Insight into association reactions on metal surfaces: Density-functional theory studies of hydrogenation reactions on Rh(111)

Hydrogenation reaction, as one of the simplest association reactions on surfaces, is of great importance both scientifically and technologically. They are essential steps in many industrial processes in heterogeneous catalysis, such as ammonia synthesis (N-2+3H(2)-->2NH(3)). Many issues in hydrogenation reactions remain largely elusive. In this work, the NHx (x=0,1,2) hydrogenation reactions (N+H-->NH, NH+H-->NH2 and NH2+H-->NH3) on Rh(111) are used as a model system to study the hydrogenation reactions on metal surfaces in general using density-functional theory. In addition, C and O hydrogenation (C+H-->CH and O+H-->OH) and several oxygenation reactions, i.e., C+O, N+O, O+O reactions, are also calculated in order to provide a further understanding of the barrier of association reactions. The reaction pathways and the barriers of all these reactions are determined and reported. For the C, N, NH, and O hydrogenation reactions, it is found that there is a linear relationship between the barrier and the valency of R (R=C, N, NH, and O). Detailed analyses are carried out to rationalize the barriers of the reactions, which shows that: (i) The interaction energy between two reactants in the transition state plays an important role in determining the trend in the barriers; (ii) there are two major components in the interaction energy: The bonding competition and the direct Pauli repulsion; and (iii) the Pauli repulsion effect is responsible for the linear valency-barrier trend in the C, N, NH, and O hydrogenation reactions. For the NH2+H reaction, which is different from other hydrogenation reactions studied, the energy cost of the NH2 activation from the IS to the TS is the main part of the barrier. The potential energy surface of the NH2 on metal surfaces is thus crucial to the barrier of NH2+H reaction. Three important factors that can affect the barrier of association reactions are generalized: (i) The bonding competition effect; (ii) the local charge densities of the reactants along the reaction direction; and (iii) the potential energy surface of the reactants on the surface. The lowest energy pathway for a surface association reaction should correspond to the one with the best compromise of these three factors. (C) 2003 American Institute of Physics.

Age-related differences in rapid muscle activation after rate of force development training of the elbow flexors

In young adults, improvements in the rate of force development as a result of resistance training are accompanied by increases in neural drive in the very initial phase of muscle activation. The purpose of this experiment was to determine if older adults also exhibit similar adaptations in response to rate of force development (RFD) training. Eight young (21-35 years) and eight older (60-79 years) adults were assessed during the production of maximum rapid contractions, before and after four weeks of progressive resistance training for the elbow flexors. Young and older adults exhibited significant increases (P<0.01) in peak RFD, of 25.6% and 28.6% respectively. For both groups the increase in RFD was accompanied by an increase in the root mean square (RMS) amplitude and in the rate of rise (RER) in the electromyogram (EMG) throughout the initial 100 ms of activation. For older adults, however, this training response was only apparent in the brachialis and brachioradialis muscles. This response was not observed in surface EMG recorded from the biceps brachii muscle during either RFD testing or throughout training, nor was it observed in the pronator teres muscle. The minimal adaptations observed for older adults in the bifunctional muscles biceps brachii and pronator teres are considered to indicate a compromise of the neural adaptations older adults might experience in response to resistance training.

Segmentation of optic disc in retinal images using an improved gradient vector flow algorithm

Image segmentation plays an important role in the analysis of retinal images as the extraction of the optic disk provides important cues for accurate diagnosis of various retinopathic diseases. In recent years, gradient vector flow (GVF) based algorithms have been used successfully to successfully segment a variety of medical imagery. However, due to the compromise of internal and external energy forces within the resulting partial differential equations, these methods can lead to less accurate segmentation results in certain cases. In this paper, we propose the use of a new mean shift-based GVF segmentation algorithm that drives the internal/external energies towards the correct direction. The proposed method incorporates a mean shift operation within the standard GVF cost function to arrive at a more accurate segmentation. Experimental results on a large dataset of retinal images demonstrate that the presented method optimally detects the border of the optic disc.

