Grain and potato production in 19th-century Estonia

This article is based on the annual reports of the governors of Estland (Northern Estonia) and Livland. Although the statistical correctness of the information is questionable, it can be used to find out relative tendencies. Especially we are interested in the similarities and differences involved in the economic development of the large estates of Baltic-German landowners

Typological-regional differences in the development of productive forces and demographic processes in the course of the transformation of European society

The transition process from feudalist to capitalist (from dominantly agrarian to dominantly industrial) society developed differently and at a different time in different regions of Europe. The nature of these processes was influenced by the type of the social relations and by the results of the socio-political (revolutionary or by the way of reforms) changes taking place in different ways in different European states. The nature of agricultural development depended on the nature of the economic activity of great landlords and peasantry and on the nature of their mutual relations. The following types of social structure and development can be distinguished in Europe in 18-19th centuries: 1. capitalist farmers - hired workers (England-Northern France), 2. aristocracy - peasant smallholders (Mediterranian, Central Europe), 3. great landowners - free peasant landowners - landless peasantry and hired workers (Scandinavia), 4. the "Junker" type entrepreneur landlord - dependent peasant smallholders - landless peasantry and hired workers (Eastern Europe)

Spectroscopic studies of IrO2 and Bi2Ir2O7

The oxides of iridium, a 5d transition metal, have recently attracted interest in a number of scientific disciplines, ranging from fundamental solid state physics, to more applied areas of research such as spintronics and catalysis. The metallic oxides IrO2 and Bi2Ir2O7, in particular, are known to be good catalysts of the commercially important oxygen evolution reaction; IrO2 has also been identified as a promising material for spin current detection, and Bi2Ir2O7 has received attention due to its unusual magnetic response at low temperatures. In the work reported in this thesis, X-ray photoelectron spectroscopy using an Al Kα photon source (XPS), synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES), X-ray emission spectroscopy (XES), X-ray absorption spectroscopy (XAS), and resonant inelastic X-ray scattering (RIXS) were used to characterize the electronic structures of IrO2 and Bi2Ir2O7. The results were compared to simulated spectra derived from the results of density functional theory calculations performed by collaborators, and analyzed in terms of qualitative models of the electronic structure. Excellent agreement between theory and experiment was observed, especially if the effects of final state lifetime broadening were accounted for. A new formalism was derived that allows final state lifetime effects to be included in band structure based RIXS simulations. The results of the theoretical calculations were also used to analyze the properties of the low energy electronic states in IrO2 and Bi2Ir2O7, and it was found that in both cases there are strong deviations from the predictions of the popular jeff = 1/2 model. The results of preliminary high pressure photoemission measurements of IrO2 are also presented in this thesis, alongside a more detailed discussion of fundamental aspects of this relatively new technique. In particular, the issue of the pressure profile that is formed around the sample and the first aperture in differentially pumped spectrometers is addressed using a combination of experimental measurements and computational fluid dynamics simulations. For the flow of N2 through a 0.3 mm aperture, the calculated pressures at the plane of the sample are tabulated for a range of sample-to-cone distances and pressures of 5.0 mbar, 9.4 mbar and 30 mbar.Open Acces

Accurate absolute core-electron binding energies of molecules, solids and surfaces from first-principles calculations

Core-electron x-ray photoelectron spectroscopy is a powerful technique for studying the electronicstructure and chemical composition of molecules, solids and surfaces. However, the interpretationof measured spectra and the assignment of peaks to atoms in specific chemical environments is oftenchallenging. Here, we address this problem and introduce a parameter-free computational approachfor calculating absolute core-electron binding energies. In particular, we demonstrate that accurateabsolute binding energies can be obtained from the total energy difference of the ground state anda state with an explicit core hole when exchange and correlation effects are described by a recentlydeveloped meta-generalized gradient approximation and relativistic effects are included even forlight elements. We carry out calculations for molecules, solids and surface species and find excellentagreement with available experimental measurements. For example, we find a mean absolute errorof only 0.16 eV for a reference set of 103 molecular core-electron binding energies. The capability tocalculate accurate absolute core-electron binding energies will enable new insights into a wide rangeof chemical surface processes that are studied by x-ray photoelectron spectroscopy

Predicting core electron binding energies in elements of the first transition series using the Δ-self-consistent-field method.

The Δ-Self-Consistent-Field (ΔSCF) method has been established as an accurate and computationally efficient approach for calculating absolute core electron binding energies for light elements up to chlorine, but relatively little is known about the performance of this method for heavier elements. In this work, we present ΔSCF calculations of transition metal (TM) 2p core electron binding energies for a series of 60 molecular compounds containing the first row transition metals Ti, V, Cr, Mn, Fe and Co. We find that the calculated TM 2p3/2 binding energies are less accurate than the results for the lighter elements with a mean absolute error (MAE) of 0.73 eV compared to experimental gas phase photoelectron spectroscopy results. However, our results suggest that the error depends mostly on the element and is rather insensitive to the chemical environment. By applying an element-specific correction to the binding energies the MAE is reduced to 0.20 eV, similar to the accuracy obtained for the lighter elements

Combining the Δ--self-consistent-field and gw methods for predicting core electron binding energies in periodic solids

For the computational prediction of core electron binding energies in solids, two distinct kinds of modeling strategies have been pursued: the Δ-Self-Consistent-Field method based on density functional theory (DFT), and the GW method. In this study, we examine the formal relationship between these two approaches and establish a link between them. The link arises from the equivalence, in DFT, between the total energy difference result for the first ionization energy, and the eigenvalue of the highest occupied state, in the limit of infinite supercell size. This link allows us to introduce a new formalism, which highlights how in DFT─even if the total energy difference method is used to calculate core electron binding energies─the accuracy of the results still implicitly depends on the accuracy of the eigenvalue at the valence band maximum in insulators, or at the Fermi level in metals. We examine whether incorporating a quasiparticle correction for this eigenvalue from GW theory improves the accuracy of the calculated core electron binding energies, and find that the inclusion of vertex corrections is required for achieving quantitative agreement with experiment