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11.
Keivan Esfarjani Yuichi Hashi Satoshi Itoh Sigeo Ihara Yoshiyuki Kawazoe 《Zeitschrift für Physik D Atoms, Molecules and Clusters》1997,41(1):73-76
To study the thermodynamic and mechanical stability of toroidal isomers of C 240, we use a semi-empirical tight-binding theory and calculate their electronic structure, cohesive energy and vibrational spectra within the harmonic approximation. From these, we deduce their free energy at temperatures up to 1500K. The results are also compared to the isomer with icosahedral symmetry. Finally, we discuss within this approach, their stability and abundance. 相似文献
12.
Shimazaki Y Tashiro M Motoyama T Iwatsuki S Yajima T Nakabayashi Y Naruta Y Yamauchi O 《Inorganic chemistry》2005,44(17):6044-6051
Synthetic, structural, spectroscopic, and kinetic studies have been carried out on the Pd(II) complexes of new 2N1O-donor ligands containing a pendent indole, 3-(N-2-pyridylmethyl-N-2-hydroxy-5-methoxybenzylamino)ethylindole (HMeO-iepp), 3-(N-2-pyridylmethyl-N-2-hydroxy-5-nitrobenzylamino)ethylindole (HNO2-iepp), and (N-2-pyridylmethyl-3-indolylethylamino)acetic acid (Hiepc) (H denotes a dissociable proton). [Pd(MeO-iepp)Cl] (2), [Pd(NO2-iepp)Cl] (3), and [Pd(iepc)Cl] (4) were prepared and revealed by X-ray analysis to have a pyridine nitrogen, an amine nitrogen, a phenolate or carboxylate oxygen, and a chloride ion in the coordination plane. UV absorption and 1H NMR spectral changes indicated that all the complexes could be converted to the indole-binding complexes where the O donor was replaced by the indole C2 atom by cyclopalladation in DMSO or DMF in the temperature range of 40-60 degrees C. Formation of the indole-binding complex species obeyed the first-order kinetics, from which the activation parameters were estimated. The formation rate was dependent on the properties of the O-donor group, a lower pKa value of its conjugate acid causing faster conversion to the indole-binding species in the order 2 (methoxyphenolate) < 3 (nitrophenolate) < 4 (carboxylate). On the other hand, the ratio of the indole-binding complex to the O-donor complex as a result of the conversion was greater for the complexes with a higher pKa value of the ligand OH group, the order being 2 > 3 > 4. 相似文献
13.
A linearized optimal control method in combination with mixed quantum/classical molecular dynamics simulation is used for numerically investigating the possibility of controlling photodissociation wave packets of I(2)(-) in water. Optimal pulses are designed using an ensemble of photodissociation samples, aiming at the creation of localized dissociation wave packets. Numerical results clearly show the effectiveness of the control although the control achievement is reduced with an increase in the internuclear distance associated with a target region. We introduce effective optimal pulses that are designed using a statistically averaged effective dissociation potential, and show that they semiquantitatively reproduce the control achievements calculated by using optimal pulses. The control mechanisms are interpreted from the time- and frequency-resolved spectra of the effective optimal pulses. 相似文献
14.
Hossain MJ Yamasaki M Mikuriya M Kuribayashi A Sakiyama H 《Inorganic chemistry》2002,41(15):4058-4062
A new end-off type acyclic ligand with four hydroxyethyl arms, 2,6-bis[bis(2-hydroxyethyl)aminomethyl]-4-methylphenol [H(bhmp)], formed dinuclear cobalt(II) complexes [Co(2)(bhmp)(OAc)(2)]BPh(4) (1) and [Co(2)(bhmp)(OBz)(2)]BPh(4) (2). The complex 1.2.5CH(3)CN (C(50)H(62.5)BCo(2)N(4.5)O(9)) crystallizes in the monoclinic space group C2/c with dimensions a = 25.424(5) A, b = 13.376(2) A, c = 29.913(6) A, beta = 105.930(3) degrees, and V = 9781(3) A(3) and with Z = 8. X-ray diffraction analysis revealed a mu-phenoxo-bis(mu-acetato)dicobalt(II) core structure containing two octahedral cobalt(II) ions. Electronic spectra were investigated for 1 and 2 in the range 400-1800 nm, and the data were typical for the octahedral high-spin cobalt(II) complexes. Magnetic susceptibility was measured for 1 and 2 over the temperature range 4.5-300 K, and the data were analyzed well using our theoretical method. The best fitting parameters were kappa = 0.77, lambda = -116 cm(-1), Delta = 572 cm(-1), and J = -0.44 cm(-1) for complex 1 and kappa = 0.96, lambda = -93 cm(-1), Delta = 616 cm(-1), and J = -0.33 cm(-1) for complex 2. 相似文献
15.
