The present paper is a review of the current studies of quantum beats in recombination of spin-correlated radical pairs in solutions as well as of future applications of quantum beats technique for studying these pairs. Examples are given of the use of this method for determining the hfi constants and relaxation times of short-lived radical ions, for finding the rate constants of the reactions of alkane radical cations and for estimating a fraction of singlet-correlated pairs in the pairs in the tracks of ionizing particles. The potentialities of this method, its advantages and limitations are discussed.

The present paper is a review of the current studies of quantum beats in recombination of spin-correlated radical pairs in solutions as well as of future applications of quantum beats technique for studying these pairs. Examples are given of the use of this method for determining the hfi constants and relaxation times of short-lived radical ions, for finding the rate constants of the reactions of alkane radical cations and for estimating a fraction of singlet-correlated pairs in the pairs in the tracks of ionizing particles. The potentialities of this method, its advantages and limitations are discussed.

Stability characteristics of hyperbolic reaction-diffusion equations with a reversible Brusselator model are investigated as an extension of the previous work. Intensive stability analysis is performed for three important parameters, Nrd, β and Dx, where Nrd is the reaction-diffusion number which is a measure of hyperbolicity, β is a measure of reversibility of autocatalytic reaction and Dx is a diffusion coefficient of intermediate X. Especially, the dependence on Nrd of stability exhibits some interesting features, such as hyperbolicity in the small Nrd region and parabolicity in the large Nrd region. The hyperbolic reaction-diffusion equations are solved numerically by a spectral method which is modified and adjusted to hyperbolic partial differential equations. The numerical method gives good accuracy and efficiency even in a stiff region in the case of small Nrd, and it can be extended to a two-dimensional system. Four types of solution, spatially homogeneous, spatially oscillatory, spatio-temporally oscillatory and chaotic can be obtained. Entropy productions for reaction are also calculated to get some crucial information related to the bifurcation of the system. At the bifurcation point, entropy production changes discontinuously and it shows that different structures of the system have different modes in the dissipative process required to maintain the structure of the system. But it appears that magnitude of entropy production in each structure give no important information related for states of system itself.

We have performed a quantum-chemical investigation on the conformations and electronic properties of a variety of methoxy-substituted poly(p-phenylenevinylenes) (PPVs) to elucidate the effects of alkoxy substitution. Geometrical parameters for the polymers were fully optimized through Austin Model I (AM I) semi-empirical Hartree-Fock (HF) band calculations. Electronic properties of the polymers were obtained by applying the AM I optimized structures to the modified extended Huckel method. To confirm validity of the AM I conformational results, we also carried out ab initio HF calculations with the 6-31G (d) basis set for a variety of methoxy-substituted divinylbenzenes. It is found that the potential energy surfaces of alkoxy-substituted PPVs are quite shallow around the planar conformations, suggesting that the prepared films possess a variety of conformations with different torsion angle in the solid state, depending on the synthetic conditions. When two alkoxy groups are concurrently substituted at the adjacent sites in the phenylene ring, these groups are subject to rotating around the C(sp2)-O bonds by 70-80° to avoid the strong steric repulsion between them. Consequently, the overlap between the π-type p orbital of oxygen and the π molecular orbitals of the polymer decreases. This leads to a wide gap and a high oxidation potential for tetramethoxy-substituted PPV, compared to those of dialkoxy-substituted PPV.

Various metal oxides such as Fe2O3, FeO, TiO2, MnO2, MoO3, WO3 and ZnO have been used as a catalyst for Gif-KRICT type cyclohexane oxidation. In this reaction, the conversion of cyclohexane to cyclohexanone and cyclohexanol and the selectivity ratio of cyclohexanone to cyclohexanol were greatly affected by the acidity of metal oxides. When metal oxide has more acidic property, the reactivity on oxidation is increased and the formation of cyclohexanone is more favored. From this result, we proposed a new mechanism for the biomimetic Gif-KRICT oxidation system.

We synthesize the spinel lithium manganese oxides of the LiCrxMn2-xO4 from x=0.00 to 0.70 at 750 ℃ in air and identifiy them with X-ray crystallography.

Based on the study of hydrolysis behaviour of U(Ⅵ) ion and major fission product metal ions such as Cs(Ⅰ), Ce(Ⅲ), Nd(Ⅲ), Mo(Ⅵ), Ru(Ⅱ), and ZR(Ⅳ) in the titration media, the performance of noncomplexing-alkalimetric titration method for the determination of free acid in the presence of these metal ions was investigated and its results were compared to those from the completing methods. The free acidities could be determined as low as 0.05 meq in uranium solutions in which the molar ratio of U(Ⅵ)/H+ was less than 5, when the end-point of titration was estimated by Gran plot. The biases in the determinations were less than 1% and about +3% respectively for 0.4 meq and 0.05 meq of free acid at the U(Vl)/H+ molar ratio of up to 5. Applicability of this method to the determination of free acid in spent fuel solutions was confirmed by the analysis of nitric acid content in simulated spent fuel solutions and in a real spent fuel solution.

