102 research outputs found
Discourse structuring of dynamic content
Uno de los desafíos de la Generación de Lenguaje Natural es la adaptación de
la estructura y las palabras de la salida lingüística a la habilidad del usuario, el contenido,
el género apropiado, el estilo, etc. Nos centramos en la determinación de la estructura
del discurso. En general, se supone que entre dos unidades de contenido ocurre siempre
la misma relación de discurso. Propuestas que varían el tipo de relación discursiva y el
orden de las proposiciones según la interpretación del contenido siguen siendo escasas. Sin
embargo, tal interpretación es extremadamente importante especialmente si el contenido es
altamente dinámico como por ejemplo, cuando los datos son series temporales. Presentamos
un planificador de textos que considera las restricciones que imponen los datos dinámicos
para tomar decisiones a cada etapa de la planificación, en particular para la selección de las
relaciones discursivas y la ordenación de las proposiciones.One of Natural Language Generation’s continuing challenges is to determine the
structure and words of the generated linguistic output in accordance with the expertise of
the user, the content, the appropriate genre, style, etc. We focus on the determination of
the discourse structure. Most often, it is assumed that between two content units always
the same discourse relation holds. Approaches in which the choice of discourse relations
and the ordering of propositions depends on the interpretation of the content are still scarce.
However, such an interpretation is extremely important especially if the content is highly
dynamic as, e.g., in the case of data parameter time series. We present a text planner that
takes into account the constraints imposed by dynamic data to make decisions at every
stage of the text planning, and in particular, for the selection of discourse relations and the
ordering of propositions.The work reported on in this paper has been carried out in
the framework of the MARQUIS-project funded by the European
Commission in the framework of the eContent programme
under the contract number EDC-11258; duration:
2005-2007
Influence of electron correlations on ground-state properties of III-V semiconductors
Lattice constants and bulk moduli of eleven cubic III-V semiconductors are
calculated using an ab initio scheme. Correlation contributions of the valence
electrons, in particular, are determined using increments for localized bonds
and for pairs and triples of such bonds; individual increments, in turn, are
evaluated using the coupled cluster approach with single and double
excitations. Core-valence correlation is taken into account by means of a core
polarization potential. Combining the results at the correlated level with
corresponding Hartree-Fock data, we obtain lattice constants which agree with
experiment within an average error of -0.2%; bulk moduli are accurate to +4%.
We discuss in detail the influence of the various correlation contributions on
lattice constants and bulk moduli.Comment: 4 pages, Latex, no figures, Phys. Rev. B, accepte
Correlated ab-initio calculations for ground-state properties of II-VI semiconductors
Correlated ab-initio ground-state calculations, using relativistic
energy-consistent pseudopotentials, are performed for six II-VI semiconductors.
Valence () correlations are evaluated using the coupled cluster approach
with single and double excitations. An incremental scheme is applied based on
correlation contributions of localized bond orbitals and of pairs and triples
of such bonds. In view of the high polarity of the bonds in II-VI compounds, we
examine both, ionic and covalent embedding schemes for the calculation of
individual bond increments. Also, a partitioning of the correlation energy
according to local ionic increments is tested. Core-valence ()
correlation effects are taken into account via a core-polarization potential.
Combining the results at the correlated level with corresponding Hartree-Fock
data we recover about 94% of the experimental cohesive energies; lattice
constants are accurate to \sim 1%; bulk moduli are on average 10% too large
compared with experiment.Comment: 10 pages, twocolumn, RevTex, 3 figures, accepted Phys. Rev.
A high-resolution infrared spectroscopic investigation of the halogen atom-HCN entrance channel complexes solvated in superfluid helium droplets
Rotationally resolved infrared spectra are reported for the X-HCN (X = Cl,
Br, I) binary complexes solvated in helium nanodroplets. These results are
directly compared with that obtained previously for the corresponding X-HF
complexes [J. M. Merritt, J. K\"upper, and R. E. Miller, PCCP, 7, 67 (2005)].
For bromine and iodine atoms complexed with HCN, two linear structures are
observed and assigned to the and ground
electronic states of the nitrogen and hydrogen bound geometries, respectively.
