A comparison of techniques for embedding defect cluster calculations

Cluster calculations have proved one of the most fruitful means of extracting useful information about solid-state defect properties at finite computational expense, but large clusters are necessary to obtain reliable results and uncertainty always remains concerning the effects of edge states, with ad hoc boundary conditions such as the saturation of the surface with hydrogen atoms being frequently employed. Recently methods have been developed for embedding the cluster in the perfect crystal so that the solution obtained from the cluster calculation is the same as would have been obtained from a full calculation on the whole defective solid. Here the relationships of these methods with each other and with perturbed crystal methods which modify the perfect crystal solution to account for the presence of the defect are explored. It is shown that the embedding potential technique is preferable and is equivalent to methods that have been used in other fields.This paper was presented at the International Conference on The Impact of Supercomputers on Chemistry, held at the University of London, London, UK, 13–16 April 1987     

Mass spectral and thermogravimetric studies of some iron(III) binuclear complexes with bridging thiuram disulfide ligands

Mass spectral and thermal studies by TG and DTG of some iron(III) binuclear complexes of the general type Fe₂(R₂dtc)₂(tds)X₂X/ have been carried out to determine their modes of decomposition. Fragmentation patterns are given and possible mechanisms are discussed.

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Zusammenfassung Massenspektrometrische und thermische Untersuchungen (TG und DTG) einiger zweikerniger Eisen(III)-Komplexe des allgemeinen Typs (R₂dtc)₂(tds)X₂X₂ wurden ausgeführt, um deren Zersetzungsmechanismus zu ermitteln. Fragmentspektren werden angegeben und mögliche Mechanismen diskutiert.

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- ( ) Fe₂(R₂dtc)₂(tds)X₂X₂ . .

     

Chemical oscillations in the uncatalyzed bromate oxidation of hydroquinone and nitrophenols

Chemical oscillatory behavior in the uncatalyzed bromate oxidation of hydroquinone and nitrophenols is reported. The reaction is strongly inhibited by stirring. Effect of one-electron redox couples (EZ catalysts) on the system is described.

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. . - ( EZ) .

     

Interplay of Thermochemistry and Structural Chemistry,the Journal (Volume 13, 2002) and the Discipline

As practiced disciplines, structural chemistry and thermochemistry need not be related. In the current study they are: the contents of the journal Structural Chemistry (Vol. 13) for the year 2002 have been reviewed and then most articles that appeared therein were given a thermochemical commentary, spin or slant.     

Computer-aided library search of combined LC-Retention and diode-array-UV-spectral data

An automated library search system for computer-aided identification of organic compounds using combined UV-spectral and LC-retention data, as acquired by HPLC with linear diodearray-UV-detection, is presented.The keystone of the system is a set of similarity indices which have been developed on the basis of mathematical-statistical models of the reproducibility of the spectral and retention data. The similarity indices have the form of a significance probability, a quantity originating from the general theory of hypothesis testing. The output of the LC-UV retrieval system is a compound identity or a list of identities (if any) for which the relevant similarity index has a value above a preset threshold. The data base used in this investigation contained 186 sets of UV-spectral and LC-retention data of 74 organophosphorus pesticides measured from standard solutions under various experimental conditions. A test set consisted of 186 alternative data sets of the same compounds as contained in the data base, however measured under different experimental conditions. The performance of the LC-UV reproducibility-based retrieval (LUVRR) system was evaluated using recall/reliability plots. The results appeared to be quite promising: for 95% of the unknowns, the target reference (correct positive) was on top of the hit list with a similarity index value being significantly higher than values found for false positives.The software is written in Pascal. The present (experimental) version of the system runs on a Data General Eclipse MV/4000 minicomputer.     

