On Predicting Mössbauer Parameters of Iron-Containing Molecules with Density-Functional Theory

The performance of six frequently used density functional theory (DFT) methods (RPBE, OLYP, TPSS, B3LYP, B3LYP*, and TPSSh) in the prediction of Mössbauer isomer shifts(δ) and quadrupole splittings (ΔEQ) is studied for an extended and diverse set of Fe complexes. In addition to the influence of the applied density functional and the type of the basis set, the effect of the environment of the molecule, approximated with the conducting-like screening solvation model (COSMO) on the computed Mössbauer parameters, is also investigated. For the isomer shifts the COSMO-B3LYP method is found to provide accurate δ values for all 66 investigated complexes, with a mean absolute error (MAE) of 0.05 mm s–1 and a maximum deviation of 0.12 mm s–1. Obtaining accurate ΔEQ values presents a bigger challenge; however, with the selection of an appropriate DFT method, a reasonable agreement can be achieved between experiment and theory. Identifying the various chemical classes of compounds that need different treatment allowed us to construct a recipe for ΔEQ calculations; the application of this approach yields a MAE of 0.12 mm s–1 (7% error) and a maximum deviation of 0.55 mm s–1 (17% error). This accuracy should be sufficient for most chemical problems that concern Fe complexes. Furthermore, the reliability of the DFT approach is verified by extending the investigation to chemically relevant case studies which include geometric isomerism, phase transitions induced by variations of the electronic structure (e.g., spin crossover and inversion of the orbital ground state), and the description of electronically degenerate triplet and quintet states. Finally, the immense and often unexploited potential of utilizing the sign of the ΔEQ in characterizing distortions or in identifying the appropriate electronic state at the assignment of the spectral lines is also shown

Gardens of happiness: Sir William Temple, temperance and China

This is the author accepted manuscript. The final version is available from Taylor & Francis via the DOI in this recordSir William Temple, an English statesman and humanist, wrote “Upon the Gardens of Epicurus” in 1685, taking a neo-epicurean approach to happiness and temperance. In accord with Pierre Gassendi’s epicureanism, “happiness” is characterised as freedom from disturbance and pain in mind and body, whereas “temperance” means following nature (Providence and one’s physiopsychological constitution). For Temple, cultivating fruit trees in his garden was analogous to the threefold cultivation of temperance as a virtue in the humoral body (as food), the mind (as freedom from the passions), and the bodyeconomic (as circulating goods) in order to attain happiness. A regimen that was supposed to cure the malaise of Restoration amidst a crisis of unbridled passions, this threefold cultivation of temperance underlines Temple’s reception of China and Confucianism wherein happiness and temperance are highlighted. Thus Temple’s “gardens of happiness” represent not only a reinterpretation of classical ideas, but also his dialogue with China.European CommissionLeverhulme Trus

Political Economy of Civil Society

This chapter explores the role of civil society in relation to the economy and the polity by focusing on three distinct yet related dimensions: (1) the conceptual history of civil society in relation to political economy; (2) the theory underpinning a political economy of civil society; (3) the implications of a political economy of civil society for policy-making. The main argument is that there is a fundamental difference between ancient and medieval conceptions, which emphasise natural sociability, and modern accounts that accentuate a violent ‘state of nature’. As a result, civil society either reflects the fundamental embeddedness of economic and political processes in social relations or is an artificial construct. The chapter develops a typology of four modern models, provides a theory of the political economy of civil society and outlines a series of policy ideas

Sociability

How are individuals able to establish peaceful and enduring societies? Although the problem of sociability has been a recurrent concern for moral and political philosophers since antiquity, the early modern period marks an important shift in the conceptualization of human sociability. Moral skepticism, numerous ferocious wars, and the rise of sovereign states prompted the novel needed to study the normative and psychological underpinnings of social order. From the sixteenth century onward, sociability began to function as a bridge concept that was applied to theories of morality and moral psychology, political philosophy, history, international relations, and political economy (see, e.g., Piirimäe and Schmidt 2015; Sagar 2018; Ahnert and Manning 2011; Fiorillo and Grunert 2009; Vollhardt 2001). This entry introduces the early modern conceptions of sociability by focusing on the debate concerning the question how are men turned into social and political animals. Is sociability natural for human beings, or is it merely an artificial device that restrains and motivates the actions of naturally unsociable individuals? During the course of the early modern period, the notion of sociability as an innate inclination that could provide sufficient foundations for mutual sociability in large societies was questioned. As a result, the view of man as a naturally social and political being was gradually replaced by the idea of sociability as an artificial product of historically situated societies.Peer reviewe