Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements

The 6‐31G* and 6‐31G** basis sets previously introduced for first‐row atoms have been extended through the second‐row of the periodic table. Equilibrium geometries for one‐heavy‐atom hydrides calculated for the two‐basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6‐31G* structures, obtained for two‐heavy‐atom hydrides and for a variety of hypervalent second‐row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first‐row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6‐31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split‐valance 3‐21G basis set for both normal‐ and hypervalent compounds. Normal‐mode vibrational frequencies derived from 6‐31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3‐21G basis set. Hydrogenation energies calculated for normal‐ and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences

National Mesothelioma Virtual Bank: A standard based biospecimen and clinical data resource to enhance translational research

Background: Advances in translational research have led to the need for well characterized biospecimens for research. The National Mesothelioma Virtual Bank is an initiative which collects annotated datasets relevant to human mesothelioma to develop an enterprising biospecimen resource to fulfill researchers' need. Methods: The National Mesothelioma Virtual Bank architecture is based on three major components: (a) common data elements (based on College of American Pathologists protocol and National North American Association of Central Cancer Registries standards), (b) clinical and epidemiologic data annotation, and (c) data query tools. These tools work interoperably to standardize the entire process of annotation. The National Mesothelioma Virtual Bank tool is based upon the caTISSUE Clinical Annotation Engine, developed by the University of Pittsburgh in cooperation with the Cancer Biomedical Informatics Grid™ (caBIG™, see http://cabig.nci.nih.gov). This application provides a web-based system for annotating, importing and searching mesothelioma cases. The underlying information model is constructed utilizing Unified Modeling Language class diagrams, hierarchical relationships and Enterprise Architect software. Result: The database provides researchers real-time access to richly annotated specimens and integral information related to mesothelioma. The data disclosed is tightly regulated depending upon users' authorization and depending on the participating institute that is amenable to the local Institutional Review Board and regulation committee reviews. Conclusion: The National Mesothelioma Virtual Bank currently has over 600 annotated cases available for researchers that include paraffin embedded tissues, tissue microarrays, serum and genomic DNA. The National Mesothelioma Virtual Bank is a virtual biospecimen registry with robust translational biomedical informatics support to facilitate basic science, clinical, and translational research. Furthermore, it protects patient privacy by disclosing only de-identified datasets to assure that biospecimens can be made accessible to researchers. © 2008 Amin et al; licensee BioMed Central Ltd

Self‐consistent molecular orbital methods. XXIII. A polarization‐type basis set for second‐row elements

The 6‐31G* and 6‐31G** basis sets previously introduced for first‐row atoms have been extended through the second‐row of the periodic table. Equilibrium geometries for one‐heavy‐atom hydrides calculated for the two‐basis sets and using Hartree–Fock wave functions are in good agreement both with each other and with the experimental data. HF/6‐31G* structures, obtained for two‐heavy‐atom hydrides and for a variety of hypervalent second‐row molecules, are also in excellent accord with experimental equilibrium geometries. No large deviations between calculated and experimental single bond lengths have been noted, in contrast to previous work on analogous first‐row compounds, where limiting Hartree–Fock distances were in error by up to a tenth of an angstrom. Equilibrium geometries calculated at the HF/6‐31G level are consistently in better agreement with the experimental data than are those previously obtained using the simple split‐valance 3‐21G basis set for both normal‐ and hypervalent compounds. Normal‐mode vibrational frequencies derived from 6‐31G* level calculations are consistently larger than the corresponding experimental values, typically by 10%–15%; they are of much more uniform quality than those obtained from the 3‐21G basis set. Hydrogenation energies calculated for normal‐ and hypervalent compounds are in moderate accord with experimental data, although in some instances large errors appear. Calculated energies relating to the stabilities of single and multiple bonds are in much better accord with the experimental energy differences

Hyperfine resolved spectrum of the molecular dication DCl

We have obtained hyperfine-resolved infrared spectra of a PQ23(N) branch line in the v = 2-1 band of the X 3Σ- state of the molecular dication D35Cl2+. Analysis of the hyperfine structure allows us to estimate the magnitude of the Fermi contact interaction for the chlorine nucleus; bF(Cl) = 167 (25) MHz

In Situ NMR Spectroscopy of Supercapacitors: Insight into the Charge Storage Mechanism

Electrochemical capacitors, commonly known as supercapacitors, are important energy storage devices with high power capabilities and long cycle lives. Here we report the development and application of in situ nuclear magnetic resonance(NMR) methodologies to study changes at the electrode−electrolyte interface in working devices as they charge and discharge. For a supercapacitor comprising activated carbon electrodes and an organic electrolyte, NMR experiments carried out at different charge states allow quantification of the number of charge storing species and show that there are at least two distinct charge storage regimes. At cell voltages below 0.75 V, electrolyte anions are increasingly desorbed from the carbon micropores at the negative electrode, while at the positive electrode there is little change in the number of anions that are adsorbed as the voltage is increased. However, above a cell voltage of 0.75 V, dramatic increases in the amount of adsorbed anions in the positive electrode are observed while anions continue to be desorbed at the negative electrode. NMR experiments with simultaneous cyclic voltammetry show that supercapacitor charging causes marked changes to the local environments of charge storing species, with periodic changes of their chemical shift observed. NMR calculations on a model carbon fragment show that the addition and removal of electrons from a delocalized system should lead to considerable increases in the nucleus-independent chemical shift of nearby species, in agreement with our experimental observations

The correspondence between the molecular orbital and differential ionization energies methods

The correspondence between Self-Consistent Hückel MO methods and Differential Ionization Energies methods is discussed in terms of the approximations used for the diagonal matrix elements. The two methods are shown to be equivalent if electronic correlation is neglected. Ground-state properties of the hydrogen halides are calculated by these simple methods and shown to be in good overall agreement with experimental data. Die Übereinstimmung zwischen selbstkonsistenten Hückel MO-Methoden und Methoden der Differentiellen Ionisierungsenergien wird in Termen solcher Näherungen diskutiert, die für die diagonalen Matrixelemente benutzt werden. Es wird gezeigt, daß die beiden Methoden äquivalent sind, wenn die Elektronenkorrelation vernachlässigt wird. Grundzustandseigenschaften der “hydrogen halides” werden mit diesen einfachen Methoden ausgerechnet und zeigen sich in überall guter Übereinstimmung mit experimentellen Daten. La correspondance entre les méthodes SCF Hückel et d'énergie d'ionisation différentielle est discutée en fonction des approximations utilisées pour les éléments de matrice diagonaux. Les deux méthodes sont équivalentes si la corrélation électronique est négligée. Les propriétés de l'état fondamental des acides halogènés sont calculées par ces méthodes simples et l'on constate un accord raisonnable avec les données expérimentales.Peer Reviewedhttp://deepblue.lib.umich.edu/bitstream/2027.42/46451/1/214_2004_Article_BF00572780.pd

What Works in Conservation 2018

This book provides an assessment of the effectiveness of 1277 conservation interventions based on summarized scientific evidence. The 2018 edition contains new chapters covering practical global conservation of primates, peatlands, shrublands and heathlands, management of captive animals as well as an extended chapter on control of freshwater invasive species. Other chapters cover global conservation of amphibians, bats, birds and forests, conservation of European farmland biodiversity and some aspects of enhancing natural pest control, enhancing soil fertility and control of freshwater invasive species. It contains key results from the summarized evidence for each conservation intervention and an assessment of the effectiveness of each by international expert panels. The accompanying website www.conservationevidence.com describes each of the studies individually, and provides full references