A DFT study of the transition metal promotion effect on ethylene chemisorption on Co(0001)

Transition metals are often introduced to a catalyst as promoters to improve catalytic performance. In this work, we study the promotion effect of transition metals on Co, the preferred catalytic metal for Fischer-Tropsch synthesis because of its good compromise of activity, selectivity and stability, for ethylene chemisorption using density functional theory (DFT) calculations, aiming to provide some insight into improving the alpha-olefin selectivity. In order to obtain the general trend of influence on ethylene chemisorption, twelve transition metals (Zr, Mn, Re, Ru, Rh, It, Ni, Pd, Pt, Cu, Ag and Au) are calculated. We find that the late transition metals (e.g. Pd and Cu) can decrease ethylene chemisorption energy. These results suggest that the addition of the late transition metals may improve alpha-olefin selectivity. Electronic structure analyses (both charge density distributions and density of states) are also performed and the understanding of calculated results is presented. (C) 2009 Elsevier B.V. All rights reserved.

Mean shift based gradient vector flow for image segmentation

In recent years, gradient vector flow (GVF) based algorithms have been successfully used to segment a variety of 2-D and 3-D imagery. However, due to the compromise of internal and external energy forces within the resulting partial differential equations, these methods may lead to biased segmentation results. In this paper, we propose MSGVF, a mean shift based GVF segmentation algorithm that can successfully locate the correct borders. MSGVF is developed so that when the contour reaches equilibrium, the various forces resulting from the different energy terms are balanced. In addition, the smoothness constraint of image pixels is kept so that over- or under-segmentation can be reduced. Experimental results on publicly accessible datasets of dermoscopic and optic disc images demonstrate that the proposed method effectively detects the borders of the objects of interest.

Fuzzy logic-based implicit authentication for mobile access control

In order to address the increasing compromise of user privacy on mobile devices, a Fuzzy Logic based implicit authentication scheme is proposed in this paper. The proposed scheme computes an aggregate score based on selected features and a threshold in real-time based on current and historic data depicting user routine. The tuned fuzzy system is then applied to the aggregated score and the threshold to determine the trust level of the current user. The proposed fuzzy-integrated implicit authentication scheme is designed to: operate adaptively and completely in the background, require minimal training period, enable high system accuracy while provide timely detection of abnormal activity. In this paper, we explore Fuzzy Logic based authentication in depth. Gaussian and triangle-based membership functions are investigated and compared using real data over several weeks from different Android phone users. The presented results show that our proposed Fuzzy Logic approach is a highly effective, and viable scheme for lightweight real-time implicit authentication on mobile devices.

High-precision radiocarbon measurements of contemporaneous tree-ring wood from the British Isles and New Zealand: AD 1850-950.

The University of Waikato, Hamilton, New Zealand and The Queen's University of Belfast, Northern Ireland radiocarbon dating laboratories have undertaken a series of high-precision measurements on decadal samples of dendrochronologically dated oak (Quercus petraea) from Great Britain and cedar (Libocedrus bidwillii) and silver pine (Lagarostrobos colensoi) from New Zealand. The results show an average hemispheric offset over the 900 yr of measurement of 40±13 yr. This value is not constant but varies with a periodicity of about 130 yr. The Northern Hemisphere measurements confirm the validity of the Pearson et al. (1986) calibration dataset.

Calibration of the Radiocarbon Time Scale for the Southern Hemisphere: AD 1850-950

We have conducted a series of radiocarbon measurements on decadal samples of dendrochronologically dated wood from both hemispheres, spanning 1000 years (McCormac et al. 1998; Hogg et al. this issue). Using the data presented in Hogg et al., we show that during the period AD 950-1850 the 14C offset between the hemispheres is not constant, but varies periodically (~130 yr periodicity) with amplitudes varying between 1 and 10‰ (i.e. 8-80 yr), with a consequent effect on the 14C calibration of material from the Southern Hemisphere. A large increase in the offset occurs between AD 1245 and 1355. In this paper, we present a Southern Hemisphere high-precision calibration data set (SHCal02) that comprises measurements from New Zealand, Chile, and South Africa. This data, and a new value of 41 ± 14 yr for correction of the IntCal98 data for the period outside the range given here, is proposed for use in calibrating Southern Hemisphere 14C dates.