Novel mononuclear group 13 metal complexes with the formula (R2M){NC5H4C(CH3)NNC(S)NH(C6H5)} (M=Al, R=iC4H9 (1); M=Ga, R=iC4H9 (2); M=Al, R=CH2SiMe3 (3); M=Ga, R=CH2SiMe3 (4)) result when 2-acetyl pyridine 4-phenyl-thiosemicarbazone ligand is mixed with trialkyl aluminum or trialkylgallium. These compounds 1-4 are characterized by microanalysis, NMR (1H, 13C) spectroscopy, mass spectra, and singlecrystal X-ray diffraction. X-ray single-crystal diffraction analysis reveals that 1 is mononuclear metal compound with coordination number of 5 and N, N, S-coordination mode.

The silica-pillared H-kenyaites were prepared by interlarmellar base-catalyzed reaction of tetraethylorthosilicate [TEOS, Si(OC2H5)4] intercalated into the interlayer of H-kenyaite. The intercalation of TEOS was conducted by the octylamine preswelling process, resulting in a dramatic increase in gallery height to 24.7 Å. The interlamellar hydrolysis of octylamine-TEOS/H-kenyaite paste were conducted between 10 min and 40 min in 0.00%, 0.05% and 0.10% NH3-water solution respectively, and resulting in siloxane-pillared H-kenyajte with gallery height of 28.2-31.8 Å. The calcination of samples at 538 ℃ resulted in silica-pillared H-kenyaites with a large surface areas between 411 m2/g and 885 m2/g, depending on the aging time and NH3 concentration. Samples with optimum specific surface areas and well ordered-basal spacing were obtained by reaction between 10 min and 40 min in pure water and 0.05% NH3-water solution. Mesoporous samples with narrow pore size distribution were also prepared by reaction for 10-40 min in 0.05% NH3 solution. Rapid interlamellar reaction of TEOS in pure water showed that intercalated octylamine itself could act as a base catalyst during interlamellar polycondensation of TEOS.

The effects of zeolites on the intramolecular [2+2] photocycloadditions of 3-(3-butenyl)cyclohex-2-enone (la) and 3-(2-propenoxy)cyclohex-2-enone (lb) were investigated. When la adsorbed in cation-exchanged zeolites X and Y was irradiated through a Pyrex filter, the products from the 1,6-ring closure biradical increased compared to the results from the photoreaction in homogeneous solutions. In the intramolecular 1,5-ring closure photocycloaddition of la and lb, the products from the cis-fused intermediates increased in zeolites X and Y. The regiochemical and stereochemical outcomes of the photocycloadditions in the zeolites were interpreted by the binding of the guest molecules with the cations in the supercages.

The emission and excitation spectra of [Cr(NH3)5(imH)](ClO4)3·H2O (imH=imidazole) taken at 77 K are reported. The 298 K visible and far-infrared spectra are also measured. The vibrational intervals of the electronic ground state are extracted from the far-infrared and emission spectra. The ten electronic bands due to spin-allowed and spin-forbidden transitions are assigned. Using the observed transitions, a ligand field analysis has been performed to determine the bonding properties of coordinated imidazole in the title chromium(Ⅲ) complex. It is confirmed that nitrogen atom of the imidazole ligand has a medium it-acceptor property toward chromium(Ⅲ) ion. The zero-phonon line in the excitation spectrum splits into two components by 181 cm-1, and the large 2Eg splitting can be reproduced by the ligand field theory.

Me3NO selectively abstracts the proton from [IrH(CO)(PPh3)2L(A)]0.1+,2+ (1) (A: -CCPh, Cl-, CH3CN and L: CH3CN, Cl-, C1O4-) to give the trans-elimination products, Ir(CO)(PPh3)2(A) (2). The reductive elimination of H+ and Cl- from Ir(H)Cl2(CO)(PPh3)2 (lb) to give IrCl(CO)(PPh3)2 (2b) is first order in both lb and Me3NO. The rate law d[2b]/dt=kobs[lb]=k2[lb][Me3NO] suggests the formation of (PPh3)2(CI)2(CO)Ir-H-ON+Me3 in the rate determining step (k2) followed by the fast dissociation of both H-ON+Me3 and the trans ligand Cl-. The rate significantly varies with the cis liaand A and the trans ligand L and is slower with both A and L being Cl- than other ligands. Me3NO selectively eliminates CO from [Ir(H)2(CO)(PPh3)2L]0,+ (3) (L=CH3CN, C1O4-) to produce [Ir(H)2(PPh3)2L'(CH3CN)]+ (4) (L'=CH3CN, PPh3) in the presence of L. Me3NO does not readily remove either H+ or CO from cis, trans- and trans, trans-lr(H)(-CCPh)2(CO)(PPh3)2 and cis, trans-Ir(H)2Cl(CO)(PPh3)2. The choice whether hydridocarbonyls, 1 and 3 undergo the deprotonation or decarbonylation may be understood mostly in terms of thermodynamic stability of the products and partly by kinetic preference of Me3NO on proton and CO.

Carbon dioxide reforming of methane on Ni/γ-Al2O3 catalyst was studied. A new 10 wt% Ni/γ-Al2O3 catalyst prepared by the liquid phase oxidation method (L10O) exhibited much higher activity as well as resistances to both sintering and coke formation during the reaction than the catalyst prepared by the conventional impregnation method (D10). The electrically strong attractive interaction between nickel and support during the liquid phase oxidation process and the resultant high nickel dispersion made the L10 have superior activity and stability to the D10. To elucidate the results, the experiments with nickel catalysts on the other supports as well as 7-AI203 were performed. The effect of sodium as a promoter was also studied.