An efficient LDA+U based tight binding approach

The functionals usually applied in DFT calculations have deficiencies in describing systems with strongly localized electrons such as transition metals or rare earth (RE) compounds. In this work, we present the self-consistent charge density based functional tight binding (SCC-DFTB) calculation scheme including LDA+U like potentials and apply it for the simulation of RE-doped GaN. DFTB parameters for the simulation of GaN and a selection of rare earth ions, where the f electrons were explicitly included in the valence, have been created. The results of the simulations were tested against experimental data (where present) and against various more sophisticated but computationally more costly DFT calculations. Our approach is found to correctly reproduce the geometry and the energetic of the studied systems.     

Recent applications of the Cu(I)-catalysed Huisgen azide-alkyne 1,3-dipolar cycloaddition reaction in carbohydrate chemistry

This article surveys recent applications of Cu(I)-catalysed 1,3-dipolar cycloaddition of azides and alkynes in carbohydrate chemistry, highlighting developments in the preparation of simple glycoside and oligosaccharide mimetics, glyco-macrocycles, glycopeptides, glyco-clusters and carbohydrate arrays.     

Enhancement of pairwise entanglement via Z2 symmetry breaking

We study the effect of symmetry breaking in a quantum phase transition on pairwise entanglement in spin-1/2 models. We give a set of conditions on correlation functions a model has to meet in order to keep the pairwise entanglement unchanged by a parity symmetry breaking. It turns out that all mean-field solvable models do meet this requirement, whereas the presence of strong correlations leads to a violation of this condition. This results in an order-induced enhancement of entanglement, and we report on two examples where this takes place.     

Condensed-phase relaxation of multilevel quantum systems. II. Comparison of path integral calculations and second-order relaxation theory for a nondegenerate three-level system

An exactly solvable model of multisite condensed-phase vibrational relaxation was studied in Paper I (Peter, S.; Evans, D. G.; Coalson, R. D. J. Phys. Chem. B 2006, 110, 18758.), where it was shown that long-time steady-state site populations of a degenerate N-level system are not equal (hence, they are non-Boltzmann) and depend on the initial preparation of the system and the number of sites that it comprises. Here we consider a generalization of the model to the case of a nondegenerate three-level system coupled to a high-dimensional bath: such a model system has direct relevance to a large class of donor-bridge-acceptor electron transfer processes. Because the quantum dynamics of this system cannot be computed analytically, we compare numerically exact path integral calculations to the predictions of second-order time-local relaxation theory. For modest system-bath coupling strengths, the two sets of results are in excellent agreement. They show that non-Boltzmann long-time steady-state site populations are obtained when the level splitting is small but nonzero, whereas at larger values of the system bias (asymmetry) these populations become Boltzmann distributed.     

Fluorescence intermittency in blinking quantum dots: renewal or slow modulation?

We study the time series produced by blinking quantum dots, by means of an aging experiment, and we examine the results of this experiment in the light of two distinct approaches to complexity, renewal and slow modulation. We find that the renewal approach fits the result of the aging experiment, while the slow modulation perspective does not. We make also an attempt at establishing the existence of an intermediate condition.     

Isolation and structure revision of the actin-binding macrolide rhizopodin from Myxococcus stipitatus (Myxobacteria)

Rhizopodin was isolated as cytostatic and weakly antifungal macrolide (1) and later characterized as potent actin-depolymerizing agent. It is produced by the myxobacterium Myxococcus stipitatus, which enables a fermentative supply of the drug for biological studies. We here report a revised structure that characterizes rhizopodin (2) as the first known dimeric bis-lactone exhibiting side chains that terminate in N-methyl-vinylformamide groups, which are otherwise found in smaller marine toxins also targeting the actin cytoskeleton. Compound 2 might function as bivalent inhibitor forming ternary complexes with actin which would explain its high efficacy.     

Finite-size error in many-body simulations with long-range interactions

We discuss the origin of the finite-size error of the energy in many-body simulation of systems of charged particles and we propose a correction based on the random-phase approximation at long wavelengths. The correction is determined mainly by the collective charge oscillations of the interacting system. Finite-size corrections, both on kinetic and potential energy, can be calculated within a single simulation. Results are presented for the electron gas and silicon.     

Vinyllithiums from butyl-vinyl tellurides and bis-vinyl tellurides

Butyl vinyl tellurides and bis-vinyl tellurides furnish vinyllithiums with retention of configuration in good yields upon treatment with n-butyllithium at −78°C.