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In order to elucidate the mechanism of reaction M+ + SCO, both triplet and singlet potential energy surfaces (PESs) for the reaction of Sc+ + SCO have been theoretically investigated using the DFT (B3LYP/6-311+G*) level of theory. The geometries for reactants, intermediates, transition states and products were completely optimized. All the transition states were verified by the vibrational analysis and the intrinsic reaction coordinate calculations. The involving potential energy curve-crossing dramatically affects reaction mechanism, reaction rate has been discussed, and the crossing points (CPs) have been localized by the approach suggested by Yoshizawa et al. The present results show that the reaction mechanism are insertion–elimination mechanism both along the C–S and C–O bond activation branches, but the C–S bond activation is much more favorable in energy than the C–O bond activation. All theoretical results not only support the existing conclusions inferred from early experiment, but also complement the pathway and mechanism for this reaction. 相似文献
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Molecular and electronic structural properties of the hydrogen-bonded complexes of p-quinone dianions (PQ(2)(-)) were investigated by electrochemistry and spectroelectrochemistry of PQ in MeCN combined with ab initio MO calculations. Hydrogen bonding between PQ(2)(-) and MeOH was measured as the continuous positive shift of the apparent second half-wave reduction potentials with increasing concentrations of MeOH. Detailed analyses of the behavior reveal that PQ(2)(-) forms the 1:2 hydrogen-bonded complexes at low concentrations of MeOH and the 1:4 complexes at high concentrations, yielding the formation constants. Temperature dependence of the formation constants allows us to yield the formation energy as 76.6 and 118.9 kJ mol(-)(1) for the 1:2 and 1:4 complex formation of the 1,4-benzoquinone dianion (BQ(2)(-)) with MeOH, respectively. These results show that the pi-dianions involving the quinone carbonyl groups exhibit very strong hydrogen-accepting ability. The longest wavelength band of the spectra of BQ(2)(-) and the chloranil dianion (CL(2)(-)) is assigned to the (1)B(3u) <-- (1)A(g) band mainly contributed from an intramolecular charge-transfer (CT) configuration. Hydrogen bonding allows the band of BQ(2)(-) and CL(2)(-) to be blue-shifted, depending on the strength of the hydrogen bonds. CNDO/S-CI calculations reveal that the blue shift is ascribed to stabilization of the ground state by the hydrogen bonding involving strong n-sigma-type CT interaction. The HF/6-31G(d) calculation results show that the structure of PQ(2)(-) is characterized by a lengthening of the C=O bonds and a benzenoid ring. The geometrical properties of the hydrogen-bonded complexes of PQ(2)(-) are a slight lengthening of the C=O bonds and a short distance of the hydrogen bonds. It is demonstrated that this situation is due to the strong n-sigma CT interaction in the hydrogen bonds. The results suggest that the differing functions and properties of biological quinones are conferred by the n-sigma CT interaction through hydrogen bonding of the dianions with their protein environment. 相似文献
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一种新型铒镱共掺碲硅酸盐玻璃的光谱性质及荧光俘获效应研究 总被引:5,自引:1,他引:5
用高温熔制法制备了系列Er^3+/Yb^3+共掺碲硅酸盐玻璃样品,测试和分析了玻璃样品的吸收光谱、荧光光谱、上转换发光光谱及热稳定性。结果表明:这种玻璃具有较宽的荧光半高宽、较大的受激发射截面,较好的热稳定性。970nm泵浦下该系列玻璃在可见光525,546和658nm这3处存在明显的上转换现象,它们分别由Er^3+离子^2H11/2→^4 I15/2,4S3/2→^4 I15/2和^4 F9/2→^4 I15/2辐射跃迁产生。另外,测试和讨论了在不同样品厚度下玻璃的光谱特性,如荧光光谱、荧光寿命和上转换发光光谱等。结果表明,荧光俘获效应对Er^3+离子1.5μm波段荧光及上转换发光都有着较大的影响,并随着玻璃厚度的增加而增大,导致测量值与实际值产生较大的偏差。 相似文献
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