Classification of archaeologically stratified pumice by INAA

In the framework of the research program Synchronization of Civilizations in the Eastern Mediterranean Region in the 2nd Millenium B.C. instrumental neutron activation analysis (INAA) was used to determine 30 elements in pumice from archaeological excavations to reveal their specific volcanic origin. The widespread pumiceous products of several eruptions in the Aegean region were used as abrasive tools and were therefore popular trade objects. A remarkable quantity of pumice and pumiceous tephra (several km³ ) was produced by the Minoan eruption ofThera (Santorini), which is assumed to have happened between 1450 and 1650 B.C. Thus the discovery of the primary fallout of Minoan tephra in archaeologically stratified locations can be used as a relative time mark. Additionally, pumice lumps used as abrasive can serve for dating by first appearance. Essential to an identification of the primary volcanic source is the knowledge that pumices from the Aegean region can easily be distinguished by their trace element distribution patterns, as previous work has shown. The elements Al, Ba, Ca, Ce, Co, Cr, Cs, Dy, Eu, Fe, Hf, K, La, Lu, Mn, Na, Nd, Rb, Sb, Sc, Sm, Ta, Tb, Th, Ti, U, V, Yb, Zn and Zr were determined in 16 samples of pumice lumps from excavations in Tell-el-Dab'a and Tell-el-Herr (Egypt). Two irradiation cycles and five measurement runs were applied. A reliable identification of the samples is achieved by comparing these results to the database compiled in previous studies.     

Identification of exchange-coupled V4+ and Cu2+ ions in Cu?V?Mo oxide systems

ESR studies of X(CuO)·V₂O₅·8.3 MoO₃ (X=1–2) calcined in flowing nitrogen at 250–350 °C have revealed the exchange interaction of Cu²⁺ and V⁴⁺ ions that form a paramagnetic system.

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X(CuO) V₂O₅·8,3 MoO₃, X=1–2, , 250–350°C, Cu²⁺ V⁴⁺, .

     

State-of-the-art in organic elemental micro and ultramicro analysis

Summary Nernst developed a quartz torsion microbalance in 1903. In consequence of this pioneering work, Emich in the Technical University of Graz, Austria, had systematized a series of chemical operations in microscale as well as a microchemical analysis. Further advances in technique and method of organic microanalysis had been accomplished by Pregl in Graz in 1912. His work had been strongly supported by a new microbalance which was known as Kuhlmann microbalance. Pregl's original methods of analysis were arranged and published in 1916 as Die quantitative organische Mikroanalyse. It is still noteable that the Nobel prize of 1933 had been presented to Dr. Pregl. In accordance with a combination of electronic microbalance and computer techniques, organic elemental microanalysis has grown to include advanced instrumentation and on-line computation. Successful adaptation of microchemical analysis has expanded today not only to pure organic compounds, but on industrial intermediates, polymers, food additives and many other compositions. The paper includes a discussion of the relative merits of traditional and modern analytical techniques together with the progression of microbalances. Recent developments in organic micro and ultramicro analysis in Japan are also described.     

Synthesis of new condensed analogs of isoindolinium salts

Quaternary ammonium salts that contain a 3-(-naphthyl)propargyl group in addition to a group of the propargyl type undergo intramolecular cyclization of the diene-synthesis type under base-catalysis conditions to give condensed isoindolinium analogs.Communication 209 from the series Research on amines and ammonium compounds. See [1] for Communication 208.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 759–762, June, 1991.     

