Stark effect or coverage dependence? Disentangling the EC-SEIRAS vibrational shift of sulfate on Au(111)

Infrared spectroscopy is a widely employed analytical tool in (electrochemical) surface science as the spectra contain a wealth of information about the interaction of interfacial adsorbates with their environment. Separating and quantifying individual contributions, for example, of co-adsorbates, the substrate or electric field effects, on the overall spectral response, however, is often non-trivial as the various interactions manifest themselves in similar spectral behavior. Here, we present an experimental approach to differentiate between and quantify potential-induced coverage dependence and field-related Stark effects observed in a sulfate band shift of 93.5 ± 1.5 cm−1/V in electrochemical infrared spectra of the showcase sulfate/Au(111) interface. In combination with a simple linear model equation used to describe the potential-induced peak shift of the sulfate stretch vibration, we determine the coverage dependence contribution to be 15.6 ± 1.2 cm−1/θSO and the Stark effect to amount to 75.6 ± 2.7 cm−1/V. Our work provides a novel route to gain fundamental insight into interfacial adsorbate interactions in electrochemical surface science.J.H.K.P. and K.F.D. gratefully acknowledge financial support by the Max Planck Graduate Center with the Johannes Gutenberg University Mainz (MPGC). U.E.Z. is grateful for financial support from the Alexander von Humboldt Foundation. J.M.F. thanks MCINN-FEDER (Spain) for support through Project No. CTQ2016-76221-P. K.F.D. acknowledges generous support through the Emmy Noether Program of the Deutsche Forschungsgemeinschaft (No. DO1691/1-1) and through the “Plus 3” Program of the Boehringer Ingelheim Foundation

Sinking Budgets and Ballooning Prices: Recent Developments Connected to Military Spending

Military spending in the West generally declined after the Cold War. Given the economic pressures that many of these states confronted, they can be said to have experienced a fortuitous conjunction of lessening security demands with stable if not rising pressures to allocate more resources to social purposes. However, with declining financial resources a good part of military capital in these countries was reduced and most of what remains is growing obsolete. The excessive rise in relative prices associated with major military capital items, a rise only partially associated with an increase in real effectiveness, poses a challenge for many of these states if they are to retain their capacity to provide in some meaningful way for their own military defense.Nach Ende des Kalten Krieges sind allgemein in der westlichen Welt die Militärausgaben gesunken. Angesichts des wirtschaftlichen Drucks, dem sich viele dieser Länder ausgesetzt sahen, kann man sagen, dass dies Ergebnis eines zufälligen Zusammentreffens mehrerer Faktoren ist: geringere Sicherheitsanforderungen treffen auf gleich bleibende bzw. sogar zunehmende Forderungen nach alternativer Budgetverwendung, beispielsweise mehr Mittelausgaben für soziale Zwecke. Durch die verringerten Finanzmittel für die Verteidigung wurde jedoch ein großer Teil der militärischen Waffensysteme reduziert, der verbliebene Rest ist zum größten Teil veraltet. Die relativen Preise für Waffensysteme sind jedoch exzessiv gestiegen, ohne dass diese auf einem gleich großen Anstieg der tatsächlichen Effektivität der Waffensysteme beruhen. So stellt es für viele dieser Staaten eine große Herausforderung dar, wenn sie ihre Fähigkeit bewahren wollen, auf sinnvolle Weise für ihre eigene militärische Sicherheit zu sorgen

War and the Changing Global System.

Ph.D.International lawUniversity of Michiganhttp://deepblue.lib.umich.edu/bitstream/2027.42/157663/1/8007728.pd

Guns, Butter, and Growth: Expenditure Patterns in Four Advanced Democracies

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Following the crowd: Social influence and technology usage.

This study examined the impact of social influence theory on distance education technology (DET) usage. Delineation of university culture types conceptualized by Bergquist (the collegial culture, the managerial culture, the developmental culture, and the negotiating culture) were also examined in relation to technology usage. This study tested the proposed relationships in a survey of distance education technology usage at a major southeastern university, and findings support the influence of past experience with technology and social influence, and provide limited support for the influence of the culture types and individual factors on technology usage. This study encourages administrators to more closely examine their own academic cultures to identify appropriate actions to take before pursuing organizational changes like DET adoption, so that the resulting DET usage might more closely mirror the expected outcomes