Radiochemical analyses of radiologically-contaminated soil samples in support of transport modeling

In 1951, unsaturated prairie soil was contaminated with fission products and actinides. Fifty years later, in 2001, soil samples were collected from the contaminated site. This paper describes the techniques used to analyze these samples, including gamma-spectroscopy (GS) for ¹³⁷Cs, neutron activation analysis (NAA/GS) for ²³⁸U, liquid scintillation counting (LSC) for ⁹⁰Sr and inductively coupled plasma mass spectroscopy (ICP-MS) for ²³⁸U and ^113mCd. As expected, ICP-MS was found to have the lowest detection level, while the techniques were ranked in order of increasing uncertainty as GS, NAA/GS, ICP-MS and LSC.     

Infrared spectra of methylidynes formed in reactions of re atoms with methane, methyl halides, methylene halides, and ethane: methylidyne C-H stretching absorptions, bond lengths, and s character

Rhenium carbyne complexes (HC identical with ReH 3, HC identical with ReH 2X, HC identical with ReHX 2, [X = F, Cl, and Br] and CH 3C identical with ReH 3) are produced by reactions of laser-ablated Re atoms with methane, methyl halides, methylene halides, and ethane via oxidative C-H(X) insertion and alpha-hydrogen migration in favor of the carbon-metal triple bond. The stabilities of the carbyne complexes relative to other possible products are predicted by DFT calculations. The diagnostic methylidyne C-H stretching absorptions of HC identical with ReH 3 and its mono- and dihalo derivatives are observed on the blue sides of the precursor C-H stretching bands, and the frequency decreases and the bond length increases in the order of H, F, Cl, and Br, following the decreasing s character in hybridization for the C-H bond. The dihalo methylidynes have higher C-H stretching frequencies and s characters than the monohalo species. The rhenium methylidynes have C s structures, and as a result the HC identical with ReH 3 and CH 3C identical with ReH 3 complexes have two equivalent shorter and one longer Re-H bonds, as compared to the tungsten methylidyne HC identical with WH 3 with three equivalent W-H bonds.     

A combined experimental and theoretical study of uranium polyhydrides with new evidence for the large complex UH4(H2)6

Several monouranium and diuranium polyhydride molecules were investigated using quantum chemical methods. The infrared spectra of uranium and hydrogen reaction products in condensed neon and pure hydrogen were measured and compared with previous argon matrix frequencies. The calculated molecular structures and vibrational frequencies were used to identify the species present in the matrix. Major new absorptions were observed and compared with the previous argon matrix study. Spectroscopic evidence was obtained for the novel complex, UH4(H2)6, which has potential interest as a metal hydride with a large number of hydrogen atoms bound to uranium. Our calculations show that the series of complexes UH4(H2)1,2,4,6 are stable.     

Functionalised β-diketonate polynuclear lanthanoid hydroxo clusters: Synthesis,characterisation, and magnetic properties

The controlled hydrolysis of lanthanoid trichloride hexahydrate (Ln = Nd, Eu, Ho) in methanol with the β-diketone ligands dibenzoylmethane and 1,3-bis(4-ethoxyphenyl)propane-1,3-dione yielded tetranuclear and pentanuclear hydroxo clusters for Eu and Ho. In contrast, performing the reaction in the presence of 1,3-bis(4-methoxyphenyl)propane-1,3-dione yielded a mononuclear complex for Nd. The compounds were structurally characterised by means of single crystal X-ray diffraction, showing that the increased bulkiness of the ligand due to the ethoxy functionalities does not affect the capability of the diketonate to stabilize the cluster core. Variable temperature dc susceptibility magnetic measurements were made on the clusters and were indicative of very weak to zero antiferromagnetic, intra-cluster coupling. Variable frequency ac data recorded at low temperatures did not show any evidence for single molecule magnet (SMM) behaviour, unlike the recent reported case of the analogue [Dy₅(OH)₅(Ph₂acac)₁₀], where Ph₂acac⁻ is the dibenzoylmethanide ligand.     

The meaning of Ramanujan now and for the future

December 22, 2010 marks the 123th anniversary of Ramanujan’s birth. In this paper we pay homage to this towering figure whose mathematical discoveries so affected mathematics throughout the twentieth century and into the twenty-first.     

Spectroscopic observation of a group 12 oxyfluoride: a matrix-isolation and quantum-chemical investigation of mercury oxyfluorides

Getting to the root of Hg: Experiments with amalgams as a source for laser-ablated Hg atoms as reaction partners with OF(2) gave strong HgF(2) IR absorptions and new bands in the Hg?F stretching region for OHgF and FOHgF molecules trapped in solid neon and argon. Assignment of these new bands to the first oxyfluoride of mercury, OHgF, and to the FOHgF insertion product is supported by quantum-chemical methods.     

ChemInform Abstract: Infrared Spectroscopic and Theoretical Investigations of the OUF2 and OThF2 Molecules with Triple Oxo Bond Character.

The title molecules are prepared by reaction of OF₂ molecules with laser ablated uranium and thorium atoms in solid argon and neon.     

ChemInform Abstract: Matrix Infrared Spectroscopic and Theoretical of the Difluoroamino Metal Fluoride Molecules: F2NMF (M: Cu,Ag, Au).

The title molecules are obtained from spontaneous reactions of coinage metals and NF₃ in solid Ar and Ne matrices.