Thermal analysis of macromolecules

This review traces the development of thermal analysis over the last 40 years as it was experienced and contributed to by the author. The article touches upon the beginning of calorimetry and thermal analysis of polymers, the development of differential scanning calorimetry (DSC), single run DSC and other special instrumentations, up to the recent addition of modulation to calorimetry. Many new words and phrases have been introduced to the field by the author and his students, leaving a trail of the varied interests one can have over 40 years. It began with cold crystallization and most recently the term oriented, intermediate phase was coined, creating in-between: extended chain crystals, the irreversible thermodynamics of melting of polymer crystals, dynamic differential thermal analysis (DDTA), the rule of constant increase ofC _p per mobile bead within a molecule at the glass transition temperature, superheating of polymer crystals, melting kinetics, crystallization during polymerization, the chain-folding principle, molecular nucleation, rigid amorphous phase, a system of classifying molecules, macroconformations, amorphous defects, rules for the entropy of fusion based on molecular shape and flexibility, single-molecule single-crystals, a system of classifying phases and mesophases, and condis phase.First and foremost I would like to acknowledge the unwavering support through my wife, Heidel, without whom many of the projects simply could not have been completed. Similarly, our children had to grow up knowing that often research and teaching had to take precedence. Without coworkers, little could have been accomplished. Of the about 120 postdoctoral fellows, graduate students, and technicians, most of whom contributed to the listed references, and many have participated on their own in this issue, goes my thanks for the bulk of the scientific work. Many friends and colleagues contributed with discussion and constructive criticism, some of them have also contributed in this collection of papers related to thermal analysis. Little work can be done without this interplay of ideas. The limited space has not permitted to give a full appreciation of the importance of the ideas drawn from the literature. These thousands of additional references can be found in the initial papers and reviews of the subjects treated.Material support was received from the three major instrument companies for thermal analysis equipment: TA Instruments, Inc.; Perkin-Elmer Corp.; and Mettler-Toledo, Inc. Without this help we would not always have been able to be at the forefront of instrumentation. Major financial support for the research came from outside the universities. I estimate that over the 40 years about 4 Megadollars were spent by government agencies, companies, and private foundations to support coworkers, myself during the summers, research equipment, expenses, and travel. A large amount of money, but not too much if one compares it to typical expenditures in the field of athletics (about 10 k$ per paper). Major sustained funding came from the Advanced Projects Agency (ARPA), the Office of Naval Research (ONR), the National Aeronautics and Space Agency (NASA), the Department of Energy (DOE), and, most prominently, the National Science Foundation (NSF). At present our work is supported by the Division of Materials Research, National Science Foundation, Polymers Program, Grant # DMR 90-00520 and the Division of Materials Sciences, Office of Basic Energy Sciences, U.S. Department of Energy, under Contract DE-AC05-84OR21400 with Lockheed Martin Energy Systems, Inc. Industrial support is presently given by TA Instruments, Inc; ICI Paints; Exxon Res. and Eng. Co.; Shell Development Co.; Toray Research Center; and Mettler-Toledo, Inc.Last, but by no means least, I would like to thank Dr. E. Turi for the invitation to write this paper and for her untiring effort to entice so many of my students and friends to contribute to this issue of the Journal of Thermal Analysis.     

Solution of equation for a current-voltage curve describing reversible metal electrodissolution with linear boundedly semi-infinite diffusion and a linear alteration of potential in the stripping voltammetry method

An exact, sufficiently simple, explicit expression is obtained and a full contour of the stripping-voltammetry peak is calculated for a reversible process on a thin-film mercury electrode of finite thickness (linear boundedly semi-infinite diffusion is taken into account) in conditions of stripping voltammetry at a linearly altering potential. That these results were obtained at all, is due to use made of two extra boundary conditions (Nemovs and Nazarovs). The addends in the four forms of equations derived are the limiting expressions and corrections in the form of Nemovs or Nazarovs boundary conditions. It is shown that it is advisable to employ different forms of equations at large and small values of parameter H. The peaks height, full width at half-maximum, and potential are found to depend on H.Translated from Elektrokhimiya, Vol. 41, No. 1, 2005, pp. 54–68.Original Russian Text Copyright © 2005 by Nazarov, Stromberg.To the Centennial of B.N. Kabanov.Deceased.     

