Ligand Substitution Dynamics

Substitution of a ligand in an inner sphere complex by an outside group is the most fundamental reaction in metal ion chemistr

Experimentally generating and tuning robust entanglement between photonic qubits

We generate and study the entanglement properties of novel states composed of three polarisation-encoded photonic qubits. By varying a single experimental parameter we can coherently move from a fully separable state to a maximally robust W state, while at all times preserving an optimally robust, symmetric entanglement configuration. We achieve a high fidelity with these configurations experimentally, including the highest reported W state fidelity.Comment: lower print quality for arxiv figure

Ligand Substitution Processes

From the preface: The subject of the mechanistic study of ligand substitution reactions is currently undergoing an exciting growth. New fast-reaction techniques have removed the upper limit on rates that can be measured, and extension to less familiar central metal atoms has begun in earnest. This might seem the wrong moment for review of the field. As yet, definitive treatment is possible only for those complexes involving monodentate ligands with cobalt(III) and platinurn(II). But, because information is so extensive for these systems, it is clear that they are functioning as models from which concepts and experiments are generated for application over the fast-growing range of the subject. We believe that this is an important moment to reopen debate on fundamentals so that concepts will be most felicitously formulated to aid growth of understanding. This monograph is centrally concerned with three aspects of those fundamentals. We have attempted to develop an approach to classification of ligand substitution reactions that is adapted to what seem to have emerged as the characteristic features of these reactions and is susceptible to operational tests. (We do recognize that any such scheme of ideas is necessarily obsolescent once it is formulated since new experiments will certainly follow immediately.) We have tried to evaluate the basis for making generalizations about ligand substitution processes and to formulate tests to show whether new reactions fall within familiar patterns. Finally, we have sought to base the models of ligand substitution processes in the language of molecular-orbital theory. We believe that MO theory is most useful, because it may be used to correlate rate data on complexes with the extensive information available from spectral and magnetic studies, yet differs from crystal-field theory in providing a natural place for consideration of the bonding electrons, which must be a principal determinant of reaction processes. To keep this essay within bounds, we assume familiarity with the elements of experimental kinetics, transition-state theory, and the simple molecular-orbital theory of complexes. Introductory physical chemistry, some familiarity with the study of reaction mechanisms, and mastery of one of the qualitative treatments of MO theory as applied to transition-metal complexes should provide sufficient background. Thus, we hope that this book will be useful to students, relatively early in their careers, who wish to explore this field. Our debts to very many workers will be obvious throughout. We want to record here our special personal debt to Professors Ralph G. Pearson and Fred Basolo and to Dr. Martin Tobe. We particularly thank Professor George S. Hammond for his interest and enthusiasm in this project. Professor Hammond carefully read and criticized the entire manuscript in the final drafts. We received many other valuable criticisms at various stages of this project from Professors R. D. Archer, F. Basolo, J. O. Edwards, J. Finholt, P. Haake, J. Halpern, A. Kropf, R. G. Pearson, S. I. Shupack, M. S. Silver, and C. Walling, and Dr. U. Belluco and Dr. L. Cattalini. We very much appreciate their help and probably should have followed their suggestions more closely. We warmly acknowledge expert assistance from Mrs. Madeline deFriesse, Miss Jan Denby, and Mrs. Diane Celeste in preparation of the manuscript. COOPER H. LANGFORD HARRY B. GRAY Amherst, Massachusetts New York, New York October 196

Photometric Variability in Earthshine Observations

The identification of an extrasolar planet as Earth-like will depend on the detection of atmospheric signatures or surface non-uniformities. In this paper we present spatially unresolved flux light curves of Earth for the purpose of studying a prototype extrasolar terrestrial planet. Our monitoring of the photometric variability of earthshine revealed changes of up to 23 % per hour in the brightness of Earth's scattered light at around 600 nm, due to the removal of specular reflection from the view of the Moon. This variability is accompanied by reddening of the spectrum, and results from a change in surface properties across the continental boundary between the Indian Ocean and Africa's east coast. Our results based on earthshine monitoring indicate that specular reflection should provide a useful tool in determining the presence of liquid water on extrasolar planets via photometric observations.Comment: To appear in Astrobiology 9(3). 17 pages, 3 figures, 1 tabl

