Analysis of red and yellow ochre samples from Clearwell Caves and Catalhoyuk by vibrational spectroscopy and other techniques

Ochre samples excavated from the neolithic site at Qatalhoyuk, Turkey have been compared with "native" ochres from Clearwell Caves, UK using infrared spectroscopy backed up by Raman spectroscopy, scanning electron microscopy (with energy-dispersive X-rays (EDX) analysis), powder X-ray diffraction, diffuse reflection UV-Vis and atomic absorption spectroscopies. For the Clearwell Caves ochres, which range in colour from yellow-orange to red-brown, it is shown that the colour is related to the nature of the chromophore present and not to any differences in particle size. The darker red ochres contain predominantly haematite while the yellow ochre contains only goethite. The ochres from Qatalhoyuk contain only about one-twentieth of the levels of iron found in the Clearwell Caves ochres. The iron oxide pigment (haematite in all cases studied here) has been mixed with a soft lime plaster which also contains calcite and silicate (clay) minerals. (C) 2003 Elsevier B.V. All rights reserved.

Synthesis, spectroscopy and spectroelectrochemistry of chlorocarbonyl {1,2-bis[(2,6-diisopropylphenyl)imino]-acenaphthene-kappa(2)-N,N '}rhodium (I)

Reaction of the dinuclear complex [{Rh(CO)(2)}(2) (mu-Cl)(2)]with an alpha-diimine ligand, 1,2- bis[(2,6-diisopropylphenyl) imino] acenaphthene (iPr(2)Ph-bian), produces square-planar [RhCl(CO)(iPr(2)Ph-bian)]. For the first time, 2: 1 and 1: 1 alpha-diimine/dimer reactions yielded the same product. The rigidity of iPr(2)Ph-bian together with its flexible electronic properties and steric requirements of the 2,6-diisopropyl substituents on the benzene rings allow rapid closure of a chelate bond and replacement of a CO ligand instead of chloride. A resonance Raman study of [RhCl(CO)(iPr(2)Ph-bian)] has revealed a predominant Rh-to-bian charge transfer (MLCT) character of electronic transitions in the visible spectral region. The stabilisation of [RhCl(CO)(iPr(2)Ph-bian)] in lower oxidation states by the pi-acceptor iPr(2)Ph-bian ligand was investigated in situ by UV-VIS, IR and EPR spectroelectrochemistry at variable temperatures. The construction of the novel UV-VIS-NIR-IR low-temperature OTTLE cell used in these studies is described in the last part of the paper.

Electronic structure of point defects in controlled self-doping of the TiO2 (110) surface: Combined photoemission spectroscopy and density functional theory study

Point defects in metal oxides such as TiO2 are key to their applications in numerous technologies. The investigation of thermally induced nonstoichiometry in TiO2 is complicated by the difficulties in preparing and determining a desired degree of nonstoichiometry. We study controlled self-doping of TiO2 by adsorption of 1/8 and 1/16 monolayer Ti at the (110) surface using a combination of experimental and computational approaches to unravel the details of the adsorption process and the oxidation state of Ti. Upon adsorption of Ti, x-ray and ultraviolet photoemission spectroscopy (XPS and UPS) show formation of reduced Ti. Comparison of pure density functional theory (DFT) with experiment shows that pure DFT provides an inconsistent description of the electronic structure. To surmount this difficulty, we apply DFT corrected for on-site Coulomb interaction (DFT+U) to describe reduced Ti ions. The optimal value of U is 3 eV, determined from comparison of the computed Ti 3d electronic density of states with the UPS data. DFT+U and UPS show the appearance of a Ti 3d adsorbate-induced state at 1.3 eV above the valence band and 1.0 eV below the conduction band. The computations show that the adsorbed Ti atom is oxidized to Ti2+ and a fivefold coordinated surface Ti atom is reduced to Ti3+, while the remaining electron is distributed among other surface Ti atoms. The UPS data are best fitted with reduced Ti2+ and Ti3+ ions. These results demonstrate that the complexity of doped metal oxides is best understood with a combination of experiment and appropriate computations.

Rapid characterisation of archaeological midden components using FT-IR spectroscopy, SEM-EDX and micro-XRD

Samples taken from middens at the Neolithic site of Catalhoyuk in Turkey have been analysed using IR spectroscopy backed up by powder XRD and SEM-EDX. Microcomponents studied include fossil hack-berries (providing evidence of ancient diet and seasonality), mineral nodules (providing evidence of post-depositional change) and phytoliths (mineralised plant cells, providing evidence of usage of plant species). Finely laminated ashy deposits have also been investigated allowing chemical and mineralogical variations to be explored. It is found that many layers which appear visually to be quite distinctive have, in fact, very similar mineralogy. (C) 2009 Elsevier B.V. All rights reserved.

Notations and conventions in molecular spectroscopy: part 1. General spectroscopic notation

The field of Molecular Spectroscopy was surveyed in order to determine a set of conventions and symbols which are in common use in the spectroscopic literature. This document, which is Part I in a series, establishes the notations and conventions used for general spectroscopic notations and deals with quantum mechanics, quantum numbers (vibrational states, angular momentum and energy levels), spectroscopic transitions, and miscellaneous notations (e.g. spectroscopic terms). Further parts will follow, dealing inter alia with symmetry notation, permutation and permutation-inversion symmetry notation, vibration-rotation spectroscopy and electronic spectroscopy.

Notations and conventions in molecular spectroscopy: part 2. Symmetry notation

The field of Molecular Spectroscopy was surveyed in order to determine a set of conventions and symbols which are in common use in the spectroscopic literature. This document, which is Part 2 in a series, establishes the notations and conventions used for the description of symmetry in rigid molecules, using the Schoenflies notation. It deals firstly with the symmetry operators of the molecular point groups (also drawing attention to the difference between symmetry operators and elements). The conventions and notations of the molecular point groups are then established, followed by those of the representations of these groups as used in molecular spectroscopy. Further parts will follow, dealing inter alia with permutation and permutation-inversion symmetry notation, vibration-rotation spectroscopy and electronic spectroscopy.