31 resultados para dissociation threshold

em CentAUR: Central Archive University of Reading - UK


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In this review, we consider three possible criteria by which knowledge might be regarded as implicit or inaccessible: It might be implicit only in the sense that it is difficult to articulate freely, or it might be implicit according to either an objective threshold or a subjective threshold. We evaluate evidence for these criteria in relation to artificial grammar learning, the control of complex systems, and sequence learning, respectively. We argue that the convincing evidence is not yet in, but construing the implicit nature of implicit learning in terms of a subjective threshold is most likely to prove fruitful for future research. Furthermore, the subjective threshold criterion may demarcate qualitatively different types of knowledge. We argue that (1) implicit, rather than explicit, knowledge is often relatively inflexible in transfer to different domains, (2) implicit, rather than explicit, learning occurs when attention is focused on specific items and not underlying rules, and (3) implicit learning and the resulting knowledge are often relatively robust.

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Analytical potential energy functions which are valid at all dissociation limits have been derived for the ground states of SO2 and O3. The procedure involves minimizing the errors between the observed vibrational spectra and spectra calculated by a variational procedure. Good agreement is obtained between the observed and calculated spectra for both molecules. Comparisons are made between anharmonic force fields, previously determined from the spectral data, and the force fields obtained by differentiating the derived analytical functions at the equilibrium configurations.

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Recent studies into price transmission have recognized the important role played by transport and transaction costs. Threshold models are one approach to accommodate such costs. We develop a generalized Threshold Error Correction Model to test for the presence and form of threshold behavior in price transmission that is symmetric around equilibrium. We use monthly wheat, maize, and soya prices from the United States, Argentina, and Brazil to demonstrate this model. Classical estimation of these generalized models can present challenges but Bayesian techniques avoid many of these problems. Evidence for thresholds is found in three of the five commodity price pairs investigated.

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Globally there have been a number of concerns about the development of genetically modified crops many of which relate to the implications of gene flow at various levels. In Europe these concerns have led the European Union (EU) to promote the concept of 'coexistence' to allow the freedom to plant conventional and genetically modified (GM) varieties but to minimise the presence of transgenic material within conventional crops. Should a premium for non-GM varieties emerge on the market, the presence of transgenes would generate a 'negative externality' to conventional growers. The establishment of maximum tolerance level for the adventitious presence of GM material in conventional crops produces a threshold effect in the external costs. The existing literature suggests that apart from the biological characteristics of the plant under consideration (e.g. self-pollination rates, entomophilous species, anemophilous species, etc.), gene flow at the landscape level is affected by the relative size of the source and sink populations and the spatial arrangement of the fields in the landscape. In this paper, we take genetically modified herbicide tolerant oilseed rape (GM HT OSR) as a model crop. Starting from an individual pollen dispersal function, we develop a spatially explicit numerical model in order to assess the effect of the size of the source/sink populations and the degree of spatial aggregation on the extent of gene flow into conventional OSR varieties under two alternative settings. We find that when the transgene presence in conventional produce is detected at the field level, the external cost will increase with the size of the source area and with the level of spatial disaggregation. on the other hand when the transgene presence is averaged among all conventional fields in the landscape (e.g. because of grain mixing before detection), the external cost will only depend on the relative size of the source area. The model could readily be incorporated into an economic evaluation of policies to regulate adoption of GM HT OSR. (c) 2007 Elsevier B.V. All rights reserved.

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[Ru(2,2'-bipyridine)(2)(Hdpa)](BF4)(2) center dot 2H(2)O (1), [Ru(1,10-phenanthroline)(2)(Hdpa)] (PF6)(2) center dot CH2Cl2 (2) and [Ru(4,4,4',4'-tetramethyl-2,2'- bisoxazoline)(2)(Hdpa)] (PF6)(2) (3) are synthesized where Hdpa is 2,2'-dipyridylamine. The X-ray crystal structures of 1 and 2 have been determined. Hdpa in 1 and 2 is found to bind the metal via the two pyridyl N ends. Comparing the NMR spectra in DMSO-d(6), it is concluded that 3 has a similar structure. The pK(a) values (for the dissociation of the NH proton in Hdpa) of free Hdpa and its complexes are determined in acetonitrile by exploiting molar conductance. These correlate linearly with the chemical shift of the NH proton in the respective entities. (C) 2007 Elsevier B.V. All rights reserved.

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Using the I : 2 condensate of benzil dihydrazone and 2-acetylpyridine as the ligand L, two complexes of zinc, [ZnL(CH3COO)]PF6 (1) and [ZnL(H2O)CIO4]CIO4 H2O (2), are synthesised from Zn(CH3COO)(2).2H(2)O and Zn(CIO4)(2).6H(2)O, respectively. From X-ray crystallography, both the complexes are found to be single helical with the metal in distorted octahedral N4O2 environment. In 1, the two oxygen atoms come from the bidentate acetate while 2 is a monoaqua complex with a perchlorate anion bound to the metal in monodentate fashion. The perchlorate in 2 is not at all weakly bound [Zn-O(perchlorate) 2.256(4) A]. Still in acetonitrile solution, the coordinated perchlorate ion dissociates upon deprotonation [reaction (i)].

