Watching a hydroperoxyalkyl radical (•QOOH) dissociate

A prototypical hydroperoxyalkyl radical (•QOOH) intermediate, transiently formed in the oxidation of volatile organic compounds, was directly observed through its infrared fingerprint and energy-dependent unimolecular decay to hydroxyl radical and cyclic ether products. Direct time-domain measurements of •QOOH unimolecular dissociation rates over a wide range of energies were found to be in accord with those predicted theoretically using state-of-the-art electronic structure characterizations of the transition state barrier region. Unimolecular decay was enhanced by substantial heavy-atom tunneling involving O-O elongation and C-C-O angle contraction along the reaction pathway. Master equation modeling yielded a fully a priori prediction of the pressure-dependent thermal unimolecular dissociation rates for the •QOOH intermediate—again increased by heavy-atom tunneling—which are required for global models of atmospheric and combustion chemistry.

A quantum moat barrier, realized with a finite square well

The notion of a double well potential typically involves two regions of space separated by a repulsive potential barrier. The ground state is a wave function that is suppressed in the barrier region and localized in the two surrounding regions. We illustrate that an attractive potential well (a quantum moat) with a finite non-zero width also acts as a barrier, using a simple square well model. We also show how the pseudopotential method both explains the role of the well as a barrier, and greatly improves the efficiency of constructing wave functions for this system using matrix diagonalization. With this simplified model we provide an introduction to the ideas typically used to simplify calculations in solids, where in place of the double well potential, multiple potentials occur in a periodic array.

From dust till drowned: the Holocene landscape development at Norderney, East Frisian Islands

Within the multidisciplinary WASA project, 160 cores up to 5 m long have been obtained from the back-barrier area and off the coast of the East Frisian island of Norderney. Thirty-seven contained basal peats on top of Pleistocene sands of the former Geest and 10 of them also had intercalated peats. Based on 100 acclerator mass spectrometry (AMS) 14C dates and analyses of botanical as well as zoological remains from the peats, lagoonal sediments and the underlying sands, a variety of distinct habitats have been reconstructed. On the relatively steep slopes north of the present island, a swampy vegetation fringe several kilometres wide with carrs of alder (Alnus glutinosa) moved in front of the rising sea upwards of the Geest as it existed then until roughly 6 ka, when the sea level reached the current back-barrier region of Norderney at around −6 m NHN (German ordnance datum). From then on for nearly 4000 years a changing landscape with a mosaic of freshwater lakes and fens existed within this area. It was characterised by various stands of Cladium mariscus (fen sedge), alternating with brackish reed beds with Phragmites australis (common reed) and salt meadows with Aster tripolium (sea aster), Triglochin maritima (sea arrowgrass), Juncus gerardii (saltmarsh rush) as well as mudflats with Salicornia europaea (common glasswort). As far as shown by our cores, this highly diverse, and for humans potentially attractive landscape was at least some 4 km wide and followed the coast for about 10 km. Before the rising sea caused diversification of habitats, wet heath as well as dry and dusty sand areas existed. In the course of time, parts of the wet heath turned into raised Sphagnum bogs under an oceanic precipitation regime before this diverse landscape was drowned by the rising sea and finally covered by marine sediments, while the earlier sediments and peats were partly eroded and redeposited.

Non-Equilibrium Green’s Function Modeling of the Transport Characteristics of Magnetic Tunnel Junctions Containing Anderson Impurities

A nonequilibrium Green’s function (NEGF) formulation to study the transport characteristics of magnetic tunnel junctions (MTJs) that contains impurities at the barrier region and many-body interaction at the electrode region is presented. The formulation makes use of the already developed NEGF method for MTJs without any impurities and the impurity Green’s function is obtained using Haldane’s approach that explicitly takes into account the on-site Coulomb interaction ([Formula: see text]) of the impurity. The formulation is used to obtain the spin-dependent tunnel current of model MTJs as a function of the applied bias for different values of [Formula: see text] corresponding to both the parallel and antiparallel configuration of the end electrodes of the MTJ. The tunnel currents are used to obtain the tunnel magnetoresistance (TMR) of the MTJ and we observed from our study that the TMR is strongly influenced by the impurities. The TMR is found to be reduced compared to that of the MTJ without impurities and the bias dependence of the TMR is found to be strongly influenced by [Formula: see text]. Our studies revealed that the MTJ can exhibit almost completely spin polarized current at certain values of [Formula: see text].