977 resultados para fluctuating valence


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Extending the work presented in Prasad et al. (IEEE Proceedings on Control Theory and Applications, 147, 523-37, 2000), this paper reports a hierarchical nonlinear physical model-based control strategy to account for the problems arising due to complex dynamics of drum level and governor valve, and demonstrates its effectiveness in plant-wide disturbance handling. The strategy incorporates a two-level control structure consisting of lower-level conventional PI regulators and a higher-level nonlinear physical model predictive controller (NPMPC) for mainly set-point manoeuvring. The lower-level PI loops help stabilise the unstable drum-boiler dynamics and allow faster governor valve action for power and grid-frequency regulation. The higher-level NPMPC provides an optimal load demand (or set-point) transition by effective handling of plant-wide interactions and system disturbances. The strategy has been tested in a simulation of a 200-MW oil-fired power plant at Ballylumford in Northern Ireland. A novel approach is devized to test the disturbance rejection capability in severe operating conditions. Low frequency disturbances were created by making random changes in radiation heat flow on the boiler-side, while condenser vacuum was fluctuating in a random fashion on the turbine side. In order to simulate high-frequency disturbances, pulse-type load disturbances were made to strike at instants which are not an integral multiple of the NPMPC sampling period. Impressive results have been obtained during both types of system disturbances and extremely high rates of load changes, right across the operating range, These results compared favourably with those from a conventional state-space generalized predictive control (GPC) method designed under similar conditions.

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cis-2,3-Dihydrodiol metabolites of monosubstituted halobenzenes and toluene have been used as synthetic precursors of the corresponding 3,4-cis-dihydrodiols. Enantiopure syn-benzene dioxide intermediates were reduced to the 3,4-cis-dihydrodiols and thermally racemised via the corresponding 1,4-dioxocins. The syn-benzene dioxide-1,4-dioxocin valence tautomeric equilibrium ratio was found to be dependent on the substituent position. The methodology has also been applied to the synthesis of both enantiomers of the 1,2-(ipso)- and 3,4-cis-dihydrodiols of toluene. This chemoenzymatic approach thus makes available, for the first time, all three possible cis-dihydrodiol regioisomers of a monosubstituted benzene.

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The electronic and bonding properties of nitrogenated carbon nanotubes (N-CNTs) exposed to chlorine plasma were investigated using C and N K-edge x-ray absorption near-edge structure (XANES) and scanning photoelectron microscopy (SPEM). The C and N K-edge XANES spectra of chlorine-treated N-CNTs consistently reveal the formation of pyridinelike N-CNTs by the observation of 1s ->pi(*)(e(2u)) antibonding and 1s ->pi(*)(b(2g)) bonding states. The valence-band photoemission spectra obtained from SPEM images indicate that chlorination of the nanotubes enhances the C-N bonding. First-principles calculations of the partial densities of states in conjunction with C K-edge XANES data identify the presence of C-Cl bonding in chlorine treated N-CNTs. (C) 2007 American Institute of Physics.

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Saturable absorption is a phenomenon readily seen in the optical and infrared wavelengths. It has never been observed in core-electron transitions owing to the short lifetime of the excited states involved and the high intensities of the soft X-rays needed. We report saturable absorption of an L-shell transition in aluminium using record intensities over 10(16)W cm(-2) at a photon energy of 92 eV. From a consideration of the relevant timescales, we infer that immediately after the X-rays have passed, the sample is in an exotic state where all of the aluminium atoms have an L-shell hole, and the valence band has approximately a 9 eV temperature, whereas the atoms are still on their crystallographic positions. Subsequently, Auger decay heats the material to the warm dense matter regime, at around 25 eV temperatures. The method is an ideal candidate to study homogeneous warm dense matter, highly relevant to planetary science, astrophysics and inertial confinement fusion.

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Ab initio calculations for the strongly exoergic Li2+F harpoon reaction are presented using density-functional theory, complete active space self-consistent field, and multireference configuration interaction methods to argue that this reaction would be an ideal candidate for investigation with ultracold molecules. The lowest six states are calculated with the aug-correlation-consistent polarized valence triple-zeta basis set and at least two can be accessed by a ground rovibronic Li2 molecule with zero collision energy at all reaction geometries. The large reactive cross section (characteristic of harpoon reactions) and chemiluminescent products are additional attractive features of these reactions.

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Gamma-ray positron annihilation spectra of the noble gases are simulated using computational chemistry tools for the bound electron wavefunctions and plane-wave approximation for the low-energy positron. The present annihilation line shapes, i.e. the full width at half maximum, Delta epsilon, of the gamma-ray annihilation spectra for He and Ar (valence) agree well with available independent atomic calculations using a different algorithm. For other noble gases they achieve moderate agreement with the experimental measurements. It is found that the contributions of various atomic electron shells to the spectra depend significantly on their principal quantum number n and orbital angular momentum quantum number l. The present study further reveals that the outermost ns electrons of the noble gases exhibit spectral line shapes in close agreement with those measured, indicating (as expected) that the measurements are not due to a simple sum over the momentum densities for all atomic electrons. The robust nature of the present approach makes it possible for us to proceed to more complex molecular systems using the tools of modern computational chemistry.

