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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.
This article is a response to calls in prior research that we need more longitudi-nal 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 expecta-tions, 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 sixteen 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 member-ship. 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.
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.
The PSM-leadership fit
(2013)
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.