Friendly Settlements in the Framework of the Inter- American Human Rights System

The Inter-American system for the protection of human rights provides that disputesbetween States and victims of human rights violations or their representatives can beresolved through a friendly settlement. In this arrangement, conducted before the regionalorgans of protection of human rights, the State accepts its international responsibility,commits itself to investigate and judge the responsible and makes commitmentson compensation to the offended, the victims, on his part, renounce to take the caseto the Inter-American Court of Human Rights, and the Inter-American Commissionmonitors the legal consistency of the agreement and holds the role of independentobserver. What are these agreements, what possibilities and limitations provide to theopposing parties and, above all, what kind of reparation offer to victims of humanrights violations are issues to resolve in this article.

A new all-round density functional based on spin states and SN2 barriers

We report here a new empirical density functional that is constructed based on the performance of OPBE and PBE for spin states and SN 2 reaction barriers and how these are affected by different regions of the reduced gradient expansion. In a previous study [Swart, Sol̀, and Bickelhaupt, J. Comput. Methods Sci. Eng. 9, 69 (2009)] we already reported how, by switching between OPBE and PBE, one could obtain both the good performance of OPBE for spin states and reaction barriers and that of PBE for weak interactions within one and the same (SSB-sw) functional. Here we fine tuned this functional and include a portion of the KT functional and Grimme's dispersion correction to account for π- π stacking. Our new SSB-D functional is found to be a clear improvement and functions very well for biological applications (hydrogen bonding, π -π stacking, spin-state splittings, accuracy of geometries, reaction barriers)

'Back into the american continuity of crust and mantle'': da cidade inscrita à cidade em escrita

No contexto norte-americano, falar da noção de cidade implica olhar para além das complexas redes sociais, económicas, políticas e culturais que se interligam em espaços mais ou menos urbanizados. É necessário considerar o facto de que na América a cidade assenta no princípio da Cidade erguida na Colina e esta dimensão mítica e simbólica que inspira os colonos recém-chegados a Nova Inglaterra é perpetuada nas gerações seguintes, refletindo-se igualmente no panorama literário norte-americano.

Short-eared Owl (Asio flammeus) surveys in the North American Intermountain West: utilizing citizen scientists to conduct monitoring across a broad geographic scale

The Short-eared Owl (Asio flammeus) is an open-country species breeding in the northern United States and Canada, and has likely experienced a long-term, range-wide, and substantial decline. However, the cause and magnitude of the decline is not well understood. We set forth to address the first two of six previously proposed conservation priorities to be addressed for this species: (1) better define habitat use and (2) improve population monitoring. We recruited 131 volunteers to survey over 6.2 million ha within the state of Idaho for Short-eared Owls during the 2015 breeding season. We surveyed 75 transects, 71 of which were surveyed twice, and detected Short-eared Owls on 27 transects. We performed multiscale occupancy modeling to identify habitat associations, and performed multiscale abundance modeling to generate a state-wide population estimate. Our results suggest that within the state of Idaho, Short-eared Owls are more often found in areas with marshland or riparian habitat or areas with greater amounts of sagebrush habitat at the 1750 ha transect scale. At the 50 ha point scale, Short-eared Owls tend to associate positively with fallow and bare dirt agricultural land and negatively with grassland. Cropland was not chosen at the broader transect scale suggesting that Short-eared Owls may prefer more heterogeneous landscapes. On the surface our results may seem contradictory to the presumed land use by a “grassland” species; however, the grasslands of the Intermountain West, consisting largely of invasive cheatgrass (Bromus tectorum), lack the complex structure shown to be preferred by these owls. We suggest the local adaptation to agriculture represents the next best habitat to their historical native habitat preferences. Regardless, we have confirmed regional differences that should be considered in conservation planning for this species. Last, our results demonstrate the feasibility, efficiency, and effectiveness of utilizing public participation in scientific research to achieve a robust sampling methodology across the broad geography of the Intermountain West.

An interpretation of baroclinic initial value problems: results for simple basic states with nonzero interior PV gradients

In the Eady model, where the meridional potential vorticity (PV) gradient is zero, perturbation energy growth can be partitioned cleanly into three mechanisms: (i) shear instability, (ii) resonance, and (iii) the Orr mechanism. Shear instability involves two-way interaction between Rossby edge waves on the ground and lid, resonance occurs as interior PV anomalies excite the edge waves, and the Orr mechanism involves only interior PV anomalies. These mechanisms have distinct implications for the structural and temporal linear evolution of perturbations. Here, a new framework is developed in which the same mechanisms can be distinguished for growth on basic states with nonzero interior PV gradients. It is further shown that the evolution from quite general initial conditions can be accurately described (peak error in perturbation total energy typically less than 10%) by a reduced system that involves only three Rossby wave components. Two of these are counterpropagating Rossby waves—that is, generalizations of the Rossby edge waves when the interior PV gradient is nonzero—whereas the other component depends on the structure of the initial condition and its PV is advected passively with the shear flow. In the cases considered, the three-component model outperforms approximate solutions based on truncating a modal or singular vector basis.

