An analysis of the through-bond interaction using the localized molecular orbitals—IV: Long-range proton hyperfine coupling in exo- and endo-hydrogens in bicyclo[2.1.1]hex-5-yl radical

The INDO calculations were performed on bicyclo[2.1.1]hex-5-yl radical. From these calculations, it was confirmed that the hyperfine coupling constants depend largely on the geometry of the α hydrogen. The localized MO's were obtained from the canonical MO's calculated by using the INDO method. With the use of the localized MO's thus obtained, the variation in the hyperfine coupling constants at the 6exo- and 6endo-protons in this radical was explained in terms of the through-bond and/or the through-space interactions according to the procedure which we proposed previously. That is by the procedure we can selectively pick up a particular interaction between the specified localized MO's. The hyperfine coupling constant in this radical can be expressed by the summation of several interaction terms. The difference in the hyperfine spin coupling constants of the H_6exo and H_6endo in the radical now concerned has been attempted to explain using MO coefficients of the occupied orbitals.     

Numerical methods for conjunctive two‐dimensional surface and three‐dimensional sub‐surface flows

Sophisticated catchment runoff problems necessitate conjunctive modeling of overland flow and sub‐surface flow. In this paper, finite difference numerical methods are studied for simulation of catchment runoff of two‐dimensional surface flow interacting with three‐dimensional unsaturated and saturated sub‐surface flows. The equations representing the flows are mathematically classified as a type of heat diffusion equation. Therefore, two‐ and three‐dimensional numerical methods for heat diffusion equations were investigated for applications to the surface and sub‐surface flow sub‐models in terms of accuracy, stability, and calculation time. The methods are the purely explicit method, Saul'yev's methods, the alternating direction explicit (ADE) methods, and the alternating direction implicit (ADI) methods. The methods are first examined on surface and sub‐surface flows separately; subsequently, 12 selected combinations of methods were investigated for modeling the conjunctive flows. Saul'yev's downstream (S‐d) method was found to be the preferred method for two‐dimensional surface flow modeling, whereas the ADE method of Barakat and Clark is a less accurate, stable alternative. For the three‐dimensional sub‐surface flow model, the ADE method of Larkin (ADE‐L) and Brian's ADI method are unconditionally stable and more accurate than the other methods. The calculations of the conjunctive models utilizing the S‐d surface flow sub‐model give excellent results and confirm the expectation that the errors of the surface and sub‐surface sub‐models interact. The surface sub‐model dominates the accuracy and stability of the conjunctive model, whereas the sub‐surface sub‐model dominates the calculation time, suggesting the desirability of using a smaller time increment for the surface sub‐model. Copyright © 2000 John Wiley & Sons, Ltd.     

The role of the dynamic pressure in stationary heat conduction of a rarefied polyatomic gas

The effect of the dynamic pressure (non-equilibrium pressure) on stationary heat conduction in a rarefied polyatomic gas at rest is elucidated by the theory of extended thermodynamics. It is shown that this effect is observable in a non-polytropic gas. Numerical studies are presented for a para-hydrogen gas as a typical example.     

Immobilization of microbial cells by radiation-induced polymerization of glass-forming monomers and immobilization ofStreptomyces phaeochromogenes cells by polymerization of various hydrophobic monomers

The immobilization ofStreptomyces phaeochromogenes cells was studied by the radiation-induced polymerization of various hydrophobic glass-forming monomers at low temperatures. The glucose isomerase activity of cells immobilized in hydrophobic polymers showed no decrease in activity with repeated use (batch enzyme reaction). Activity increased with increasing monomer concentration in contrast to results with the immobilized enzyme. The hydrophobic polymer composite was microspheric in form. The particle diameter of the composite increased with the increasing monomer concentration.K _m values of the immobilized cells were close to that of intact cells. It was deduced that the cells were trapped on the surface part of the hydrophobic polymer ready to react with the substrate, and not within the matrix where diffusion would play an important role in reaction rates.     

Molecular vibrations and force fields of alkyl sulfides: Part XV. C-S stretching vibrations of aliphatic alkyl sulfides

The C-S stretching vibrations of 28 aliphatic sulfides including one thiol are summarized, and all of the C-S stretching bands are classified into several groups. An extraordinarily low frequency associated with the ethyl group is discussed briefly.     

Insights into sticking of radicals on surfaces for smart plasma nano-processing

In reactive plasma processing, species produced in the plasma reach the surface of a substrate and cause etching, deposition and surface modification through surface reactions. These reactions are characterized by the densities and energies of species incident on the surfaces. In order to realize nano-scale plasma processing, important species for plasma processing have been identified and characterized, and their behavior, not only in the gas phase, but also on the surface, have been clarified and controlled. One of the most critical parameters for insights into surface reaction kinetics of radicals is sticking and surface loss probability. On the basis of radical densities measured by various methods, the sticking and surface reaction loss probabilities have been compiled, and they enable the quantitative understanding of the kinetics of radicals on the surface in the plasma. In this article, the sticking and surface reaction loss probabilities measured thus far are reviewed focusing on fluorocarbon gas, silane gas and methane gas based plasma processes. The establishment of a smart plasma process and the development of an autonomous production device with control of radicals on the basis of insights into the surface reactions for nano-scale plasma processing are presented.     

Application of MCD spectroscopy and TD-DFT to nonplanar core-modified tetrabenzoporphyrins: effect of reduced symmetry on nonplanar porphyrinoids

The optical spectra of a series of core-modified tetrabenzoporphyrins were analyzed to determine the effects of core modification, ligand folding, and partial benzo substitution at the ligand periphery on the electronic structure by using magnetic circular dichroism (MCD) and NMR spectroscopy, X-ray crystallography, cyclic and differential pulse voltammetry, and TD-DFT calculations. Planar 21-carba-, 21-thia-, 21,23-dithia-, and 21-oxa-23-thiatetrabenzo[b,g,l,q]porphyrins reported previously were studied together with the previously unreported 21-oxa- and 21-carba-23-thiatetrabenzo[b,g,l,q]porphyrins. The optical properties of these compounds are compared to those of tetrabenzo[b,g,l,q]-, 5,10,15,20-tetraphenyl-, 5,10,15,20-tetraphenyltetrabenzo[b,g,l,q]-21-thia-, 5,10,15,20-tetraphenyltetrabenzodithia-, 5,10,15,20-tetraphenyldibenzo[g,q]-21,23-dithia-, 5,10,15,20-tetraphenyldibenzo[b,l]-21,23-dithia-, 5,10,15,20-tetraphenyltribenzo[g,q,l]-21-thia-, and 5,10,15,20-tetraphenylbenzo[b]-21-thiaporphyrins. Michl's perimeter model and Gouterman's four-orbital model are used to conceptualize the results and to account for red shifts commonly observed in the spectral bands of nonplanar porphyrinoids.     

Preparation and properties of aromatic polyamides and copolyamides from phenylindanedicarboxylic acid and aromatic diamines

Aromatic polyamides (aramids) having inherent viscosities of 0.5–1.10 dL/g were prepared by the direct polycondensation of 1,1,3-trimethyl-3-(4-carboxyphenyl)indane-5-carboxylic acid with various aromatic diamines using triphenyl phosphite and pyridine as the condensing agents. Copolyamides were also prepared by a similar procedure from a mixture of the phenylindane diacid, terephthalic acid, and p-phenylenediamine. Almost all of the aramids were soluble in a variety of solvents such as N-methyl-2-pyrrolidone, pyridine, and m-cresol, and afforded transparent and tough films by the solution casting. These aramids and copolyamides had glass transition temperatures in the range of 290–355°C, and started to lose weight at 340°C in air.