Efficient Parallel Translating Embedding For Knowledge Graphs

Knowledge graph embedding aims to embed entities and relations of knowledge graphs into low-dimensional vector spaces. Translating embedding methods regard relations as the translation from head entities to tail entities, which achieve the state-of-the-art results among knowledge graph embedding methods. However, a major limitation of these methods is the time consuming training process, which may take several days or even weeks for large knowledge graphs, and result in great difficulty in practical applications. In this paper, we propose an efficient parallel framework for translating embedding methods, called ParTrans-X, which enables the methods to be paralleled without locks by utilizing the distinguished structures of knowledge graphs. Experiments on two datasets with three typical translating embedding methods, i.e., TransE [3], TransH [17], and a more efficient variant TransE- AdaGrad [10] validate that ParTrans-X can speed up the training process by more than an order of magnitude.Comment: WI 2017: 460-46

Rapid continuous chemical analysis of meat chicken shed emissions by SIFT–MS

Assessing and addressing odour impacts from poultry production is extremely difficult and subjective because the odorants involved and their dynamics over time and space are poorly understood. This knowledge gap is due, in part, to the lack of suitable analytical tools for measuring and monitoring odorants in the field. The emergence of Selected Ion Flow Tube – Mass Spectrometry (SIFT–MS) and similar instruments is changing that. These tools can rapidly quantify targeted odorants in ambient air in real time, even at very low concentrations. Such data is essential for developing better odour abatement strategies, assessment methods and odour dispersion models. This project trialled a SIFT–MS to determine its suitability for assessing the odorants in meat chicken shed emissions over time and space. This report details evaluations in New Zealand and Australia to determine the potential of SIFT–MS as a tool for the chicken meat industry, including odour measurement (as a proxy for dynamic olfactometry). The report is specifically targeted at those funding and conducting poultry odour research. It will be of interest to those involved with environmental odour monitoring and assessment in general. The high upfront cost of SIFT–MS will lead to potential users wanting compelling evidence that SIFT–MS will meet their needs before they invest in one

Manipulating biphotonic qutrits

Quantum information carriers with higher dimension than the canonical qubit offer significant advantages. However, manipulating such systems is extremely difficult. We show how measurement induced non-linearities can be employed to dramatically extend the range of possible transforms on biphotonic qutrits; the three level quantum systems formed by the polarisation of two photons in the same spatio-temporal mode. We fully characterise the biphoton-photon entanglement that underpins our technique, thereby realising the first instance of qubit-qutrit entanglement. We discuss an extension of our technique to generate qutrit-qutrit entanglement and to manipulate any bosonic encoding of quantum information.Comment: 4 pages, 4 figure

Structure and giant magnetoresistance of granular Co-Cu nanolayers prepared by cross-beam PLD

A series of Co_xCu_{100-x} (x = 0, 40...75, 100) layers with thicknesses in-between 13 nm and 55 nm were prepared on silicon substrates using cross-beam pulsed laser deposition. Wide-angle X-ray diffraction (WAXRD), transmission electron microscopy (TEM) and electrical transport measurements revealed a structure consisting of decomposed cobalt and copper grains with grain sizes of about 10 nm. The influence of cobalt content and layer thickness on the grain size is discussed. Electron diffraction (ED) indicates the presence of an intermetallic Co-Cu phase of Cu3Au structure-type. Thermal treatment at temperatures between 525 K and 750 K results in the progressive decomposition of Co and Cu, with an increase of the grain sizes up to about 100 nm. This is tunable by controlling the temperature and duration of the anneal, and is directly observable in WAXRD patterns and TEM images. A careful analysis of grain size and the coherence length of the radiation used allows for an accurate interpretation of the X-ray diffraction patterns, by taking into account coherent and non-coherent scattering. The alloy films show a giant magnetoresistance of 1...2.3 % with the maximum obtained after annealing at around 725 K.Comment: 9 pages, 9 figure