A comparison of three canopy interception models for a leafless mixed deciduous forest stand in the eastern United States

Canopy interception of incident precipitation is a critical component of the forest water balance during each of the four seasons. Models have been developed to predict precipitation interception from standard meteorological variables because of acknowledged difficulty in extrapolating direct measurements of interception loss from forest to forest. No known study has compared and validated canopy interception models for a leafless deciduous forest stand in the eastern United States. Interception measurements from an experimental plot in a leafless deciduous forest in northeastern Maryland (39°42'N, 75°5'W) for 11 rainstorms in winter and early spring 2004/05 were compared to predictions from three models. The Mulder model maintains a moist canopy between storms. The Gash model requires few input variables and is formulated for a sparse canopy. The WiMo model optimizes the canopy storage capacity for the maximum wind speed during each storm. All models showed marked underestimates and overestimates for individual storms when the measured ratio of interception to gross precipitation was far more or less, respectively, than the specified fraction of canopy cover. The models predicted the percentage of total gross precipitation (PG) intercepted to within the probable standard error (8.1%) of the measured value: the Mulder model overestimated the measured value by 0.1% of PG; the WiMo model underestimated by 0.6% of PG; and the Gash model underestimated by 1.1% of PG. The WiMo model’s advantage over the Gash model indicates that the canopy storage capacity increases logarithmically with the maximum wind speed. This study has demonstrated that dormant-season precipitation interception in a leafless deciduous forest may be satisfactorily predicted by existing canopy interception models.

Comparative advantage in demand: Experimental evidence of preferences for genetically modified food in the United States and European Union

The United States (US) exports more than US$6 billion in agricultural commodities to the European Union (EU) each year, but one issue carries the potential to diminish this trade: use of biotechnology in food production. The EU has adopted more stringent policies towards biotechnology than the US. Understanding differences in European and American policies towards genetically modified (GM) foods requires a greater understanding of consumers' attitudes and preferences. This paper reports results from the first large-scale, cross-Atlantic study to analyse consumer demand for genetically modified food in a non-hypothetical market environment. We strongly reject the frequent if convenient assumption in trade theory that consumer preferences are identical across countries: the median level of compensation demanded by English and French consumers to consume a GM food is found to be more than twice that in any of the US locations. Results have important implications for trade theory, which typically focusses on differences in specialization, comparative advantage and factor endowments across countries, and for on-going trade disputes at the World Trade Organization.

Spectroscopy of highly excited vibrational states of HCN in its ground electronic state

An experimental technique based on a scheme of vibrationally mediated photodissociation has been developed and applied to the spectroscopic study of highly excited vibrational states in HCN, with energies between 29 000 and 30 000 cm(-1). The technique consists of four sequential steps: in the first one, a high power laser is used to vibrationally excite the sample to an intermediate state, typically (0,0,4), the nu(3) mode being approximately equivalent to the C-H stretching vibration. Then a second laser is used to search for transitions between this intermediate state and highly vibrationally excited states. When one of these transitions is found, HCN molecules are transferred to a highly excited vibrational state. Third, a ultraviolet laser photodissociates the highly excited molecules to produce H and CN radicals in its A (2)Pi electronic state. Finally, a fourth laser (probe) detects the presence of the CN(A) photofragments by means of an A-->B-->X laser induced fluorescence scheme. The spectra obtained with this technique, consisting of several rotationally resolved vibrational bands, have been analyzed. The positions and rotational parameters of the states observed are presented and compared with the results of a state-of-the-art variational calculation. (C) 2004 American Institute of Physics.

Highly excited vibrational states of HCN around 30 000 cm(-1)

This article describes the analysis and interpretation of rovibrational spectra involving highly excited vibrational states in the molecule of HCN. The spectra were obtained by means of the vibrationally mediated photodissociation technique. Analysis of the spectra revealed four bands with Sigma-Sigma structures that, once fitted, provided the energies and rotational constants of four new, highly excited vibrational states in the region of the potential energy surface near and above 30 000 cm(-1). All the states could be identified with the help of a state-of-the-art variational calculation. Together with the states already observed in previous works, eight highly excited states have so far been identified in this region. (c) 2006 American Institute of Physics.

