Reaction paths of some open-shell reactive intermediates

The intermolecular interaction energy for reacting systems in singlet, triplet and doublet states was partitioned by the perturbation expansion method into the chemically meaningful five interaction terms: the Coulomb, exchange-repulsion, induction, dispersion, and charge-transfer energies. In the local ZDO approximation, these energy terms were evaluated for the dimerization of methylenes (^1,3CH₂), the additions of carbenes (^1,3CH₂ and^1,3CF₂) as well as amino radicals (²NH₂ and²NF₂) toward ethylene, and the hydrogen abstractions by methylenes (^1,3CH₂), nitrene (³NH), and hydroxyl radical (²OH) from methane. It has been found that the reaction path is much influenced by the spinmultiplicity, and that the charge-transfer and exchange-repulsion terms play a dominant role in determining the course of reactions.     

Method of kinetic analysis of photodegradation: nifedipine in solutions

A rate equation for photodegradation was derived from Lambert-Beer's law and Grotthus-Draper's law: -dc/dt=k1(1-exp(-(k2c+k3(c0-c))))k2c/(k2c+k3(c0-c)) where c is the concentration of reactant, c0 is the initial concentration of reactant, t is time, k1 is the rate constant, and k2 and k3 are the absorption coefficient of reactant and its photodegradation product, respectively. In a case where the photodegradation products have no photoabsorption, k3 assumes the value of zero in the above general equation. In a case where the photodegradation products have the same spectrum and molar absorptivity as that of the reactant, k3 assumes the value of k2, and hence the photodegradation is not a first-order reaction; however, the equation itself gives the pseudo-first-order reaction rate equation. In a case where the concentration of reactant is high enough, the equation approaches a zero-order reaction rate equation. The photodegradation rate of nifedipine in solutions under a germicidal lamp, near an ultraviolet fluorescent lamp and a fluorescent lamp was analyzed using the above equation. The photodegradation rate was directly proportional to the amount of light absorbed, and fitted well with the equation. The above theoretical equation was substantiated by the photodegradation of nifedipine, and hence is expected to apply to other photosensitive drugs.     

The molecular structure and chemical reactivities of the condensation products of o-substituted benzylidenacetylacetone with hydrazine dihydrochloride

Reaction of o-nitrobenzylideneacetylacetone ( 1a ) with hydrazine dihydrochloride in methanol gave 4-(α-methoxy-o-nitrobenzyl)-3,5-dimethylpyrazole hydrochloride ( 4a ), whose structure was unambigously confirmed by an X-ray crystallographic analysis, via 4-(o-nitrobenzylidene)-3,5-dimethylisopyrazole ( 2a ). Compound 2a was synthesized by condensation of 1a with hydrazine dihydrochloride in acetonitrile. Analogously the corresponding o-chloro derivatives ( 2b, 4b ) were obtained. These were converted to N-methyl ( 6b ) and N-acetyl ( 7a,b ) derivatives and the behaviors on bromination and pyrolysis were investigated.     

Ab initio calculations on the clustering energies and stable structures of H(M)+ + M → H(M)2+ (M = CO and N2)

The clustering energies of the reactions, H(M)⁺+ M → H(M)⁺₂ (M = CO and N₂), were calculated by ab initio single configuration LCAO SCF MO and SCEP methods. The calculated energies are in good agreement with the experimental enthalpies.     

Gap states at organic-metal interfaces: A combined spectroscopic and theoretical study

A systematic understanding and controlling of gap states formed at the organic-metal interfaces is a key factor for fabricating functional organic-metal systems, as in case of heterojunctions in semiconductor devices. We report here the characterization of gap states near the Fermi level of metal substrate by metastable atom electron spectroscopy and first-principles density functional calculations. The gap states in organic-metal systems are classified into two types, i.e., chemisorption-induced gap states (CIGSs) and complex-based gap states (CBGSs). CIGSs can be further classified whether the metal wave function tails a short distance into the chemisorbed species with the exponential decay (damping type) or is exposed sufficiently to the chemisorbed species by mixing with the organic orbitals (propagating type). CIGSs observed in alkanethiolate and C₆₀ on Pt(1 1 1) are their typical examples, respectively. As a consequence, alkanethiolate serves as a poor mediator of metal wave function, whereas C₆₀ acts as a good mediator, which is responsible for tunneling mechanism and eventually electric conductivity in the relevant metal-organic-metal junctions. CBGSs are identified in bathocuproine films deposited on K-covered Au, where the K atoms migrate into the film to form an organic-metal complex. The CBGSs are distributed over the multilayer film, in contrast to the case of CIGS. With increasing film thickness, the CBGSs exhibit incommensurate energy shifts with the valence band top of the film, indicating that the Schottky-Mott model breaks down as evaluating charge transport in organic-metal systems.     

Waveform control for magnetic testers using a quasi-Newton method

A nonlinear iterative learning algorithm is proposed to make a voltage waveform in the secondary coil sinusoidal in this paper. The algorithm employs a globally convergent Jacobian-free quasi-Newton type solver that has a BFGS-like structure. This method functions well, and it is demonstrated using typical soft magnetic materials.     

Influence of Sn on the hydration of tricalcium aluminate, Ca3Al2O6

Tricalcium aluminate (Ca₃Al₂O₆, C₃A) containing 0?C5% of Sn was synthesized by solid-state method, and the products were characterized by XRD technique. Differential thermo-analytical technique (DTA) along with X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) were applied to study the hydration behaviour of different C₃A samples with and without the presence of gypsum. Results indicate that C₃A can accommodate small amount of Sn in its structure and remaining amount forms SnO₂. Hydration studies of the synthesized C₃A shows that the additions of 0.5 and 1% Sn increase and 2% Sn decrease the reactivity of C₃A at the initial period (<3?h) of hydration. Increasing additions of Sn also increase the amounts of amorphous phases and hexagonal calcium aluminate hydrates in the cement pastes. The stabilities of these hydration products also increase with increasing content of Sn in C₃A at the experimental conditions. The presence of Sn significantly changes the hydration of C₃A and gypsum solid mixture at the initial period of hydration by enhancing the formation of more amounts of AFt and AFm phases. However, at the later stage of hydration (on or after 3?days), the hydration products in C₃A and gypsum pastes with and without the presence of Sn are almost similar.