Thermochemical Bond Energy Studies Of Various Transitional-Metal Bis-Beta-Diketone Compounds And Their Inner Orbital Splittings By Bomb Calorimetry

The thermochemical technique of static bomb calorimetry was used to determine the heats of combustion for some twenty chelated metal complexes. Studied were the first row transitional metals (Mn+2 through Zn+2) bis-beta diketone complexes of acetylacetome and their related ligands and the acetyl ·· acetonates of Pd+2, Pt+2, Be+2, Ce+3, Tl+1, and Zr+4. Solid purified samples of from 1 to 2 grams were combusted in a pressurized oxygen atmosphere to the reaction products H20 (1), C02 (g) and metallic oxides. The temperature change for the exothermic reactions was standardized with benzoic acid to give the enthalpy of combustion in kcal/mol. The majority of the data for the combustion reaction are in error of 1/2 of 1% or less. The heat of combustion data were used in a suitable Born-Haber thermochemical cycle to determine the average bond energy for the metal to ligand bond. The bond cleavage can be expressed in either terms of an ionic or a coordinated bond break, known as hererelytic and hemolytic cleavage respectively, depending on the choice of the thermochemical cycle. The hemolytic bond energy cycle is suitable for the calculation of the average bond energy. For the acetylacetonate complexes of Mn+2 through Zn+2, the heterolytic thermochemical cycle was used. Thus, the heterolytic bond energies obtained are shown to vary with the electronic configuration of the central metal. These variations are predicted by crystal field theory. A plot of the total heterolytic bond energies versus atomic number will, with a knowledge of the spin state of the metal ions, give an estimation of 10Dq values for the complexes. For the complexes investigated, 10Dq values are in good agreement with those obtained by the more accurate spectroscopic method. A second series of compounds investigated consisted of various ligands similar to acetylacetone. The copper and nickel complexes were synthesized with benzoylacetone, dibenzoylmethane and salicylaldehyde. lt was expected that a pattern of decreasing bond energy could he found by the systematic replacement of first one and then the other methyl groups by a phenyl group (the substituent effect). No clear pattern emerged. This investigation provides the framework for future investigations to give a more quantitative understanding of metal chelated complexes and their metal-ligand bond energies

TESTING DECEPTION WITH A COMMERCIAL TOOL SIMULATING CYBERSPACE

Deception methods have been applied to the traditional domains of war (air, land, sea, and space). In the newest domain of cyber, deception can be studied to see how it can be best used. Cyberspace operations are an essential warfighting domain within the Department of Defense (DOD). Many training exercises and courses have been developed to aid leadership with planning and to execute cyberspace effects that support operations. However, only a few simulations train cyber operators about how to respond to cyberspace threats. This work tested a commercial product from Soar Technologies (Soar Tech) that simulates conflict in cyberspace. The Cyberspace Course of Action Tool (CCAT) is a decision-support tool that evaluates defensive deception in a wargame simulating a local-area network being attacked. Results showed that defensive deception methods of decoys and bait could be effective in cyberspace. This could help military cyber defenses since their digital infrastructure is threatened daily with cyberattacks.Marine Forces Cyberspace CommandChief Petty Officer, United States NavyChief Petty Officer, United States NavyApproved for public release. Distribution is unlimited

Further geometric restrictions on jordan structure in matrix factorization

It is known that a nonsingular, nonscalar, n-by-n complex matrix A may be factored as A = BC, in which the spectra of B and C are arbitrary, subject to det(A) = det(B)det(C). It has been shown that when two matrices have eigenvalues of high geometric multiplicity, this restricts the possible Jordan structure of the third. We demonstrate a previously unknown restriction on the Jordan structures of B and C. Furthermore, we show that this generalized geometric multiplicity restriction implies the already known geometric multiplicity restriction, show that the new more restrictive condition is not sufficient in general but is sufficient in a situation that we identify.Fundação para a Ciência e a Tecnologia (FCT), National Science Foundation Grant DMS-03-53510, US

Rex E. Lee Conference on the Office of the Solicitor General of the United States: Panel for Former Solicitors General

I agree entirely that the chain of command is clear and that the Framers managed to make it all the way through all the articles of the Constitution without even conceiving of a solicitor general, let alone bothering to mention an attorney general. It is important nonetheless to distinguish between those things the solicitor general does pursuant to the longstanding notice-and-comment regulation, and the other things a solicitor general may do pursuant to his (and, someday, her!) statutory obligation to be of general assistance to the attorney general

Arbitrariness of Jordan structure in factorization : the geometric multiplicity restriction and the 3 X 3 case

For the problem of which Jordan forms are possible for n × n complex matrices A, B and C, when A = BC, geometric multiplicity restrictions are given for the eigenvalues of the three matrices. Together with the obvious determinantal condition on the eigenvalues, these necessary conditions are shown to be sufficient for the problem when n < 4, but not for n ≥ 4. Some basic observations about the problem are given in the process.National Science Foundation, USA and FCT, Portugal