Preparation and properties of gallaborane, GaBH6: structure of the gaseous molecule H2Ga(μ-H)2BH2 as determined by vibrational, electron diffraction, and ab initio studies, and structure of the crystalline solid at 110 K as determined by x-ray diffraction``

Gallaborane (GaBH6, 1), synthesized by the metathesis of LiBH4 with [H2GaCl]n at ca. 250 K, has been characterized by chemical analysis and by its IR and 1H and 11B NMR spectra. The IR spectrum of the vapor at low pressure implies the presence of only one species, viz. H2Ga(μ-H)2BH2, with a diborane-like structure conforming to C2v symmetry. The structure of this molecule has been determined by gas-phase electron diffraction (GED) measurements afforced by the results of ab initio molecular orbital calculations. Hence the principal distances (rα in Å) and angles ( α in deg) are as follows: r(Ga•••B), 2.197(3); r(Ga−Ht), 1.555(6); r(Ga−Hb), 1.800(6); r(B−Ht), 1.189(7); r(B−Hb), 1.286(7); Hb−Ga−Hb, 71.6(4); and Hb−B−Hb, 110.0(5) (t = terminal, b = bridging). Aggregation of the molecules occurs in the condensed phases. X-ray crystallographic studies of a single crystal at 110 K reveal a polymeric network with helical chains made up of alternating pseudotetrahedral GaH4 and BH4 units linked through single hydrogen bridges; the average Ga•••B distance is now 2.473(7) Å. The compound decomposes in the condensed phases at temperatures exceeding ca. 240 K with the formation of elemental Ga and H2 and B2H6. The reactions with NH3, Me3N, and Me3P are also described.

The vibrational spectra of natural and perdeuterated monochlorogallane, H2Ga([mu]-Cl)2GaH2, and an empirical harmonic potential function

The infrared and Raman spectra of monochlorogallane and its fully deuterated isotopomer are recorded and assigned on the basis of the dimeric structures. H2Ga(μ-Cl)2GaH2 and D2Ga(μ-Cl)2GaD2, conforming to D2 symmetry. The observed frequencies are corrected for anharmonicity and fitted to a potential function in which 19 of the 33 independent force constants are refined.

The use of a multiple criteria decision analysis to evaluate the effectiveness of landscape and habitat enhancement mechanisms: an example from the South Downs

A range of funding schemes and policy instruments exist to effect enhancement of the landscapes and habitats of the UK. While a number of assessments of these mechanisms have been conducted, little research has been undertaken to compare both quantitatively and qualitatively their relative effectiveness across a range of criteria. It is argued that few tools are available for such a multi-faceted evaluation of effectiveness. A form of Multiple Criteria Decision Analysis (MCDA) is justified and utilized as a framework in which to evaluate the effectiveness of nine mechanisms in relation to the protection of existing areas of chalk grassland and the creation of new areas in the South Downs of England. These include established schemes, such as the Countryside Stewardship and Environmentally Sensitive Area Schemes, along with other less common mechanisms, for example, land purchase and tender schemes. The steps involved in applying an MCDA to evaluate such mechanisms are identified and the process is described. Quantitative results from the comparison of the effectiveness of different mechanisms are presented, although the broader aim of the paper is that of demonstrating the performance of MCDA as a tool for measuring the effectiveness of mechanisms aimed at landscape and habitat enhancement.

Observations of the diurnal cycle of outgoing longwave radiation from the Geostationary Earth Radiation Budget instrument

The Geostationary Earth Radiation Budget instrument on Meteosat-8, located over Africa, provides unprecedented temporal sampling (~17 minutes) of the broadband emitted thermal and reflected solar radiances. We analyse the diurnal cycle of the outgoing longwave radiation (OLR) fluxes derived from the thermal radiances for July 2006. Principal component (PC) analysis separates the signals of the surface temperature response to solar heating and of the development of convective clouds. The first two PCs explain most of the OLR variations: PC1 (surface heating) explains 82.3% of the total variance and PC2 (cloud development) explains 12.8% of the variance. Convection is initiated preferentially over mountainous regions and the cloud then advects downstream in the ambient flow. Diurnal variations are much weaker over the oceans, but a coherent signal over the Gulf of Guinea suggests that the cloudiness is modulated by the diurnally varying contrast between the Gulf and the adjacent land mass.

Evaluation of the Met Office global forecast model using Geostationary Earth Radiation Budget (GERB) data

Simulations of the top-of-atmosphere radiative-energy budget from the Met Office global numerical weather-prediction model are evaluated using new data from the Geostationary Earth Radiation Budget (GERB) instrument on board the Meteosat-8 satellite. Systematic discrepancies between the model simulations and GERB measurements greater than 20 Wm-2 in outgoing long-wave radiation (OLR) and greater than 60 Wm-2 in reflected short-wave radiation (RSR) are identified over the period April-September 2006 using 12 UTC data. Convective cloud over equatorial Africa is spatially less organized and less reflective than in the GERB data. This bias depends strongly on convective-cloud cover, which is highly sensitive to changes in the model convective parametrization. Underestimates in model OLR over the Gulf of Guinea coincide with unrealistic southerly cloud outflow from convective centres to the north. Large overestimates in model RSR over the subtropical ocean, greater than 50 Wm-2 at 12 UTC, are explained by unrealistic radiative properties of low-level cloud relating to overestimation of cloud liquid water compared with independent satellite measurements. The results of this analysis contribute to the development and improvement of parametrizations in the global forecast model.