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The adsorption of water and coadsorption with oxygen on Rh{111} under ultrahigh vacuum conditions was studied using synchrotron-based photoemission and photoabsorption spectroscopy. Water adsorbs intact on the clean surface at temperatures below 154 K. Irradiation with x-rays, however, induces fast dissociation and the formation of a mixed OH+H(2)O layer indicating that the partially dissociated layer is thermodynamically more stable. Coadsorption of water and oxygen at a coverage below 0.3 monolayers has a similar effect, leading to the formation of a hydrogen-bonded network of water and hydroxyl molecules at a ratio of 3:2. The partially dissociated layers are more stable than chemisorbed intact water with the maximum desorption temperatures up to 30 K higher. For higher oxygen coverage, up to 0.5 monolayers, water does not dissociate and an intact water species is observed above 160 K, which is characterized by an O 1s binding energy 0.6 eV higher than that of chemisorbed water and a high desorption temperature similar to the partially dissociated layer. The extra stabilization is most likely due to hydrogen bonds with atomic oxygen.

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Objective. This study investigated whether trait positive schizotypy or trait dissociation was associated with increased levels of data-driven processing and symptoms of post-traumatic distress following a road traffic accident. Methods. Forty-five survivors of road traffic accidents were recruited from a London Accident and Emergency service. Each completed measures of trait positive schizotypy, trait dissociation, data-driven processing, and post-traumatic stress. Results. Trait positive schizotypy was associated with increased levels of data-driven processing and post-traumatic symptoms during a road traffic accident, whereas trait dissociation was not. Conclusions. Previous results which report a significant relationship between trait dissociation and post-traumatic symptoms may be an artefact of the relationship between trait positive schizotypy and trait dissociation.

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When water is coadsorbed with oxygen at coverages above 0.25ML an intact water species is observed in high resolution X-ray photoelectron spectroscopy up to 220 K, which is significantly more stable than intact water on the clean surface. The presence of this species causes a shift in the O 1s binding energy of the pre-adsorbed oxygen, which indicates the formation of hydrogen bonds between the two adsorbates. Low coverages of oxygen induce partial dissociation and recombinative desorption in the same temperature range, which illustrates that desorption temperatures alone cannot be used to determine whether water is molecularly intact or not.

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Despite a number of earlier studies which seemed to confirm molecular adsorption of water on close-packed surfaces of late transition metals, new controversy has arisen over a recent theoretical work by Feibelman, according to which partial dissociation occurs on the Ru{0001} surface leading to a mixed (H2O + OH + H) superstructure. Here, we present a refined LEED-IV analysis of the (root3 x root3)R30degrees-D2O-Ru{0001} structure, testing explicitly this new model by Feibelman. Our results favour the model proposed earlier by Held and Menzel assuming intact water molecules with almost coplanar oxygen atoms and out-of-plane hydrogen atoms atop the slightly higher oxygen atoms. The partially dissociated model with an almost identical arrangement of oxygen atoms can, however, not unambiguously be excluded, especially when the single hydrogen atoms are not present in the surface unit cell. In contrast to the earlier LEED-IV analysis, we can, however, clearly exclude a buckled geometry of oxygen atoms.

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The low-temperature reactivity of water (D2O) adsorbed on clean and oxygen pre-covered Cu(1 1 0) was studied using high resolution X-ray photoelectron spectroscopy (HRXPS) and low energy electron diffraction (LEED). On the clean surface partial dissociation to hydroxyl was observed already at 95 K. Upon annealing to 220 K hydrogen bonded water-hydroxyl chains are formed. Upon further annealing water desorbs leaving behind a layer of hydroxyl, most of which desorbs recombinatively eventually. With pre-adsorbed oxygen water reacts to hydroxyl lifting the added-row reconstruction even below 225 K. Upon annealing this adsorbate layer passes through essentially the same stages as without pre-adsorbed oxygen.

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This topical review discusses the influence of the surface geometry (e.g. lattice parameters and termination) and electronic structure of well-defined bimetallic surfaces on the adsorption and dissociation of benzene. The available data can be divided into two categories with combinations of non-transition metals and transition metals on the one side and combinations of two transition metals on the other. The main effect of non-transition metals in surface alloys is site blocking which can suppress chemisorption and dissociation of the molecules completely. When two transition metals are combined, the effects are less dramatic. They mainly affect the strength of the chemisorption bond and the degree of dissociation due to electronic and template effects.

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Light Detection And Ranging (LIDAR) is an important modality in terrain and land surveying for many environmental, engineering and civil applications. This paper presents the framework for a recently developed unsupervised classification algorithm called Skewness Balancing for object and ground point separation in airborne LIDAR data. The main advantages of the algorithm are threshold-freedom and independence from LIDAR data format and resolution, while preserving object and terrain details. The framework for Skewness Balancing has been built in this contribution with a prediction model in which unknown LIDAR tiles can be categorised as “hilly” or “moderate” terrains. Accuracy assessment of the model is carried out using cross-validation with an overall accuracy of 95%. An extension to the algorithm is developed to address the overclassification issue for hilly terrain. For moderate terrain, the results show that from the classified tiles detached objects (buildings and vegetation) and attached objects (bridges and motorway junctions) are separated from bare earth (ground, roads and yards) which makes Skewness Balancing ideal to be integrated into geographic information system (GIS) software packages.