Development of Novel Density Functionals for Thermochemical Kinetics

A new density functional theory (DFT) exchange-correlation functional for the exploration of reaction mechanisms is proposed. This new functional, denoted BMK (Boese-Martin for Kinetics), has an accuracy in the 2 kcal/mol range for transition state barriers but, unlike previous attempts at such a functional, this improved accuracy does not come at the expense of equilibrium properties. This makes it a general-purpose functional whose domain of applicability has been extended to transition states, rather than a specialized functional for kinetics. The improvement in BMK rests on the inclusion of the kinetic energy density together with a large value of the exact exchange mixing coefficient. For this functional, the kinetic energy density appears to correct `back' the excess exact exchange mixing for ground-state properties, possibly simulating variable exchange.Comment: J. Chem. Phys., in press (303431JCP, scheduled for August 15, 2004 issue); supplementary data available at http://theochem.weizmann.ac.il/web/papers/BMK.htm

From ab initio quantum chemistry to molecular dynamics: The delicate case of hydrogen bonding in ammonia

The ammonia dimer (NH3)2 has been investigated using high--level ab initio quantum chemistry methods and density functional theory (DFT). The structure and energetics of important isomers is obtained to unprecedented accuracy without resorting to experiment. The global minimum of eclipsed C_s symmetry is characterized by a significantly bent hydrogen bond which deviates from linearity by about 20 degrees. In addition, the so-called cyclic C_{2h} structure is extremely close in energy on an overall flat potential energy surface. It is demonstrated that none of the currently available (GGA, meta--GGA, and hybrid) density functionals satisfactorily describe the structure and relative energies of this nonlinear hydrogen bond. We present a novel density functional, HCTH/407+, designed to describe this sort of hydrogen bond quantitatively on the level of the dimer, contrary to e.g. the widely used BLYP functional. This improved functional is employed in Car-Parrinello ab initio molecular dynamics simulations of liquid ammonia to judge its performance in describing the associated liquid. Both the HCTH/407+ and BLYP functionals describe the properties of the liquid well as judged by analysis of radial distribution functions, hydrogen bonding structure and dynamics, translational diffusion, and orientational relaxation processes. It is demonstrated that the solvation shell of the ammonia molecule in the liquid phase is dominated by steric packing effects and not so much by directional hydrogen bonding interactions. In addition, the propensity of ammonia molecules to form bifurcated and multifurcated hydrogen bonds in the liquid phase is found to be negligibly small.Comment: Journal of Chemical Physics, in press (305335JCP

PHASE ANALYSIS OF NITI WIRE BASED ON SYNCHROTRON 2D X-RAY DIFFRACTION PATTERN IN MATLAB

This paper deals with simplified phase analysis of 2D diffraction patterns obtained using microfocused X-ray at various places of superelastic NiTi wire under combined load. For this purpose, MATLAB routines and functions were created, which carry out integration of the patterns in various sectors of Debye ring, fitting of the patterns by a mixture of austenite and martensite (having neglected the R-phase) and successive evaluation of the quantitative phase content. The most crucial simplificating assumptions were: the neglection of the R-phase and the assumption of a) fibre texture or b) no texture

Sedimentary petrological characteristics of lateral and frontal moraine and proglacial glaciofluvial sediments of Bertilbreen, Central Svalbard