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The correlated process of photodetaching two electrons from the F- ion following the absorption of a single photon has been investigated over an energy range 20-62 eV. In the experiment, a beam of photons from the Advanced Light Source was collinearly merged with a counter-propagating beam of F- ions from a sputter ion source. The F+ ions produced in the interaction region were detected, and the normalized signal was used to monitor the relative cross section for the double-detachment reaction. An absolute scale for the cross section was established by measuring the spatial overlap of the two beams and by determining the efficiency for collection and detection of the F+ ions. The measured cross section is compared with R-matrix and random phase approximation calculations. These calculations show that the Auger decay of the 2s2p(6) core-excited state of the F atom plays a minor role in the production of F+ ions and that double detachment is likely to be dominated by simultaneous correlated ejection of two valence electrons at energies well above threshold.

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We conducted multi-proxy geochemical analyses (including measurements of organic carbon, nitrogen and sulphur stable isotope composition, and carbonate carbon and oxygen isotope composition) on a 13.5 m sediment core from Lake Bliden, Denmark, which provide a record of shifting hydrological conditions for the past 6,700 years. The early part of the stratigraphic record (6,700-5,740 cal year BP) was wet, based on delta O-18(carb) and lithology, and corresponds to the Holocene Thermal Maximum. Shifts in primarily delta O-18(carb) indicate dry conditions prevailed from 5,740 to 2,800 cal year BP, although this was interrupted by very wet conditions from 5,300 to 5,150, 4,300 to 4,050 and 3,700 to 3,450 cal year BP. The timing of the latter two moist intervals is consistent with other Scandinavian paleoclimatic records. Dry conditions at Lake Bliden between 3,450 and 2,800 cal year BP is consistent with other paleolimnological records from southern Sweden but contrasts with records in central Sweden, possibly suggesting a more northerly trajectory of prevailing westerlies carrying moisture from the North Atlantic at this time. Overall, fluctuating moisture conditions at Lake Bliden appear to be strongly linked to changing sea surface temperatures in the Greenland, Iceland and Norwegian seas. After 2,800 cal year BP, sedimentology, magnetic susceptibility, delta C-13(ORG), delta C-13(carb) and delta O-18(carb) indicate a major reduction on water level, which caused the depositional setting at the coring site to shift from the profundal to littoral zone. The Roman Warm Period (2,200-1,500 cal year BP) appears dry based on enriched delta O-18(carb) values. Possible effects of human disturbance in the watershed after 820 cal year BP complicate attempts to interpret the stratigraphic record although tentative interpretation of the delta O-18(carb), magnetic susceptibility, delta C-13(ORG), delta C-13(carb) and delta O-18(carb) records suggest that the Medieval Warm Period was dry and the Little Ice Age was wet.

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The feasibility of laser cooling AlH and AlF is investigated using ab initio quantum chemistry. All the electronic states corresponding to the ground and lowest two excited states of the Al atom are calculated using multi-reference configuration interaction (MRCI) and the large AV6Z basis set for AlH. The smaller AVQZ basis set is used to calculate the valence electronic states of AlF. Theoretical Franck-Condon factors are determined for the A(1)Pi -> X(1)Sigma(+) transitions in both radicals and found to agree with the highly diagonal factors found experimentally, suggesting computational chemistry is an effective method for screening suitable laser cooling candidates. AlH does not appear to have a transition quite as diagonal as that in SrF (which has been laser cooled) but the A(1)Pi -> X(1)Sigma(+) transition transition of AlF is a strong candidate for cooling with just a single laser, though the cooling frequency is deep in the UV. Furthermore, the a (3)Pi -> X(1)Sigma(+) transitions are also strongly diagonal and in AlF is a practical method for obtaining very low final temperatures around 3 mu K.

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The most promising way to maintain reliable data transfer across the rapidly fluctuating channels used by next generation multiple-input multiple-output communications schemes is to exploit run-time variable modulation and antenna configurations. This demands that the baseband signal processing architectures employed in the communications terminals must provide low cost and high performance with runtime reconfigurability. We present a softcore-processor based solution to this issue, and show for the first time, that such programmable architectures can enable real-time data operation for cutting-edge standards
such as 802.11n; furthermore, by exploiting deep processing pipelines and interleaved task execution, the cost and performance of these architectures is shown to be on a par with traditional dedicated circuit based solutions. We believe this to be the first such programmable architecture to achieve this, and the combination of implementation efficiency and programmability makes this implementation style the most promising approach for hosting such dynamic architectures.