Excited states of nitro-polypyridine metal complexes and their ultrafast decay. Time-resolved IR absorption, spectroelectrochemistry, and TD-DFT calculations of fac-[Re(Cl)(CO)3(5-Nitro-1,10-phenanthroline)]

The lowest absorption band of fac-[Re(Cl)(CO)(3)(5-NO2-phen)] encompasses two close-lying MLCT transitions. The lower one is directed to LUMO, which is heavily localized on the NO2 group. The UV-vis absorption spectrum is well accounted for by TD-DFT (G03/PBEPBE1/CPCM), provided that the solvent, MeCN, is included in the calculations. Near-UV excitation of fac-[Re(Cl)(CO)(3)(5-NO2-phen)] populates a triplet metal to ligand charge-transfer excited state, (MLCT)-M-3, that was characterized by picosecond time-resolved IR spectroscopy. Large positive shifts of the v(CO) bands upon excitation (+70 cm(-1) for the A'(1) band) signify a very large charge separation between the Re(Cl)(CO)3 unit and the 5-NO2-phen ligand. Details of the excited-state character are revealed by TD-DFT calculated changes of electron density distribution. Experimental excited-state v(CO) wavenumbers agree well with those calculated by DFT. The (MLCT)-M-3 state decays with a ca. 10 ps lifetime (in MeCN) into another transient species, that was identified by TRIR and TD-DFT calculations as an intraligand (3)n pi* excited state, whereby the electron density is excited from the NO2 oxygen lone pairs to the pi* system of 5-NO2-phen. This state is short-lived, decaying to the ground state with a similar to 30 ps lifetime. The presence of an n pi* state seems to be the main factor responsible for the lack of emission and the very short lifetimes of 3 MLCT states seen in all d(6)-metal complexes of nitro-polypyridyl ligands. Localization of the excited electron density in the lowest (MLCT)-M-3 states parallels localization of the extra electron in the reduced state that is characterized by a very small negative shift of the v(CO) IR bands (-6 cm(-1) for A'(1)) but a large downward shift of the v(s)(NO2) IR band. The Re-Cl bond is unusually stable toward reduction, whereas the Cl ligand is readily substituted upon oxidation.

Rhenium-to-benzoylpyridine and rhenium-to-bipyridine MLCT excited states offac-[Re(Cl)(4-benzoylpyridine)2(CO)3] andfac-[Re(4-benzoylpyridine)(CO)3(bpy)]+: a time-resolved spectroscopic and spectroelectrochemical study

The lowest allowed electronic transition of fac-[Re(Cl)(CO)(3)(bopy)(2)] (bopy = 4-benzoylpyridine) has a Re --> bopy MLCT character, as revealed by UV-vis and stationary resonance Raman spectroscopy. Accordingly, the lowest-lying, long-lived, excited state is Re --> bopy (MLCT)-M-3. Electronic depopulation of the Re(CO)(3) unit and population of a bopy pi* orbital upon excitation are evident by the upward shift of v(Cequivalent toO) vibrations and a downward shift of the ketone v(C=O) vibration, respectively, seen in picosecond time-resolved IR spectra. Moreover, reduction of a single bopy ligand in the (MLCT)-M-3 excited state is indicated by time-resolved visible and resonance Raman (TR3) spectra that show features typical of bopy(.-). In contrast, the lowest allowed electronic transition and lowest-lying excited state of a new complex fac-[Re(bopy)(CO)(3)(bpy)](+) (bpy = 2,2'-bipyridine) have been identified as Re --> bpy MLCT with no involvement of the bopy ligand, despite the fact that the first reduction of this complex is bopy-localized, as was proven spectroelectrochemically. This is a rare case in which the localizations of the lowest MLCT excitation and the first reduction are different. (MLCT)-M-3 excited states of both fac-[Re(Cl)(CO)(3)(bopy)(2)] and fac-[Re(bopy)(CO)(3)(bpy)](+) are initially formed vibrationally hot. Their relaxation is manifested by picosecond dynamic shifts of v(Cequivalent toO) IR bands. The X-ray structure of fac-[Re(bopy)(CO)(3)(bpy)](PF6CH3CN)-C-. has been determined.

Beyond the American century: Walter Lippmann and American grand strategy, 1943-1950

As the United States became a world Power, journalist and intellectual Walter Lippmann feared that it would become its own worst enemy. During and after the Second World War, he tried to steer the country towards coherent statecraft, to define the national interest and the limits of power, and give geopolitical expression to the role of the United States as the core of an Atlantic strategic system. But in response to world war, the Truman Doctrine, and the Korean War, he became pessimistic about the country's ability to conduct strategy effectively. In the prophetic tradition, he believed that a fatal symbiosis between America's growing strength and domestic politics led it towards crisis. Though at times ahistorical, Lippmann's concept of strategy deserves attention for its dialogue between power and identity, for its questioning of “ends” as well as means, and for its focus on the danger of self-defeating behaviour.