Divergent Paths of Development: The Modern World-System and Democratization in South Africa and Zambia

This article examines whether a Modern World- Systems (MWS) perspective can provide an improved understanding of the processes of democratization in Africa (and other developing regions of the world) by conducting a comparative case study of South Africa and Zambia in the 1990s, examining the transitions to democracy and divergent processes of democratic consolidation in each country. Semiperipheral South Africa has, due to its more advantageous position in the world-system, been better equipped than peripheral Zambia to safeguard democracy against erosion and reversal. Th e central irony of the MWS is that the weakest states in the MWS can be pushed around by core powers and are more easily forced to democratize while at the same time they are least likely to possess the resources necessary for democratic consolidation. Semiperipheral states can maintain their independence vis-à-vis the core to a higher degree, but if the decision is made to undertake a democratic transition they are more likely to possess the resources necessary for successful consolidation. Th e MWS perspective allows for an improved understanding of the causal pathway of how position in the MWS translates into the ability to consolidate democracy than does approaches that emphasize domestic factors.

Conformations, vibrational frequencies and Raman intensities of short-chain fatty acid methyl esters using DFT with 6-31G(d) and Sadlej pVTZ basis sets

Density functional calculations, using B3LPY/6-31G(d) methods, have been used to investigate the conformations and vibrational (Raman) spectra of three short-chain fatty acid methyl esters (FAMEs) with the formula CnH2nO2 (n = 3-5). In all three FAMEs, the lowest energy conformer has a simple 'all-trans' structure but there are other conformers, with different torsions about the backbone, which lie reasonably close in energy to the global minimum. One result of this is that the solid samples we studied do not appear to consist entirely of the lowest energy conformer. Indeed, to account for the 'extra' bands that were observed in the Raman data but were not predicted for the all-trans conformer, it was necessary to add-in contributions from other conformers before a complete set of vibrational assignments could be made. Provided this was done, the agreement between experimental Raman frequencies and 6-31G(d) values (after scaling) was excellent, RSD = 12.6 cm(-1). However, the agreement between predicted and observed intensities was much less satisfactory. To confirm the validity of the approach followed by the 6-3 1 G(d) basis set, we used a larger basis set, Sadlej pVTZ, and found that these calculations gave accurate Raman intensities and simulated spectra (summed from two different conformers) that were in quantitative agreement with experiment. In addition, the unscaled Sadlej pVTZ, and the scaled 6-3 1 G(d) calculations gave the same vibrational mode assignments for all bands in the experimental data. This work provides the foundation for calculations on longer-chain FAMEs (which are closer to those found as triglycerides in edible fats and oils) because it shows that scaled 6-3 1 G(d) calculations give equally accurate frequency predictions, and the same vibrational mode assignments, as the much more CPU-expensive Sadlej pVTZ basis set calculations.