Bertilbreen is a valley glacier located in the central part of the Spitsbergen Island, Svalbard. Glacier bedrock is composed of Devonian Old Red facies sedimentary rocks, Carboniferous clastic sedimentary rocks and Carboniferous to Permian limestones. Cobble clasts from the right-hand lateral moraine, frontal moraine and proglacial glaciofluvial sediments were studied. The upper part of the lateral moraine is composed mostly of passively transported supraglacial debris (originally unmodified scree, snow and scree/rock avalanche deposits) with a small proportion of actively transported clasts or reworked glaciofluvial sediments. Clasts in the middle part of the lateral moraine originate predominantly from the frontal moraine of a small glacier in the lateral valley. The lower part of the lateral moraine and frontal moraine of Bertilbreen are rich in subglacially transported material, which is supported by isometric clast shapes, roundness degree and common clast surface striations. Coarse gravel forms longitudinal bars in the glaciofluvial stream flowing from the glacier front. In the southern mouth of the valley, the proglacial stream grades into a braided outwash fan. Clast nature is affected by the source from the surrounding glacial deposits and bedrock outcrops, the impact of glaciofluvial transport on the clast nature increases in the braided outwash fan. Clast shapes are primarily influenced by bedding and fractures of source rocks, but are also significantly influenced by the type and proximity of material sources. Striation is cleared away the clast surface during the glaciofluvial transport. A morphostrati-graphically older glaciofluvial terrace formed by glaciofluvial sediments deposited during the glacier advance culminating during the Little Ice Age (LIA) is located at the southern end of the valley. The comparison of active proglacial stream sediments and those from older glaciofluvial terrace was done using the coarse pebble fraction

Conceptualizing smart service systems.

Recent years have seen the emergence of physical products that are digitally networked with other products and with information systems to enable complex business scenarios in manufacturing, mobility, or healthcare. These "smart products", which enable the co-creation of "smart service" that is based on monitoring, optimization, remote control, and autonomous adaptation of products, profoundly transform service systems into what we call "smart service systems". In a multi-method study that includes conceptual research and qualitative data from in-depth interviews, we conceptualize "smart service" and "smart service systems" based on using smart products as boundary objects that integrate service consumers' and service providers' resources and activities. Smart products allow both actors to retrieve and to analyze aggregated field evidence and to adapt service systems based on contextual data. We discuss the implications that the introduction of smart service systems have for foundational concepts of service science and conclude that smart service systems are characterized by technology-mediated, continuous, and routinized interactions

High frequency oscillations in epileptic and non-epileptic human hippocampus during a cognitive task

Hippocampal high-frequency electrographic activity (HFOs) represents one of the major discoveries not only in epilepsy research but also in cognitive science over the past few decades. A fundamental challenge, however, has been the fact that physiological HFOs associated with normal brain function overlap in frequency with pathological HFOs. We investigated the impact of a cognitive task on HFOs with the aim of improving differentiation between epileptic and non-epileptic hippocampi in humans. Hippocampal activity was recorded with depth electrodes in 15 patients with focal epilepsy during a resting period and subsequently during a cognitive task. HFOs in ripple and fast ripple frequency ranges were evaluated in both conditions, and their rate, spectral entropy, relative amplitude and duration were compared in epileptic and non-epileptic hippocampi. The similarity of HFOs properties recorded at rest in epileptic and non-epileptic hippocampi suggests that they cannot be used alone to distinguish between hippocampi. However, both ripples and fast ripples were observed with higher rates, higher relative amplitudes and longer durations at rest as well as during a cognitive task in epileptic compared with non-epileptic hippocampi. Moreover, during a cognitive task, significant reductions of HFOs rates were found in epileptic hippocampi. These reductions were not observed in non-epileptic hippocampi. Our results indicate that although both hippocampi generate HFOs with similar features that probably reflect non-pathological phenomena, it is possible to differentiate between epileptic and non-epileptic hippocampi using a simple odd-ball task

PREDICTORS OF BOULDER CLIMBING PERFORMANCE IN YOUTH BOULDER CLIMBERS

The purpose of this study was to determine if a simple measurement using hand dynamometer could be used as predictors of boulder climbing performance in youth climbers. The study cohort consisted of 12 competitive climbers (8 males, 4 females) who competed at European Bouldering Youth Championships (B) in Slany, Czech Republic in the year 2017. The hand grip force was measured at fingertips-thumbtip grip at three wrist positions and during free holding. The effect of hand dominance in grip strength was not observed except for free holding. It could be concluded that the elite young climbers has balanced grip strength between the left and the right hand. The performance in competitions was assed by total number of number of achieved tops. The best predictor of number of top holds achieved in qualification round was the strength at free grip as it describes also upper body fitness level