Mitsunori Honda Yuichi Yamamoto Hideki Tsuchida Masahito Segi Tadashi Nakajima 《Tetrahedron letters》2005,46(38):6465-6468
Treatment of cyclopropylsilylmethanols derived from cyclopropyl silyl ketones with acid catalyst gives the corresponding silyl-substituted homoallyl derivatives in high yields with good stereoselectivity, independent of the substituents on the cyclopropyl ring. Cyclopropylsilylmethanols having a n-, s-butyl or phenyl group on the carbinyl carbon react to afford the E-homoallyl derivatives selectively. On the other hand, the reaction of cyclopropylsilylmethanols having a tert-butyl group gives Z-isomers exclusively. The following protiodesilylation of the resulting homoallyl derivatives proceeds with retention of configuration. 相似文献
16.
Oguchi T Tozuka Y Hanawa T Mizutani M Sasaki N Limmatvapirat S Yamamoto K 《Chemical & pharmaceutical bulletin》2002,50(7):887-891
The solid-state complexation between cholic acid (CA) and either methyl p-hydroxybenzoate (MPB) or ibuprofen (IBP) was investigated. Powder X-ray diffractometry, IR spectroscopy and thermal analysis suggested the complex formation between CA and MPB as well as between CA and IBP by co-grinding method. The stoichiometry of CA-MPB was 1 : 1 while that of CA-IBP was 2 : 1, reflecting the effect of guest size on complex formation. The guest compounds were assumed to be included in the channel of complexes formed by hydrogen bonds among CA molecules. 相似文献
17.
Attenuated total reflection spectrometry with a slab optical waveguide (SOWG) was explored for the simple, rapid and sensitive measurement of total anionic surfactants by the methylene blue active substance (MBAS) method. A fused-silica sheet used as a guiding layer was modified with trimethylsilane (TMS) to extract and concentrate the MBASs on the SOWG surface. Based on preliminary studies of the adsorption behavior and visible ATR spectrum of MB on the modified silica surface, a detection wavelength of 600 nm was chosen for the sensitive measurement of anionic surfactants. When the concentration of MB was set at 10 microM in the final measurement solution, the calibration curve for a typical anionic surfactant (sodium dodecylbenzenesulfonate) was linear up to 0.6 microM and the detection limit was 0.07 microM. The proposed method was applied to the determination of total anionic surfactants in river water. 相似文献
18.
Geometry optimizations at the UHF/6-31G* and UMP2/6-31G* levels of theory were performed to find the transition state in the interconversion between norbornadiene (N) and quadricyclane (Q) radical cations. Two transition structures, TS+·1 and TS+·2, were obtained which have C1 and C2 symmetry, respectively. Vibrational analysis at the UHF and UMP2 levels of theory and IRC calculation showed that TS+·1 is the true transition state connecting N+· and Q+·, while TS+·2 is a second order saddle point. 相似文献
19.
Akira Yamasaki 《Analytica chimica acta》1981,133(4):741-746
The TOOL-IR. PDB and COOD systems are compared for the construction of data bases for 59Co-n.m.r. bibliographic and spectral data. The spectral data used are the chemical shifts from several different standards, and the line widths and coupling constants (if present). The PDB system is effective for storage and retrieval of bibliographic data, but the COOD system is better for the retrieval of spectral data, and for combination of data files on literature and chemical shifts. 相似文献
20.