Improving the energies of approximate wave functions using the concepts of density functional theory

A simple method, derived from DFT, for improving the energy of a trial density is modified for the case of atoms. It is assumed that errors in the interelectronic repulsion are the only significant ones. The errors in the energies of single‐ζ Slater orbitals for the atoms from He to Ne are reduced an average factor of 21. © 2001 John Wiley & Sons, Inc. Int J Quantum Chem, 2001     

Measurements of NH3 in the ν2 = 1 state by a solid-state, photomixing, THz spectrometer, and a simultaneous analysis of the microwave, terahertz, and infrared transitions between the ground and ν2 inversion-rotation levels

In this paper, we report 30 THz measurements of ammonia in its excited, ν₂ = 1, inversion state. These measurements include transition frequencies and pressure shifts (where significant enough to be observed). Included in the data are two forbidden and three ro-inversion transitions, as well as 18 transitions never directly measured before. The measurements were made with an all-solid-state, diode-laser, difference-frequency spectrometer. Using an innovative laser-frequency locking scheme, this spectrometer provided accurately determined and continuously tuned THz-frequencies without requiring accurate knowledge of the absolute laser frequencies. The details of the spectrometer’s frequency calibration is discussed. A global analysis of NH₃ based on the available ground state, ν₂ = 1 state, and ν₂-band transitions was carried out, and the resulting set of recommended molecular effective-Hamiltonian parameters for ammonia is presented. In addition, calculated center frequencies and intensities for all possible transitions up to J = 20 between rotation, inversion, and vibration levels in the ground and ν₂ = 1 states are included as supplementary material.     

On the Fermi functionsI −(n+1/2)

We point out that an integral representation is possible for the Fermi functionsI _?3/2,I _?5/2,I _?7/2,I _?9/2, andI _?11/2 that arise in the extended Thomas-Fermi theory of hot, non-relativistic fermion systems. These functions can thus be computed by straightforward numerical integration, thereby avoiding problems previously encountered.     

Intramolecular cross-linking experiments on cytochrome c and ribonuclease A using an isotope multiplet method.

Mass spectral analysis of tryptic digests of cross-linked proteins offers considerable promise as a simple technique to probe protein structure and study protein-protein interactions. We describe the use of a 1:1 mixture of isotopically labeled and unlabeled cross-linkers, disuccinimidyladipate (DSA) and dimethyladipimidate (DMA), to enhance visualization of cross-linked peptides in a tryptic digest. Optimized intramolecular reactions of cytochrome c and ribonuclease A (RNase A) with DSA yielded an average of two cross-links per protein molecule. After digestion of the cross-linked cytochrome c with trypsin and analysis by liquid chromatography/mass spectrometry (LC/MS) and matrix-assisted laser desorption/ionization (MALDI), eight modified peptides, five cross-linked and two end-capped, were detected by virtue of their doublet character. An eighth modified peptide's identity remained ambiguous because of its inability to fragment. The lysine-lysine distance constraints obtained are discussed in the context of the known NMR and X-ray structures of cytochrome c. Analysis of cross-linked RNase A by LC/MS and MALDI yielded nine modified peptides, four of which were modified twice, as indicated by the isotopic triplets. Although seven of these peptides contained cross-links, few distance constraints were gained due to the fact that the cross-linked products were variations of modification of the same three lysine residues.     

International Intercomparison of Solar UVR Spectral Measurement Systems in Melbourne in 2013

