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51.
The density functional theory was employed to investigate Eu(III) complexes with three beta-diketonates and two phosphine oxides (complex M1: Eu(bdk)3(TPPO)2, complex M2: Eu(bdk)3(TMPO)2, and complex M3: Eu(bdk)3(TPPO)(TMPO)) deemed to be the model complexes of the fluorescence compounds for the ultraviolet LED devices we have recently developed. For each complex, two minimum energy points corresponding to two different optimized geometries (structures A and B) have been found, and the difference of the energy between two minimum energy points is found to be quite small (less than 1 kcal/mol). Vertical excitation energies and oscillator strengths for each complex at two optimized geometries have been obtained by the time-dependent density functional theory, and the character of the excited states has been investigated. For complex M3, the absorption edge is red-shifted, and the oscillator strengths are relatively large. The efficiency of intersystem crossing and energy transfer from the triplet excited state to the Eu(III) ion is considered by calculating DeltaE(ISC) (the energy difference between the first singlet excited state and the first triplet excited state) and DeltaE(ET) (the difference between the excitation energy of the complex for the first triplet excited state and the emission energy of the Eu(III) ion for 5D to 7F). 相似文献
52.
Fumiyuki Ozawa Takashi Ito Yoshiyuki Nakamura Akio Yamamoto 《Journal of organometallic chemistry》1979,168(3):375-391
New palladium(0) complexes with a variety of coordinated olefins [Pd(olefin)(PMePh2)2] (II) (olefin = styrene, ethyl methacrylate, methyl methacrylate, methyl acrylate, methacrylonitrile, and dimethyl maleate), were prepared by the reactions of [PdEt2(PMePh2)2] (I) with corresponding olefins in toluene. These complexes were characterized by means of elemental analysis, IR and 1H NMR spectroscopy and the chemical reactions. The dissociation of the coordinated olefin from complex II in solution was confirmed by spectroscopic studies of [Pd(mma)(PMePh2)2] (mma = methyl methacrylate). From the variable temperature NMR study, kinetic parameters for the dissociation process were determined as Ea = 7 kcal/mol, and ΔS3 (293 K) = -30 cal/deg · mol. Some new hydrido complexes, [Pd(H)ClL2] (IV) (L = PMePh2, PEtPh2 and PEt2Ph), were prepared by the reactions of [Pd(olefin)L2] with dry HCl. 相似文献
53.
A critical review is presented on the studies of the internal rotation potential function which is indispensable in understanding rotational isomerism from a dynamical point of view. Molecules so far investigated are classified into a few groups to clarify what factors govern the potential function. As an application of these results, the molecular structures of some bicyclic compounds are discussed, where the internal rotation is shown to play an important role. The recent microwave studies on two molecules of fundamental importance in the internal rotation problem, namely ethane and dimethylacetylene, are briefly mentioned. 相似文献
54.
Baba T Abe Y Nomoto K Inazu K Echizen T Ishikawa A Murai K 《The journal of physical chemistry. B》2005,109(9):4263-4268
Methane is shown to react with ethene over In-loaded ZSM-5 to higher hydrocarbons such as propene and toluene at around 673 K. Such methane conversion is not catalyzed by proton-exchanged ZSM-5 (H-ZSM-5) under the same conditions, only C2H4 being converted to higher hydrocarbons. By using 13C-labeled methane (13CH4) as a reactant, the reaction paths for the formation of propene, benzene and toluene were examined. 13C-labeled propene (13CC2H6) is formed by the reaction of 13CH4 with C2H4. The lack of 13C-labeled benzene revealed that propene is not transformed to benzene, which instead originates entirely from C2H4. The 13C atom is inserted both into the methyl group and benzene ring in the toluene formed. This indicates that toluene is formed by two reaction paths; the reaction of 13CC2H6 with butenes formed by the dimerization of C2H4 and the reaction of benzene with 13CH4. The existence of the latter path was proved by the direct reaction of 13CH4 with benzene. The reaction of methane with benzene was also carried out in a continuous flow system over In-loaded ZSM-5. The reaction afforded 7.6% and 0.9% yields of toluene and xylenes, respectively, at 623 K. 相似文献
55.
Motohisa Kaneko Akio Matsuyama Chikayoshi Nagata 《Photochemistry and photobiology》1978,27(3):359-361
Abstract. Photodimerization of thymine in aqueous solution in the presence of tyrosine was studied with monochromatic UV irradiation. The total dimer formation was sensitized in the presence of tyrosine. The action spectrum of sensitized total dimer formation has a peak near 280 nm corresponding to the absorption maximum of tyrosine. Triplet quenchers reduced the sensitization substantially. It seems probable that tyrosine-sensitized photodimerization of thymine occurred via triplet-triplet energy transfer from tyrosine to thymine. 相似文献
56.
57.
58.
Akio Hosoya 《Nuclear Physics B》1980,165(1):34-44
The variational calculation of the path-ordered phase factor is streamlined. We propose that the wave functional for a string state is approximately of the form .The real factor K is shown to be proportional to the square root of the dielectric permeability in the Kogut-Susskind-'t Hooft model of colour flux collimation. 相似文献
59.
About two hundred Stark resonances of the ν2 and ν5 vibration-rotation bands of CD335Cl, using a 9.4 μm CO2 laser as a source, have been measured. By combining these data with the zero-field microwave spectra the following molecular constants have been determined (with the standard deviations in parentheses):
1 028.67275 (15) | 1 059.96970 (11) | (cm?1) | ||||
78 765.20 (89) | 78 030.21 (109) | (MHz) | ||||
10 805.29 (26) | 10 860.10 (13) | (MHz) | ||||
?25 080.77 (99) | (MHz) | |||||
8 756.0 (43) | (MHz) | |||||
μ | 1.90741 (33) | 1.90607 (36) | (D) | |||
μ(ground state) | 1.90597 (33) | (D) |