Neutral rare-gas containing charge-transfer molecules in solid matrices : I. HXeCl, HXeBr, HXeI, and HKrCl in Kr and Xe

Ultraviolet-irradiation of hydrogen halide containing rare gas matrices yields the formation of linear centrosymmetric cations of type (XHX)⁺, (X=Ar, Kr, Xe). Annealing of the irradiated doped solids produces, along with thermoluminescence, extremely strong absorptions in the 1700–1000 cm⁻¹ region. Based on isotopic substitution and halogen dependence of these bands, the presence of hydrogen and halogen atom(s) in these species is evident. In the present paper we show the participation of rare gas atom(s) in these new compounds. The evidence is based on studies of the thermally generated species in mixed rare gas matrices. The new species are assigned as neutral charge-transfer molecules HX⁺Y⁻ (Y=halogen), and their vibrational spectra are discussed and compared with those calculated with ab initio methods. This is the first time hydrogen and a rare gas atom has been found to make a chemical bond in a neutral stable compound. The highest level ab initio calculations on the existence of compounds of type HXY corroborate the experimental observations. The mechanism responsible for the formation of these species is also discussed. PACS: 61.80.Ba, 33.15.Fm, 81.40.Ef, 78.50.-

Cohesive properties of alkali halides

We calculate cohesive properties of LiF, NaF, KF, LiCl, NaCl, and KCl with ab-initio quantum chemical methods. The coupled-cluster approach is used to correct the Hartree-Fock crystal results for correlations and to systematically improve cohesive energies, lattice constants and bulk moduli. After inclusion of correlations, we recover 95-98 % of the total cohesive energies. The lattice constants deviate from experiment by at most 1.1 %, bulk moduli by at most 8 %. We also find good agreement for spectroscopic properties of the corresponding diatomic molecules.Comment: LaTeX, 10 pages, 1 figure, accepted by Phys. Rev.

Electron affinities of the first- and second- row atoms: benchmark ab initio and density functional calculations

A benchmark ab initio and density functional (DFT) study has been carried out on the electron affinities of the first- and second-row atoms. The ab initio study involves basis sets of $spdfgh$ and $spdfghi$ quality, extrapolations to the 1-particle basis set limit, and a combination of the CCSD(T), CCSDT, and full CI electron correlation methods. Scalar relativistic and spin-orbit coupling effects were taken into account. On average, the best ab initio results agree to better than 0.001 eV with the most recent experimental results. Correcting for imperfections in the CCSD(T) method improves the mean absolute error by an order of magnitude, while for accurate results on the second-row atoms inclusion of relativistic corrections is essential. The latter are significantly overestimated at the SCF level; for accurate spin-orbit splitting constants of second-row atoms inclusion of (2s,2p) correlation is essential. In the DFT calculations it is found that results for the 1st-row atoms are very sensitive to the exchange functional, while those for second-row atoms are rather more sensitive to the correlation functional. While the LYP correlation functional works best for first-row atoms, its PW91 counterpart appears to be preferable for second-row atoms. Among ``pure DFT'' (nonhybrid) functionals, G96PW91 (Gill 1996 exchange combined with Perdew-Wang 1991 correlation) puts in the best overall performance. The best results overall are obtained with the 1-parameter hybrid modified Perdew-Wang (mPW1) exchange functionals of Adamo and Barone [J. Chem. Phys. {\bf 108}, 664 (1998)], with mPW1LYP yielding the best results for first-row, and mPW1PW91 for second-row atoms. Indications exist that a hybrid of the type $a$ mPW1LYP + $(1-a)$ mPW1PW91 yields better results than either of the constituent functionals.Comment: Phys. Rev. A, in press (revised version, review of issues concerning DFT and electron affinities added

Correlation effects in MgO and CaO: Cohesive energies and lattice constants

A recently proposed computational scheme based on local increments has been applied to the calculation of correlation contributions to the cohesive energy of the CaO crystal. Using ab-initio quantum chemical methods for evaluating individual increments, we obtain 80% of the difference between the experimental and Hartree-Fock cohesive energies. Lattice constants corrected for correlation effects deviate by less than 1% from experimental values, in the case of MgO and CaO.Comment: LaTeX, 4 figure

Extinction Risk and Diversification Are Linked in a Plant Biodiversity Hotspot

Plant extinction risks in the Cape, South Africa differ from those for vertebrates worldwide, with young and fast-evolving plant lineages marching towards extinction at the fastest rate, but independently of human effects

Diversity and Functional Traits of Lichens in Ultramafic Areas: A Literature Based Worldwide Analysis Integrated by Field Data at the Regional Scale

While higher plant communities found on ultramafics are known to display peculiar characteristics, the distinguishability of any peculiarity in lichen communities is still a matter of contention. Other biotic or abiotic factors, rather than substrate chemistry, may contribute to differences in species composition reported for lichens on adjacent ultramafic and non-ultramafic areas. This work examines the lichen biota of ultramafics, at global and regional scales, with reference to species-specific functional traits. An updated world list of lichens on ultramafic substrates was analyzed to verify potential relationships between diversity and functional traits of lichens in different Köppen–Geiger climate zones. Moreover, a survey of diversity and functional traits in saxicolous communities on ultramafic and non-ultramafic substrates was conducted in Valle d’Aosta (North-West Italy) to verify whether a relationship can be detected between substrate and functional traits that cannot be explained by other environmental factors related to altitude. Analyses (unweighted pair group mean average clustering, canonical correspondence analysis, similarity-difference-replacement simplex approach) of global lichen diversity on ultramafic substrates (2314 reports of 881 taxa from 43 areas) displayed a zonal species distribution in different climate zones rather than an azonal distribution driven by the shared substrate. Accordingly, variations in the frequency of functional attributes reflected reported adaptations to the climate conditions of the different geographic areas. At the regional scale, higher similarity and lower species replacement were detected at each altitude, independent from the substrate, suggesting that altitude-related climate factors prevail over putative substrate–factors in driving community assemblages. In conclusion, data do not reveal peculiarities in lichen diversity or the frequency of functional traits in ultramafic areas

Roles of spatial scale and rarity on the relationship between butterfly species richness and human density in South Africa

Wildlife and humans tend to prefer the same productive environments, yet high human densities often lead to reduced biodiversity. Species richness is often positively correlated with human population density at broad scales, but this correlation could also be caused by unequal sampling effort leading to higher species tallies in areas of dense human activity. We examined the relationships between butterfly species richness and human population density at five spatial resolutions ranging from 2′ to 60′ across South Africa. We used atlas-type data and spatial interpolation techniques aimed at reducing the effect of unequal spatial sampling. Our results confirm the general positive correlation between total species richness and human population density. Contrary to our expectations, the strength of this positive correlation did not weaken at finer spatial resolutions. The patterns observed using total species richness were driven mostly by common species. The richness of threatened and restricted range species was not correlated to human population density. None of the correlations we examined were particularly strong, with much unexplained variance remaining, suggesting that the overlap between butterflies and humans is not strong compared to other factors not accounted for in our analyses. Special consideration needs to be made regarding conservation goals and variables used when investigating the overlap between species and humans for biodiversity conservation