Experiments for HCN + chlorine atoms give rise to only a single band which is
attributed to the nitrogen bound isomer. That the hydrogen bound isomer is not
stabilized is rationalized in terms of a lowering of the isomerization barrier
by spin-orbit coupling. Theoretical calculations with and without spin-orbit
coupling have also been performed and are compared with our experimental
results. The possibility of stabilizing high-energy structures containing
multiple radicals is discussed, motivated by preliminary spectroscopic evidence
for the di-radical Br-HCCCN-Br complex. Spectra for the corresponding molecular
halogen HCN-X complexes are also presented.Comment: 20 pages, 15 figures, 6 tables, RevTe
Synthesis and Electronic Structure Determination of Uranium(VI) Ligand Radical Complexes
Pentagonal bipyramidal uranyl complexes of salen ligands, N,N’-bis(3-tert-butyl-(5R)-salicylidene)-1,2-phenylenediamine, in which R = tBu (1a), OMe (1b), and NMe2 (1c), were prepared and the electronic structure of the one-electron oxidized species [1a-c]+ were investigated in solution. The solid-state structures of 1a and 1b were solved by X-ray crystallography, and in the case of 1b an asymmetric UO22+ unit was found due to an intermolecular hydrogen bonding interaction. Electrochemical investigation of 1a-c by cyclic voltammetry showed that each complex exhibited at least one quasi-reversible redox process assigned to the oxidation of the phenolate moieties to phenoxyl radicals. The trend in redox potentials matches the electron-donating ability of the para-phenolate substituents. The electron paramagnetic resonance spectra of cations [1a-c]+ exhibited gav values of 1.997, 1.999, and 1.995, respectively, reflecting the ligand radical character of the oxidized forms, and in addition, spin-orbit coupling to the uranium centre. Chemical oxidation as monitored by ultraviolet-visible-near-infrared (UV-vis-NIR) spectroscopy afforded the one-electron oxidized species. Weak low energy intra-ligand charge transfer (CT) transitions were observed for [1a-c]+ indicating localization of the ligand radical to form a phenolate / phenoxyl radical species. Further analysis using density functional theory (DFT) calculations predicted a localized phenoxyl radical for [1a-c]+ with a small but significant contribution of the phenylenediamine unit to the spin density. Time-dependent DFT (TD-DFT) calculations provided further insight into the nature of the low energy transitions, predicting both phenolate to phenoxyl intervalence charge transfer (IVCT) and phenylenediamine to phenoxyl CT character. Overall, [1a-c]+ are determined to be relatively localized ligand radical complexes, in which localization is enhanced as the electron donating ability of the para-phenolate substituents is increased (NMe2 > OMe > tBu)
Pseudo electron-deficient organometallics: limited reactivity towards electron-donating ligands
YesHalf-sandwich metal complexes are of considerable interest in medicine, material, and nanomaterial chemistry. The design of libraries of such complexes with particular reactivity and properties is therefore a major quest. Here, we report the unique and peculiar reactivity of eight apparently 16-electron half-sandwich metal (ruthenium, osmium, rhodium, and iridium) complexes based on benzene-1,2-dithiolato and 3,6-dichlorobenzene-1,2-dithiolato chelating ligands. These electron-deficient complexes do not react with electron-donor pyridine derivatives, even with the strong σ-donor 4-dimethylaminopyridine (DMAP) ligand. The Ru, Rh, and Ir complexes accept electrons from the triphenylphosphine ligand (σ-donor, π-acceptor), whilst the Os complexes were found to be the first examples of non-electron-acceptor electron-deficient metal complexes. We rationalized these unique properties by a combination of experimental techniques and DFT/TDFT calculations. The synthetic versatility offered by this family of complexes, the low reactivity at the metal center, and the facile functionalization of the non-innocent benzene ligands is expected to allow the synthesis of libraries of pseudo electron-deficient half-sandwich complexes with unusual properties for a large range of applications
A comprehensive study of Interatomic Coulombic Decay in argon dimers: Extracting R-dependent absolute decay rates from the experiment
In this work we present a comprehensive and detailed study of Interatomic Coulombic Decay (ICD) occurring after irradiating argon dimers with XUV-synchrotron radiation. A manifold of different decay channels is observed and the corresponding initial and final states are assigned. Additionally, the effect of nuclear dynamics on the ICD electron spectrum is examined for one specific decay channel. The internuclear distance-dependent width Γ(R) of the decay is obtained from the measured kinetic energy release distribution of the ions employing a classical nuclear dynamics model
Definitions of Textual Conventions for Pseudowire (PW) Management Status of This Memo
This document specifies an Internet standards track protocol for the Internet community, and requests discussion and suggestions for improvements. Please refer to the current edition of the "Internet Official Protocol Standards " (STD 1) for the standardization state and status of this protocol. Distribution of this memo is unlimited. Copyright Notice Copyright (c) 2009 IETF Trust and the persons identified as th
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