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Ab initio calculations for the strongly exoergic Li-2 + F harpoon reaction are presented using density-functional theory, complete active space self-consistent field, and multireference configuration interaction methods to argue that this reaction would be an ideal candidate for investigation with ultracold molecules. The lowest six states are calculated with the aug-correlation-consistent polarized valence triple-zeta basis set and at least two can be accessed by a ground rovibronic Li-2 molecule with zero collision energy at all reaction geometries. The large reactive cross section (characteristic of harpoon reactions) and chemiluminescent products are additional attractive features of these reactions.

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Background: Studies of cross-cultural variations in the perception of emotion have typically compared rates of recognition of static posed stimulus photographs. That research has provided evidence for universality in the recognition of a range of emotions but also for some systematic cross-cultural variation in the interpretation of emotional expression. However, questions remain about how widely such findings can be generalised to real life emotional situations. The present study provides the first evidence that the previously reported interplay between universal and cultural influences extends to ratings of natural, dynamic emotional stimuli.

Methodology/Principal Findings: Participants from Northern Ireland, Serbia, Guatemala and Peru used a computer based tool to continuously rate the strength of positive and negative emotion being displayed in twelve short video sequences by people from the United Kingdom engaged in emotional conversations. Generalized additive mixed models were developed to assess the differences in perception of emotion between countries and sexes. Our results indicate that the temporal pattern of ratings is similar across cultures for a range of emotions and social contexts. However, there are systematic differences in intensity ratings between the countries, with participants from Northern Ireland making the most extreme ratings in the majority of the clips.

Conclusions/Significance: The results indicate that there is strong agreement across cultures in the valence and patterns of ratings of natural emotional situations but that participants from different cultures show systematic variation in the intensity with which they rate emotion. Results are discussed in terms of both ‘in-group advantage’ and ‘display rules’ approaches. This study indicates that examples of natural spontaneous emotional behaviour can be used to study cross-cultural variations in the perception of emotion.

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For many years psychological research on facial expression of emotion has relied heavily on a recognition paradigm based on posed static photographs. There is growing evidence that there may be fundamental differences between the expressions depicted in such stimuli and the emotional expressions present in everyday life. Affective computing, with its pragmatic emphasis on realism, needs examples of natural emotion. This paper describes a unique database containing recordings of mild to moderate emotionally coloured responses to a series of laboratory based emotion induction tasks. The recordings are accompanied by information on self-report of emotion and intensity, continuous trace-style ratings of valence and intensity, the sex of the participant, the sex of the experimenter, the active or passive nature of the induction task and it gives researchers the opportunity to compare expressions from people from more than one culture.

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A quantitative research on S and SO2 poisoning Pt/Vulcan carbon (Pt/VC) catalysts for fuel cells was conducted by the three-electrode method. Pt/VC electrodes were contaminated by submersion in a SO2- containing solution made up of 0.2 mM Na2SO3 and 0.5 M H2SO4 for different periods of time, and held at 0.05 V (vs. RHE) in 0.5 M H2SO4 solutions in order to gain zero-valence sulfur (S0) poisoned electrodes. The sulfur coverage of Pt was determined from the total charge consumed as the sulfur was oxidized from S0 at 0.05 V (vs. RHE) to sulfate at >1.1 V (vs. RHE). The summation of initial coverage of S0 (S) and coverage of H (H) are approximately equal to 1 (H + S = 1) when 0.5

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The gain coefficient of the strongest 3p --> 3s, J = 2 --> 1 lasing transition at 23.6 nm in the Ne-like Ge collisional excitation scheme has been measured, using the fundamental wavelength from a Nd:glass laser (1.06-mu-m), for a range of incident intensities on massive stripe targets up to 2.2 cm in length. From a threshold incident laser intensity of approximately 6 x 10(12) W/cm2, the gain coefficient rises to approximately 4.5 cm-1 for an irradiation intensity of approximately 2.5 x 10(13) W/cm2, tending towards still higher gain coefficients at higher incident intensities. For targets of maximum length, a gain-length product gL almost-equal-to 10 was reached with a resultant output power at 23.6 nm estimated to be at the approximately kW level. The beam divergence decreased with length to a minimum of approximately 7 mrad but no significant trend in beam pointing with plasma length was observed. From the trend in the gain coefficient, it appears that for a fixed energy laser irradiating a approximately 100-mu-m wide slab targets, an incident intensity of I(i) approximately 1.2 x 10(13) W/cm2 represents an optimum working level, assuming that plasma length is not limited by refractive effects. In addition to the usual valence electron excited 3p --> 3s transitions, the gain coefficient for the core excited 1s(2)2s2p(6)3d --> 1s(2)2s2p(6)3p transition at 19.9 nm has been measured to be approximately 1.5 cm-1 for an incident irradiance of approximately 2.5 x 10(13) W/cm2.