Infrared spectra of aluminum hydrides in solid hydrogen: Al2H4 and Al2H6

The reaction of laser-ablated Al atoms and normal-H(2) during co-deposition at 3.5 K produces AlH, AlH(2), and AlH(3) based on infrared spectra and the results of isotopic substitution (D(2), H(2) + D(2) mixtures, HD). Four new bands are assigned to Al(2)H(4) from annealing, photochemistry, and agreement with frequencies calculated using density functional theory. Ultraviolet photolysis markedly increases the yield of AlH(3) and seven new absorptions for Al(2)H(6) in the infrared spectrum of the solid hydrogen sample. These frequencies include terminal Al-H(2) and bridge Al-H-Al stretching and AlH(2) bending modes, which are accurately predicted by quantum chemical calculations for dibridged Al(2)H(6), a molecule isostructural with diborane. Annealing these samples to remove the H(2) matrix decreases the sharp AlH(3) and Al(2)H(6) absorptions and forms broad 1720 +/- 20 and 720 +/- 20 cm(-1) bands, which are due to solid (AlH(3))(n). Complementary experiments with thermal Al atoms and para-H(2) at 2.4 K give similar spectra and most product frequencies within 2 cm(-1). Although many volatile binary boron hydride compounds are known, binary aluminum hydride chemistry is limited to the polymeric (AlH(3))( solid. Our experimental characterization of the dibridged Al(2)H(6) molecule provides an important link between the chemistries of boron and aluminum.     

Zinc and cadmium dihydroxide molecules: matrix infrared spectra and theoretical calculations

Laser-ablated zinc and cadmium atoms were mixed uniformly with H2 and O2 in excess argon or neon and with O2 in pure hydrogen or deuterium during deposition at 8 or 4 K. UV irradiation excites metal atoms to insert into O2 producing OMO molecules (M = Zn, Cd), which react further with H2 to give the metal hydroxides M(OH)2 and HMOH. The M(OH)2 molecules were identified through O-H and M-O stretching modes with appropriate HD, D2, (16,18)O2, and (18)O2 isotopic shifts. The HMOH molecules were characterized by O-H, M-H, and M-O stretching modes and an M-O-H bending mode, which were particularly strong in pure H2/D2. Analogous Zn and Cd atom reactions with H2O2 in excess argon produced the same M(OH)2 absorptions. Density functional theory and MP2 calculations reproduce the IR spectra of these molecules. The bonding of Group 12 metal dihydroxides and comparison to Group 2 dihydroxides are discussed. Although the Group 12 dihydroxide O-H stretching frequencies are lower, calculated charges show that the Group 2 dihydroxide molecules are more ionic.     

The absorption spectra of the phenoxyl radical in solid argon

Vacuum ultraviolet photolysis of phenol, phenol-d₆ and anisole during condensation with excess argon at 20 K has produced and trapped the phenoxyl radical as evidenced by structured absorptions at 397.2 and 628.1 nm. A broad photosensitive 416 ± 2 nm band is tentatively assigned to the phenol cation.     

Absorption spectra and photochemistry of the toluene cation and benzyl radical in solid argon

Toluene diluted in argon subjected to continuous argon discharge radiation during condensation at 21 K revealed absorptions at 310.5 and 449.6 nm due to benzyl radical, and 317 nm due to a C₇7H₉ radical. A photosensitive 430 nm band, in agreement with photodissociation spectra of the toluene parent cation, is assigned to this species.     

Speciation of arsenic in ground water samples: A comparative study of CE-UV, HG-AAS and LC-ICP-MS

The performance of capillary electrophoresis-ultraviolet detector (CE-UV), hydride generation-atomic absorption spectrometry (HG-AAS) and liquid chromatography-inductively coupled plasma mass spectrometry (LC-ICP-MS) have been compared for the speciation of arsenic (As) in groundwater samples. Two inorganic As species, arsenite (As^III), arsenate (As^V) and one organo species dimethyl arsenic acid (DMA) were mainly considered for this study as these are known to be predominant in water. Under optimal analytical conditions, limits of detection (LD) ranging from 0.10 (As^III, AsT) to 0.19 (DMA) μg/l for HG-AAS, 100 (As^III, DMA) to 500 (As^V) μg/l for CE-UV and 0.1 (DMA, MMA) to 0.2 (As^III, As^V) μg/l for LC-ICP-MS, allowed the determination of the above three species present in these samples. Results obtained by all the three methods are well correlated (r² = 0.996*** for total As) with the precision of <5% R.S.D. except CE-UV. The effect of interfering ions (e.g. Fe²⁺, Fe³⁺, SO₄²⁻ and Cl⁻) commonly found in ground water on separation and estimation of As species were studied and corrected for. Spike recovery was tested and found to be 80-110% at 0.5 μg/l As standard except CE-UV where only 50% of the analyte was recovered. Comparison of these results shows that LC-ICP-MS is the best choice for routine analysis of As species in ground water samples.     