Metal concentrations in scleractinean corals determined by instrumental neutron activation analysis and atomic absorption spectrometry

Five species of scleractinean corals, extracted from the Northern Havana reef, were studied by INAA and AAS. Selected specimens were sectioned in foot, center and head parts before pulverization procedure. INAA for different irradiation and decay time regimes in a reactor allowed the determination of: Na, Mg, Al, Cl, Sc, Cr, Co, Th, Lu, Eu, Ce, Hf, La and Sr. AAS was performed in a Pye Unicam Model 929 spectrometer. Cu, Mn, Ni, Zn, and Fe were detected. Ca concentration in all species was also established. Obtained Metal-Calcium ratios for Sr, Cu, Zn, Cr, Co, Fe, Mn, Ni and Sc are compared with reported values.     

Untersuchung der Stabilisierung von Polyacrylnitrilfasern „Bulana” mittels Differentialthermoanalyse

Zusammenfassung Mittels DTA und DSC wird das Verhalten der Polyacrylnitrilfaser Bulana mit und ohne Vorbehandlung mit einer Lösung von 2-Phenyl-2-(3,5 Dinitro-4-Hydroxyphenyl)-Propan in Nitrobenzol beim Erhitzen an der Luft und in Stickstoff erforscht. Dabei werden erhöhte Temperaturen für Beginn und Maximum der exothermen Prozesse Zyklisierung und Oxydation sowie verminderte Enthalpieveränderungen (H) beobachtet. Die Aktivierungsenergie der Prozesse betrug für die Ausgangsfaser 29,8 kcal/mol und für die mit DNKPh vorbehandelte Faser 32,4 kcal/mol.

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Summary DTA and DSC measurements were used for studying the behaviour of crude PAN-fibre Bulana as well as PAN treated with a solution of 2-phenyl-2-(3,5 dinitro-4 hydroxyphenyl)-propane in nitrobenzene during heating in air and in nitrogen. As a result of the treatment an increase of the temperatures of initiation result of the treatment an increase of the temperatures of initiation and maximum of the exothermic reaction as well as a decrease of the enthalpy (H) were found. The calculated activation energy of cyclization and oxydation was 29,8 kcal/mol in case of PAN-fibre Bulana and increased to 32,4 kcal/mol in case of PAN-fibre Bulana treated with DNKPh.

     

A new gamma-ray spectrum catalog and library for PGAA

New measurements have been performed at the PGAA facility at the Budapest Research Reactor (BRR) in order to create a prompt -ray catalog for qualitative and quantitative analysis. The measured spectra were accurately analyzed by HYPERMET-PC. Prompt -ray energies and associated -ray production cross-sections have been determined by internal standardization. The resulting catalog contains prompt -ray data from neutron capture and other reactions such as (n,), and decay -ray data from short-lived reaction products. Data have been measured for nearly all stable elements, from hydrogen to uranium. Generally, data for several isotopes are given, to enable isotopic analysis as well. The whole library, including elemental spectra, will be available as a book.     

A constitutional diagram of the system VC0.88−HfC0.98−(MoC)

The system VC_0.88–HfC_0.98–MoC was investigated by means of melting point, differential-thermoanalytical, X-ray diffraction and metallographic techniques on hot pressed and heat treated as well as melted alloy specimens and a constitutional diagram from 1500°C through the melting range established.The small miscibility gap within the HfC–MoC system (T _c=1630°C) interacts at lower temperatures with the solvus in a monotectoid-like reaction at 1575°C. Additions of VC to the HfC–MoC solid solution gradually increase its critical temperature.Solid state phase behaviour and melting behaviour was established within the isopleths VC_0.88–MoC as well as within (V_0.5Hf_0.5)C–MoC and (V_0.75Hf_0.25)C–(Hf_0.75Mo_0.25)C.Phase equilibria within VC_0.88–HfC–MoC are characterized by an extreme large miscibility gap at 1500°C connecting the VC–HfC and HfC–MoC systems.Originating at the VC–HfC binary an eutectic trough proceeds into the VC–HfC–MoC ternary with rising temperatures, connecting the maximum critical point of the disappearing miscibility gap [(V_0.31Hf_0.49Mo_0.20)C] by a limiting tie line (2750±20°C). Isothermal sections have been calculated assuming regular solutions.With 5 Figures     

Aryloxydihydropyrans. XII. Configuration and conformations of 8-(3,4-dihydro-2-pyranyloxy)quinoline derivatives

The configuration and conformations of stereoisomeric 4R-8-(3,4-dihydro-2-pyranyloxy)quinolines were studied by means of their PMR spectra. It was established that the trans isomers of the investigated compounds have primarily a half-chair conformation and display an anomeric effect. A sofa conformation is proposed for the labile cis isomers.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 607–610, May, 1976.     

