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X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. (C) 2016 Optical Society of America
We present an excerpt of the document "Quantum Information Processing and Communication: Strategic report on current status, visions and goals for research in Europe", which has been recently published in electronic form at the website of FET (the Future and Emerging Technologies Unit of the Directorate General Information Society of the European Commission, http://www.cordis.lu/ist/fet/qipc-sr.htm). This document has been elaborated, following a former suggestion by FET, by a committee of QIPC scientists to provide input towards the European Commission for the preparation of the Seventh Framework Program. Besides being a document addressed to policy makers and funding agencies (both at the European and national level), the document contains a detailed scientific assessment of the state-of-the-art, main research goals, challenges, strengths, weaknesses, visions and perspectives of all the most relevant QIPC sub-fields, that we report here
The literature on performance information use explains how public managers deal with mainly quantitative data that are systematically collected and formally reported. This article argues that such a narrow understanding is incomplete, as it excludes all kinds of nonroutine performance information, including verbal, ad hoc, and qualitative feedback. To understand how responsive public managers are to performance feedback, alternative sources of performance information need to be taken into account. A literature review suggests considering two important sources of nonroutine feedback: organizational insiders and relevant external stakeholders. Using survey data from German local government, this article shows that public managers prefer to use nonroutine feedback over routine data from performance reports. Furthermore, a regression analysis indicates that different sources of performance information require different determinants to trigger their use. This finding is essential because it suggests that explanations of performance information use can covary with the information source studied.
"Bürokratieabbauer" im Aufwind : erste Erfahrungen mit der Anwendung des Standardkosten-Modells
(2009)
This article examines the use of performance information by public managers. It conceptualizes purposeful data use as a type of extra-role behaviour which requires additional effort on the part of the managers and which is not extrinsically rewarded. The article sheds light on one potential antecedent of performance information use - the motivation of the users. It argues that we can observe high levels of data use if managers driven by public service motivation (PSM) work under transformational leaders. Using a needs-supply perspective on supervisors and followers, we suggest that there is a PSM-leadership fit which fosters the performance of this extra-role behaviour. The article is based on data from German local government and its findings contribute to the literatures on PSM as well as on performance management.
This article is a response to calls in prior research that we need more longitudinal analyses to better understand the foundations of PSM and related prosocial values. There is wide agreement that it is crucial for theory building but also for tailoring hiring practices and human resource development programs to sort out whether PSM-related values are stable or developable. The article summarizes existent theoretical expectations, which turn out to be partially conflicting, and tests them against multiple waves of data from the German Socio-Economic Panel Study which covers a time period of 16 years. It finds that PSM-related values of public employees are stable rather than dynamic but tend to increase with age and decrease with organizational membership. The article also examines cohort effects, which have been neglected in prior work, and finds moderate evidence that there are differences between those born during the Second World War and later generations.
Explaining the Use of Performance Information by Public Managers: A Planned-Behavior Approach
(2015)
This article examines the use of performance information by public managers. It reviews literature on the impact of attitudes and social norm and puts forward a psychological-cognitive model based on the theory of planned behavior. The article finds support for this model emphasizing that performance data use is a goal-directed, reasoned action. Another critical result is that managers who consciously intend to use performance data also make sure that the data in their division are of good quality which, in turn, fosters information use. These findings indicate thatin addition to organizational routinescognitive factors are promising starting points for interventions to foster managers' data use. The article is based on survey data from German cities.
Transition metals in inorganic systems and metalloproteins can occur in different oxidation states, which makes them ideal redox-active catalysts. To gain a mechanistic understanding of the catalytic reactions, knowledge of the oxidation state of the active metals, ideally in operando, is therefore critical. L-edge X-ray absorption spectroscopy (XAS) is a powerful technique that is frequently used to infer the oxidation state via a distinct blue shift of L-edge absorption energies with increasing oxidation state. A unified description accounting for quantum-chemical notions whereupon oxidation does not occur locally on the metal but on the whole molecule and the basic understanding that L-edge XAS probes the electronic structure locally at the metal has been missing to date. Here we quantify how charge and spin densities change at the metal and throughout the molecule for both redox and core-excitation processes. We explain the origin of the L-edge XAS shift between the high-spin complexes Mn-II(acac)(2) and Mn-III(acac)(3) as representative model systems and use ab initio theory to uncouple effects of oxidation-state changes from geometric effects. The shift reflects an increased electron affinity of Mn-III in the core-excited states compared to the ground state due to a contraction of the Mn 3d shell upon core-excitation with accompanied changes in the classical Coulomb interactions. This new picture quantifies how the metal-centered core hole probes changes in formal oxidation state and encloses and substantiates earlier explanations. The approach is broadly applicable to mechanistic studies of redox-catalytic reactions in molecular systems where charge and spin localization/delocalization determine reaction pathways.
X-ray absorption spectroscopy at the L-edge of 3d transition metals provides unique information on the local metal charge and spin states by directly probing 3d-derived molecular orbitals through 2p-3d transitions. However, this soft x-ray technique has been rarely used at synchrotron facilities for mechanistic studies of metalloenzymes due to the difficulties of x-ray-induced sample damage and strong background signals from light elements that can dominate the low metal signal. Here, we combine femtosecond soft x-ray pulses from a free-electron laser with a novel x-ray fluorescence-yield spectrometer to overcome these difficulties. We present L-edge absorption spectra of inorganic high-valent Mn complexes (Mn similar to 6-15 mmol/l) with no visible effects of radiation damage. We also present the first L-edge absorption spectra of the oxygen evolving complex (Mn4CaO5) in Photosystem II (Mn < 1 mmol/l) at room temperature, measured under similar conditions. Our approach opens new ways to study metalloenzymes under functional conditions. (C) 2017 Author(s).