4,947 research outputs found
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
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
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
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
Integrated Photonic Sensing
Loss is a critical roadblock to achieving photonic quantum-enhanced
technologies. We explore a modular platform for implementing integrated
photonics experiments and consider the effects of loss at different stages of
these experiments, including state preparation, manipulation and measurement.
We frame our discussion mainly in the context of quantum sensing and focus
particularly on the use of loss-tolerant Holland-Burnett states for optical
phase estimation. In particular, we discuss spontaneous four-wave mixing in
standard birefringent fibre as a source of pure, heralded single photons and
present methods of optimising such sources. We also outline a route to
programmable circuits which allow the control of photonic interactions even in
the presence of fabrication imperfections and describe a ratiometric
characterisation method for beam splitters which allows the characterisation of
complex circuits without the need for full process tomography. Finally, we
present a framework for performing state tomography on heralded states using
lossy measurement devices. This is motivated by a calculation of the effects of
fabrication imperfections on precision measurement using Holland-Burnett
states.Comment: 19 pages, 7 figure
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