlations. We prove that these states are negligible in the whole Hilbert space: typically a state picked out at random has positive discord and, given a state with zero discord, a generic arbitrarily small perturbation drives it to a positive-discord state. These results hold for any Hilbert-space dimension and have direct implications for quantum computation and for the foundations of the theory of open systems. In addition, we provide a simple necessary criterion for zero quantum discord. Finally, we show that, for almost all positive-discord states, an arbitrary Markovian evolution cannot lead to a sudden, permanent vanishing of discord.

A multiconfigurational time-dependent Hartree-Fock method for excited electronic states. I. General formalism and application to open-shell states

The solution of the time-dependent Schrodinger equation for systems of interacting electrons is generally a prohibitive task, for which approximate methods are necessary. Popular approaches, such as the time-dependent Hartree-Fock (TDHF) approximation and time-dependent density functional theory (TDDFT), are essentially single-configurational schemes. TDHF is by construction incapable of fully accounting for the excited character of the electronic states involved in many physical processes of interest; TDDFT, although exact in principle, is limited by the currently available exchange-correlation functionals. On the other hand, multiconfigurational methods, such as the multiconfigurational time-dependent Hartree-Fock (MCTDHF) approach, provide an accurate description of the excited states and can be systematically improved. However, the computational cost becomes prohibitive as the number of degrees of freedom increases, and thus, at present, the MCTDHF method is only practical for few-electron systems. In this work, we propose an alternative approach which effectively establishes a compromise between efficiency and accuracy, by retaining the smallest possible number of configurations that catches the essential features of the electronic wavefunction. Based on a time-dependent variational principle, we derive the MCTDHF working equation for a multiconfigurational expansion with fixed coefficients and specialise to the case of general open-shell states, which are relevant for many physical processes of interest. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3600397]

A no-go result on the purification of quantum states

The information encoded in a quantum system is generally spoiled by the influences of its environment, leading to a transition from pure to mixed states. Reducing the mixedness of a state is a fundamental step in the quest for a feasible implementation of quantum technologies. Here we show that it is impossible to transfer part of such mixedness to a trash system without losing some of the initial information. Such loss is lower-bounded by a value determined by the properties of the initial state to purify. We discuss this interesting phenomenon and its consequences for general quantum information theory, linking it to the information theoretical primitive embodied by the quantum state-merging protocol and to the behaviour of general quantum correlations.

Is Use of Optional Attributes and Associations in Conceptual Modeling Always Problematic? Theory and Empirical Tests

Prior research has argued that use of optional properties in conceptual models results in loss of information about the semantics of the domains represented by the models. Empirical research undertaken to date supports this argument. Nevertheless, no systematic analysis has been done of whether use of optional properties is always problematic. Furthermore, prior empirical research might have deliberately or unwittingly employed models where use of optionality always causes problems. Accordingly, we examine analytically whether use of optional properties is always problematic. We employ our analytical results to inform the design of an experiment where we systematically examined the impact of optionality on users’ ability to understand domains represented by different types of conceptual models. We found evidence that use of optionality undermines users’ ability to understand the domain represented by a model but that this effect weakens when use of mandatory properties to replace optional properties leads to more-complex models.

A belief revision framework for revising epistemic states with partial epistemic states

Belief revision performs belief change on an agent’s beliefs when new evidence (either of the form of a propositional formula or of the form of a total pre-order on a set of interpretations) is received. Jeffrey’s rule is commonly used for revising probabilistic epistemic states when new information is probabilistically uncertain. In this paper, we propose a general epistemic revision framework where new evidence is of the form of a partial epistemic state. Our framework extends Jeffrey’s rule with uncertain inputs and covers well-known existing frameworks such as ordinal conditional function (OCF) or possibility theory. We then define a set of postulates that such revision operators shall satisfy and establish representation theorems to characterize those postulates. We show that these postulates reveal common characteristics of various existing revision strategies and are satisfied by OCF conditionalization, Jeffrey’s rule of conditioning and possibility conditionalization. Furthermore, when reducing to the belief revision situation, our postulates can induce Darwiche and Pearl’s postulates C1 and C2.

The Shifting Battleground of Article 4(2) TEU: Evolving National Identities and the corresponding need for EU management?

Article 4(2) TEU requires that the European Union (EU) respect the Member States’ national identities, creating a legal obligation enforceable before the CJEU and valuable in political negotiations. However, the concept of national identities is unclear, leaving open questions about the scope or parameters of the provision and its applicability. The CJEU appears likely to take a relatively flexible approach in light of Article 4(2) TEU’s relationship with national constitutional courts’ reserves. This flexible approach would enable Member States to rely upon a range of aspects as part of their national identity, including ones that were previously unidentified. This is a crucial feature if one considers that national identities may evolve gradually or even dramatically, including where Member States purposefully attempt to develop their national identities further. This possibility of an evolved national identity is exemplified by the French Charte de l’Environnement. It may thereby be possible for Member States to stretch the scope and application of Article 4(2) TEU through reference to these evolving national identities. This potential raises significant challenges for the EU regarding the management of Article 4(2) TEU, which it will need to address if it wishes to ensure harmonisation and uniformity in the relevant areas.

Identifying the distinct features of geometric structures for hole trapping to generate radicals on rutile TiO2(110) in photooxidation using density functional theory calculations with hybrid functional

Using density functional theory calculations with HSE 06 functional, we obtained the structures of spin-polarized radicals on rutile TiO2(110), which is crucial to understand the photooxidation at the atomic level, and further calculate the thermodynamic stabilities of these radicals. By analyzing the results, we identify the structural features for hole trapping in the system, and reveal the mutual effects among the geometric structures, the energy levels of trapped hole states and their hole trapping capacities. Furthermore, the results from HSE 06 functional are compared to those from DFT + U and the stability trend of radicals against the number of slabs is tested. The effect of trapped holes on two important steps of the oxygen evolution reaction, i.e. water dissociation and the oxygen removal, is investigated and discussed.