Methods of composite molecular wave functions. I. Variational principle and multiconfiguration SCF theory

The Silverstone–Stuebing variational principle for the discontinuous wave functions of one-electron systems is generalized for many-electron systems. The variational functional of energy takes real or complex value. The condition that it is real is given. Using the generalized variational principle, a multiconfiguration SCF theory for the composite molecular wave function is formulated. According to the theory, we may divide the whole space into space-filling cells, solve the SCF equations in each cell and build up the wave functions of the system by gathering the wave functions obtained in the cells. For use in the basis-set expansion method, the SCF equations are rewritten as matrix forms in which only one- and two-center integrals appear if an expansion center is located in each cell.     

Synthesis, characterization, and detailed electrochemistry of binuclear ruthenium(III) complexes bridged by bisacetylacetonate. Crystal and molecular structures of [[Ru(acac)2]2(tae)] (acac = 2,4-pentanedionate ion, tae = 1,1,2,2-tetraacetylethanate dianion)

Binuclear beta-diketonatoruthenium(III) complexes [[Ru(acac)(2)](2)(tae)], [[Ru(phpa)(2)](2)(tae)], and [(acac)(2)Ru(tae)Ru(phpa)(2)] and binuclear and mononuclear bipyridine complexes [[Ru(bpy)(2)](2)(tae)](PF(6))(2) and [Ru(bpy)(2)(Htae)]PF(6) (acac = 2,4-pentanedionate ion, phpa = 2,2,6,6-tetramethyl-3,5-heptanedionate ion, tae = 1,1,2,2-tetraacetylethanate dianion, and bpy = 2,2'-bipyridine) were synthesized. The new complexes have been characterized by (1)H NMR, MS, and electronic spectral data. Crystal and molecular structures of [[Ru(acac)(2)](2)(tae)] have been solved by single-crystal X-ray diffraction studies. Crystal data for the meso isomer of [[Ru(acac)(2)](2)(tae)] have been confirmed by the dihedral angle result that two acetylacetone units of the bridging tae ligand are almost perpendicular to one another. A detailed investigation on the electrochemistry of the binuclear complexes has been carried out. The electrochemical behavior details of the binuclear complexes have been compared with those of the mononuclear complexes obtained from the half-structures of the corresponding binuclear complexes. Studies on the effects of solvents on the mixed-valence states of Ru(II)-Ru(III) and Ru(III)-Ru(IV) complexes have been carried out by various voltammetric and electrospectroscopic techniques. A correlation between the comproportionation constant (K(c)) and the donor number of the solvent has been obtained. The K(c) values for the binuclear complexes have been found to be low because of the fact that two acetylacetone units of the bridging tae ligand are not in the same plane, as revealed by the crystal structure of [[Ru(acac)(2)](2)(tae)].     

Substituent effect on the IR and PMR spectra of diphenylamines

PMR chemical shifts of various m- and p-substituted diphenylamines were correlated with σ-constants. However, the NH stretching frequencies of these amines were not linear with the σ- constants, and the irregularity in the ν_NHvs σ plot was interpreted by taking into accounts the following factors: the changes in hybridization of the imino N atoms, the normal electronic effect of the substituent and the steric effect on the planarity of the amine molecules. Results on the CN stretching absorptions were also presented.     

A novel calamitic mesophase semiconductor with the fastest mobility of charged carriers: 1,4-di(5'-octyl-2'-thienyl)benzene

The carrier mobility of highly ordered lamellar mesophases was evaluated by a Time-of-Flight (TOF) method for mesogenic 1,4-di(5'-octyl-2'-thienyl)benzene (8-TPT-8) to reveal the fastest drift mobility (0.1 cm(2) V(-1) s(-1) for the lowest temperature mesophase) in calamitic liquid crystals reported to date.     

Immobilized cells of a unicellular green alga and a photosynthetic bacterium for use in a biophotolysis system

Applied Biochemistry and Biotechnology - Immobilization of algal and bacterial cells was investigated, and found applicable to our hydrogen production system. Both a unicellular green alga,...     

Determination of three metabolites of a new angiotensin-converting enzyme inhibitor, imidapril, in plasma and urine by gas chromatography-mass spectrometry using multiple ion detection.

A specific and sensitive gas chromatographic-mass spectrometric method for the determination of three metabolites of the angiotensin-converting enzyme inhibitor, imidapril, in plasma and urine was developed. The metabolites were isolated from plasma and urine using a Bond Elut C18 solid-phase extraction cartridge. The isolated metabolites were converted to sensitive derivatives by pentafluorobenzyl bromide and heptafluoro-n-butyric acid anhydride. Following derivatization, the sample solutions were analysed by wide-bore column gas chromatography-mass spectrometry with multiple ion detection. The detection limits of the three metabolites were each 1 ng/ml in plasma and 5 ng/ml in urine. Analysis of the spiked plasma and urine samples demonstrated the good accuracy and precision of the method. This method was very useful for use in pharmacokinetic and bioavailability studies of the three metabolites of imidapril in humans.     

Crystal Structure of Europium C60 Compounds

Abstract

We have studied crystal structures of europium C₆₀ compounds by high resolution x-ray diffraction measurements. In the systematic synthesis of Eu _x C₆₀ for x (0 ≤ x ≤ 6), two stable phases appear at x = 3 and 6. Eu₆C₆₀ has a bcc structure, which is an isostructure to M ₆C₆₀ (M represents an alkali or alkaline earth metal). Eu₃C₆₀ has a superstructure derived by doubling the fcc pristine C₆₀ crystal along three principal axes. This superstructure comes from an ordering of cation vacancies, which is analogous to Yb_2.75C₆₀.