Zur Frage des Einsatzes ionenspezifischer Elektroden in der Automation

Zusammenfassung Es wurden Untersuchungen mit anionenspezifischen Membranelektroden nach Pungor durchgeführt. Dazu werden Reproduzierbarkeit, Eichfunktion, Einstellzeiten bei auf- und absteigender Konzentration und Querempfindlichkeit im Hinblick auf den Einsatz in automatischen Systemen behandelt. Es wird vorgeschlagen, für die Angabe der Selektivität einen p-Sel analog zum pH zu verwenden, die Behandlung eines Analysensensorsystems wird vorgenommen.

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On the use of ion-specific electrodes in automation

Investigations on anion-specific membrane electrodes are described. Problems of reproducibility, calibration, time-response in respect of in- and decreasing concentrations and sensitivity to interfering ions are demonstrated and discussed with regard to automation. It is proposed to define a p-sel for the selectivity constant analogue to pH and a calculation method for an Analysis-Sensor-System is shown.

     

Zero-Dimensional Nanodots on One-Dimensional Nanowires: Reductive Deposition of Metal Nanoparticles on Silicon Nanowires

We review herein the surface chemical properties of silicon nanowires (SiNWs) and show how SiNWs can be used as platforms in doing chemistry in the nanorealm. In particular, the surfaces of HF-treated SiNWs (which are H-terminated) exhibit interesting chemical reactivities towards reductive deposition of metal ions such as silver, copper, palladium, etc., giving rise to metal particles or aggregates on the SiNW surfaces. By varying the concentration of the metal ions in solution, nanostructures of these metals of different shapes, sizes, and morphologies can be fabricated. The reductive growth of ligated Au–Ag clusters of single size, shape, composition, and structure, on the SiNWs was also investigated. Two interesting phenomena, the sinking cluster and the cluster fusion processes, were observed by TEM. These assemblies of metal nanoparticles on silicon nanowires may be considered as zero-dimensional nanodots, on one-dimensional nanowires. It is hoped that fabrication of these metallic nanodots on silicon nanowires will lead to new and novel composite materials of importance in nanotechnology.     

Analysis of gamma-radioactivity of “hot particles” released after the Chernobyl accident

A particulate form (hot particles) of the radioactive fallout in Poland after the accident at the Chernobyl Nuclear Plant has been studied. Parameters of the effective reactor campaign are obtained from the characteristics of -activity of the hot particles. The numerical INV program written to calculate time evolution of eight isotopes in the reactor is described. On the basis of these calculations the measured hot particles are classified into two groups: those originating from the first load and those from younger fuel rods. A procedure for dating younger hot particles is proposed. The results of the analyses constitute a basis for other investigations of hot particles.     

Thermal plasma composition in the presence of easily and noneasily ionized components

The influence of easily and noneasily ionized components on equilibrium particle density ratios in thermal plasmas has been investigated. Particular emphasis is given to the modeling of metal halide discharges with iodine as a halide. The calculations were done for standard air with lithium or iodine, standard argon with aluminum, and with a mixture of aluminum and iodine. The system setup is in agreement with spectroscopic results for an open-chamber gas-stabilized d.c. arc, with a pressure of 1×10⁵ Pa and temperatures corresponding to the radial distribution of temperature for this type of discharge. It is shown that the behavior of the plasma core is dominated by the easily ionized component (Li or Al) while the periphery is characterized by the noneasily ionized component (iodine).