The 3C/3D line ratio in Ni XIX: New Ab Initio theory and experimental results

We report a fully relativistic close-coupling calculation of the electron impact excitation of Ni xix to derive the 3C/3D line intensity ratio, with an uncertainty of 5%. Convergence of the calculation with respect to both channel coupling effects and the many interacting Rydberg series of resonances has been achieved. New measurements in an electron beam ion trap agree with our calculation. We show that the 3C/3D x-ray line ratio depends sensitively on both electron energy and beamwidth in an optically thin plasma. Accounting for this dependence improves the accuracy of the Ni abundance determination in astrophysical sources.     

Thermodynamic calculations in the system CH4-H2O and methane hydrate phase equilibria

Using the Gibbs function of reaction, equilibrium pressure, temperature conditions for the formation of methane clathrate hydrate have been calculated from the thermodynamic properties of phases in the system CH4-H2O. The thermodynamic model accurately reproduces the published phase-equilibria data to within +/-2 K of the observed equilibrium boundaries in the range 0.08-117 MPa and 190-307 K. The model also provides an estimate of the third-law entropy of methane hydrate at 273.15 K, 0.1 MPa of 56.2 J mol(-1) K(-1) for 1/nCH4.H2O, where n is the hydrate number. Agreement between the calculated and published phase-equilibria data is optimized when the hydrate composition is fixed and independent of the pressure and temperature for the conditions modeled.     

Kinetics and mechanism of the cyclization of omega-(p-nitrophenyl)-hydantoic acid amides: steric hindrance to proton transfer causes a 10(4)-fold change in rate

The pH-rate profiles for the cyclization of primary 2,3-dimethyl and 2,2,3-trimethyl-hydantoinamides (2-UAm and 3-UAm respectively) differ strikingly from those for the cyclizations of the corresponding N-methylated amides 2-MUAm and 3-MUAm; which are dominated by the water reaction, spanning some 6 pH units. For the cyclization of UAm the plateau extends over no more than two pH units. The difference is due to the slower base-catalyzed cyclization of the N-methylamides. The solvent kinetic isotope effect for this hydroxide-catalyzed reaction is close to 1.2, consistent with a slow protonation by water of the amino-group of the negatively charged tetrahedral intermediate. General base catalysis was observed with bases of pKBH up to 8. The Br?nsted beta are compatible with a hydrogen bonding mechanism for the GBC. In the gem-dimethyl compounds 3 the leaving group is flanked by substituents on both sides. The N-methyl group in 3-MUAm hinders frontal access of the proton, causing a 14000 fold decrease in rate. This is only 3800 fold in the compound with one methyl group at position 2.     

Microwave and photoelectron study of cis- and trans-isocyanato ethene,CH2CHNCO (vynyl isocyanate)

The microwave and photoelectron spectra of isocyanato ethene CH₂CHNCO have been studied. The microwave results indicate that the species is planar and possesses both a cis and a trans form. The appearance of dense and complicated vibrational satellite lines indicates that the molecule is quite flexible, a general property of molecules containing the isocyanate group. The rotational constants are:

$\text{cis: A}{}_0\text{= 20 146.8, B}{}_0\text{= 3107.267, C}{}_0\text{= 2689.513}\text{MHz}\text{; trans: A}{}_0\text{= 62 584.051, B}{}_0\text{= 2437.730, C}{}_0\text{= 2346.507}\text{MHz}$

These constants are shown to be consistent with structures in which $\text{r(}\text{CN}\text{) = 1.382 ± 0.005}\text{A}\text{?}$, ∠(CCN) = 122 ± 1° (for both conformers), and ∠(CNC) = 142.4 ± 0.5° (cis) and 138.4 ± 1.5° (trans). The dipole moments are μ(cis) = 2.120 ± 0.015 and μ(trans) = 2.207 ± 0.007 D. Several distinct peaks are observed in the photoelectron spectrum; however, the structure is not resolved into features belonging to the different isomers. The first ionization potential lies at 9.80 ± 0.1 eV. The spectrum has been assigned with the aid of theoretical calculations.     

On the recognition of structural features: Some general problems illustrated by hamiltonian paths in polyhexes

Human and machine recognition skills are discussed, though not comprehensively reviewed, and some of the difficulties are illustrated by algorithms written to search for Hamiltonian paths in polyhexes. The most successful strategy for this is based upon the branching graph, a recently introduced graph-theoretical device which can aid the recognition of edges that arenot part of a Hamiltonian path. Another, more widely applicable approach that is interesting, although in this preliminary form only a little better than random methods, uses the metaphor of biological evolution, and tries to breed and grow paths subjected to natural selection.     

Zeta potential of microfluidic substrates: 2. Data for polymers

Zeta potential data are reviewed for a variety of polymeric microfluidic substrate materials. Many of these materials currently used for microchip fabrication have only recently been employed for generation of electroosmotic flow. Despite their recent history, polymeric microfluidic substrates are currently used extensively for microchip separations and other techniques, and understanding of the surface zeta potential is crucial for experimental design. This paper proposes the use of pC (the negative logarithm of the counterion concentration) as a useful normalization for the zeta potential on polymer substrates in contact with indifferent univalent counterions. Normalizing zeta by pC facilitates comparison of results from many investigators. The sparseness of available data for polymeric substrates prevents complete and rigorous justification for this normalization; however, it is consistent with double layer and adsorption theory. For buffers with indifferent univalent cations, normalization with the logarithm of the counterion concentration in general collapses data onto a single zeta/pC vs. pH curve, and (with the exception of PMMA) the repeatability of the data is quite encouraging. Normalization techniques should allow improved ability to predict zeta potential performance on microfluidic substrates and compare results observed with different parameters.     

The origins and diffusion of operational research in the UK

This paper analyses the origins and diffusion of operational research in the UK from the end of the Second World War to 1970. After acknowledging ORs military origins, the paper discusses the process of diffusion into the civilian sector. In this context, the critical role fulfilled by OR groups in the coal and iron and steel industries is highlighted, as well as the individual advocacy of key individuals such as Sir Charles Goodeve. The paper also comments on the development of OR in the UK corporate sector by presenting a number of representative case studies. It concludes with an examination of the factors which encouraged the diffusion of OR into civil government after 1965, contrasting this development with the muted response of Whitehall departments in the late 1940s.     

An extension of Willard’s Finite Basis Theorem: Congruence meet-semidistributive varieties of finite critical depth

Ross Willard proved that every congruence meet-semidistributive variety of algebras that has a finite residual bound and a finite signature can be axiomatized by some finite set of equations. We offer here a simplification of Willards proof, avoiding its use of Ramseys Theorem. This simplification also extends Willards theorem by replacing the finite residual bound with a weaker condition.In Celebration of the Sixtieth Birthday of Ralph N. McKenzieReceived February 26, 2004; accepted in final form August 2, 2004.