Pd-catalysed cross coupling of terminal alkynes to diynes in the absence of a stoichiometric additive

An efficient, room temperature procedure for the cross-coupling of a range of terminal alkynes, using standard Sonogashira cross-coupling conditions (Pd/Cu) is presented. At higher reaction temperatures, head-to-tail or head-to-head dimerisation affords 1,3- and 1,4-disubstituted enynes, respectively as minor products.     

A cation-pi binding interaction with a tyrosine in the binding site of the GABAC receptor

GABA(C) (rho) receptors are members of the Cys-loop superfamily of neurotransmitter receptors, which includes nicotinic acetylcholine (nACh), 5-HT(3), and glycine receptors. As in other members of this family, the agonist binding site of GABA(C) receptors is rich in aromatic amino acids, but while other receptors bind agonist through a cation-pi interaction to a tryptophan, the GABA(C) binding site has tyrosine at the aligning positions. Incorporating a series of tyrosine derivatives at position 198 using unnatural amino acid mutagenesis reveals a clear correlation between the cation-pi binding ability of the side chain and EC(50) for receptor activation, thus demonstrating a cation-pi interaction between a tyrosine side chain and a neurotransmitter. Comparisons among four homologous receptors show variations in cation-pi binding energies that reflect the nature of the cationic center of the agonist.     

Berechnung der Bandstruktur vom Vanadiumcarbid VC

Zusammenfassung Die Bandstruktur von stöchiometrischem Vanadiumcarbid VC wird mit Hilfe der quasi-selbstkonsistenten APW-Methode ermittelt. Als Austauschpotential wird ein parametrisiertes Slatersches Austauschpotential verwendet. Die Energie-Eigenwerte werden für 256k-Punkte in der 1. Brillouin-Zone berechnet. Zur Berechnung der Zustandsdichte werden weitere Energiewerte (für insgesamt 16384k-Punkte) nach der LCAO-Interpolationsmethode von Slater und Koster bestimmt und mit diesen die Zustandsdichte ermittelt. Die partiellen LCAO-Zustandsdichten zeigen weitgehende Übereinstimmung mit den APW-Charakterdichten und geben Aufschluß über denl-Charakter der Energiebänder. Die Ladungsverteilung im Kristall weist auf eine Ladungsüberführung vom Vanadium zum Kohlenstoff und damit auf eine gewisse Ionizität der Verbindung VC hin.

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Calculation of the band structure of vanadium carbide VC

The energy band structure of stoichiometric VC has been calculated by the quasi-self-consistent APW method. For the exchange potential a parametrized Slater-free-electron approximation has been used. The energy eigenvalues have been calculated for 256k-points in the first Brillouin zone. Further energy values (for a total number of 16384k-points) have been obtained by the LCAO interpolation method of Slater and Koster. From these energy values the density-of-states histogram has been calculated. The partial LCAO-densities-of-states are largely in agreement with the APW-character-densities. Both quantities give information about thel-character of the energy bands. The charges in the APW-spheres indicate a charge transfer from vanadium to carbon.

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Résumé La structure des bandes énergétiques du VC de composition stoichiométrique a été calculée par la méthode APW quasiautoconsistante. On s'est servi d'un potentiel d'échange paramétrisé selon Slater. Les eigen-valeurs d'énergie sont déterminées pour 256 pointsk dans la premiere zone de Brillouin. Pour dériver la densité d'états énergétiques ainsi que les densités d'états partielles (densités d'états du caractère 2s, 2p et3d) des valeurs d'énergie pour d'autres pointsk (en somme 16384) sont trouvées avec l'aide de la méthode d'interpolation LCAO de Slater et Koster. Il n'y a pas des différences significantes entre ces quantités et les densités des caractèresl calculées directement par la méthode APW. Des densités d'états partielles on peut dériver le caractèrel des bandes énergétiques.De la distribution des charges dans le cristal résulte un transfer de charge du vanadium au carbon ce qui signifie que le VC possède une certaine ionicité.

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Dem Gedenken an Herrn Prof. Dr. K. H. Hansen gewidmet.

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Dem Jubiläumsfonds der österreichischen Nationalbank sind wir für die gewährte finanzielle Unterstützung zu großem Dank verpflichtet. Herrn Prof. Dr. H. Nowotny danken wir für die Förderung, die er dieser Arbeitsrichtung angedeihen läßt. Die große Hilfe von Herrn Dr. K. Schwarz, University of Florida, Gainesville, wird dankbar anerkannt.