Monitoring ambient solar UVR levels provides information on how much there is in both real time and historically. Quality assurance of ambient measurements of solar UVR is critical to ensuring accuracy and stability and this can be achieved by regular intercomparisons of spectral measurement systems with those of other organizations. In October and November of 2013 a solar UVR spectroradiometer from Public Health England (PHE) was brought to Melbourne for a campaign of intercomparisons with a new Bentham spectrometer of Australian Radiation Protection and Nuclear Safety Agency (ARPANSA) and one at the Australian Bureau of Meteorology (BOM), supported by New Zealand's National Institute for Water and Atmosphere (NIWA). Given all three spectroradiometers have calibrations that are traceable to various national standards, the intercomparison provides a chance to determine measurement uncertainties and traceability that support UV measurement networks in Australia, New Zealand and the UK. UV Index measurements from all three systems were compared and ratios determined for clear sky conditions when the scans from each instrument were within 2 min of each other. While wavelengths below 305 nm showed substantial differences between the PHE unit and the two other systems, overall the intercomparison results were encouraging, with mean differences in measured UV Index between the BOM/NIWA and those of PHE and ARPANSA of <0.1% and 7.5%, respectively.     

Calibration and use of the Epprecht Rheomat

Summary This paper deals with the calibration and use of an Epprecht Rheomat with particular reference to non Newtonian liquids. A method of calculating accurate rates of shear for non-Newtonian flow is derived using theEuler-Maclaurin sum formula. Some examples are given of the calculation of shear of poly vinyl chlorideplasticiser suspensions.

---

Zusammenfassung Die vorliegende Abhandlung befaßt sich mit der Eichung und dem Gebrauch eines Epprecht-Rheomats mit besonderer Hinsicht auf nicht-Newtonische Flüssigkeiten.Ein Verfahren zur exakten Berechnung von Scherwerten für nicht-Newtonische Flüssigkeiten läßt sich aus derEuler-Maclaurinschen Summenformel ableiten.Einige Beispiele zur Berechnung von Scherwerten für Weichmacher von Polyvinylchlorid sind beigefügt.

---

---

Paper presented at the Conference on Experimental Rheology, University of Bradford, April 17–19, 1968.     

Experimental investigations into an isothermal spinning threadline: Extensional rheology of a Separan AP 30 solution in glycerol and water

Summary Experimental observations on a steady isothermally extending filament of a water/glycerol solution of Separan AP 30 are presented. Photographic records were analysed to give filament diameter (and hence filament speed) as a function of distance below the extrusion die (a glass capillary). Measurements of inline tension were also made. When effects of weight, surface tension and air drag were accounted for, the extensional stress at every point along the filament could be calculated. Results for stress versus extension rate are presented for various flow situations.Independent rheogoniometric measurements of simple shear viscosity, first and second normal stress differences, and of a crude relaxation time were also made at comparable rates of deformation.Comparison shows that apparent extensional viscosities are several orders of magnitude larger than corresponding simple shear viscosities. After discussion, no conclusion can be drawn about what constitutive equation is most suitable to describe the results.An analysis to predict air drag is given.With 18 figures     

Gold nanoparticle-decorated keggin ions/TiO2 photococatalyst for improved solar light photocatalysis

We demonstrate a facile localized reduction approach to synthesizing a Au nanoparticle-decorated Keggin ion/TiO(2) photococatalyst for improved solar light photocatalysis application. This has been achieved by exploiting the ability of TiO(2)-bound Keggin ions to act as a UV-switchable, highly localized reducing agent. Notably, the approach proposed here does not lead to contamination of the resultant cocatalyst with free metal nanoparticles during aqueous solution-based synthesis. The study shows that for Keggin ions (phosphotungstic acid, PTA), being photoactive molecules, the presence of both Au nanoparticles and PTA on the TiO(2) surface in a cocatalytic system can have a dramatic effect on increasing the photocatalytic performance of the composite system, as opposed to a TiO(2) surface directly decorated with metal nanoparticles without a sandwiched PTA layer. The remarkable increase in the photocatalytic performance of these materials toward the degradation of a model organic Congo red dye correlates to an increase of 2.7-fold over that of anatase TiO(2) after adding Au to it and 4.3-fold after introducing PTA along with Au to it. The generalized localized reduction approach to preparing TiO(2)-PTA-Au cocatalysts reported here can be further extended to other similar systems, wherein a range of metal nanoparticles in the presence of different Keggin ions can be utilized. The composites reported here may have wide potential implications toward the degradation of organic species and solar cell applications.