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971.
Rui Yan Li Zhi Ru Li Di Wu Xi Yun Hao Ru Jiao Li Chia Chung Sun 《International journal of quantum chemistry》2005,103(2):157-166
Using four basis bets, (6‐311G(d,p), 6‐31+G(d,p), 6‐31++G(2d,2p), and 6‐311++G(3df,3pd), the optimized structures with all real frequencies were obtained at the MP2 level for the dimers CH2O? HF, CH2O? H2O, CH2O? NH3, and CH2O? CH4. The structures of CH2O? HF, CH2O? H2O, and CH2O? NH3 are cycle‐shaped, which result from the larger bend of σ‐type hydrogen bonds. The bend of σ‐type H‐bond O…H? Y (Y?F, O, N) is illustrated and interpreted by an attractive interaction of a chemically intuitive π‐type hydrogen bond. The π‐type hydrogen bond is the interaction between one of the H atoms of CH2O and lone pair(s) on the F atom in HF, the O atom in H2O, or the N atom in NH3. In contrast with the above three dimers, for CH2O? CH4, because there is not a π‐type hydrogen bond to bend its linear hydrogen bond, the structure of CH2O? CH4 is noncyclic shaped. The interaction energy of hydrogen bonds and the π‐type H‐bond are calculated and discussed at the CCSD (T)/6‐311++G(3df,3pd) level. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005 相似文献
972.
973.
Yao Chang Jiayue Yang Zhichao Chen Zhiguo Zhang Yong Yu Qingming Li Zhigang He Weiqing Zhang Guorong Wu Rebecca A. Ingle Matthew Bain Michael N. R. Ashfold Kaijun Yuan Xueming Yang Christopher S. Hansen 《Chemical science》2020,11(19):5089
Chemical processing in the stratospheres of the gas giants is driven by incident vacuum ultraviolet (VUV) light. Ethane is an important constituent in the atmospheres of the gas giants in our solar system. The present work describes translational spectroscopy studies of the VUV photochemistry of ethane using tuneable radiation in the wavelength range 112 ≤ λ ≤ 126 nm from a free electron laser and event-triggered, fast-framing, multi-mass imaging detection methods. Contributions from at least five primary photofragmentation pathways yielding CH2, CH3 and/or H atom products are demonstrated and interpreted in terms of unimolecular decay following rapid non-adiabatic coupling to the ground state potential energy surface. These data serve to highlight parallels with methane photochemistry and limitations in contemporary models of the photoinduced stratospheric chemistry of the gas giants. The work identifies additional photochemical reactions that require incorporation into next generation extraterrestrial atmospheric chemistry models which should help rationalise hitherto unexplained aspects of the atmospheric ethane/acetylene ratios revealed by the Cassini–Huygens fly-by of Jupiter.The vacuum ultraviolet photodissociation dynamics of ethane provide clues for modelling the atmospheric chemistry of the gas giants. 相似文献
974.
Zhiyong Wu Duanjun Xu Jingyun Wu Michael Y. Chiang 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):m374-m376
The title compound, [CuCl(CH4N2S)2]·2C11H6N2O·H2O, consists of molecules of a CuI–thiourea complex, free 4,5‐diazafluoren‐9‐one (dafone) and crystalline water. The planar complex molecule has trigonal coordination geometry around the CuI atom. The dafone and water molecules, which are hydrogen bonded to the CuI complex, are approximately coplanar with this complex. The crystal displays a sheet structure and π–π stacking is observed between neighbouring sheets. 相似文献
975.
A simple and effective chemically modified carbon paste electrode (CMCPE) for the simultaneous determination of lead(II) and cadmium(II) was developed in this work. The electrode was prepared by the addition of diacetyldioxime into a carbon paste mixture. Pb2+ and Cd2+ were preconcentrated on the surface of the modified electrode by complexing with diacetyldioxime and reduced at a negative potential (−1.10 V). Then the reduced products were oxidized by differential pulse stripping. The fact that two stripping peaks appeared on the voltammograms at the potentials of −0.65 V (Cd2+) and −0.91 V (Pb2+) demonstrates the possibility of simultaneous determination of Pb2+ and Cd2+. Under the optimized working conditions, calibration graphs were linear in the concentration ranges of 1.0×10−7-1.5×10−5 mol l−1 (Pb2+) and 2.5×10−7-2.5×10−5 mol l−1 (Cd2+), respectively. For 5 min preconcentration, detection limits of 1×10−8 mol l−1 (Pb2+) and 4×10−8 mol l−1 (Cd2+) were obtained at the signal noise ratio (SNR) of 3. To evaluate the reproducibility of the newly developed electrode, the measurements of 5×10−7 mol l−1 Pb2+ and Cd2+ were parallel carried out for six times at different electrodes and the relative standard deviations were 2.9% (Pb2+) and 3.2% (Cd2+), respectively. Interferences by some metals were investigated. Only Ni2+ and Hg2+ apparently affected the peak currents of Pb2+ and Cd2+. The diacetyldioxime modified carbon paste electrode was applied to the determination of Pb2+ and Cd2+ in water samples. The results indicate that this electrode is sensitive and effective for the simultaneous determination of Pb2+ and Cd2+. 相似文献
976.
采用共沉淀并加法制备了B位掺杂烧绿石型稀土复合氧化物纳米微晶Y2Sn2-xFexO7-δ(x=00~10)。制备的纳米微晶属于立方晶系,Fd3m,晶胞参数与掺杂量呈线性关系。通过Msbauer、TGDTA,气相色谱和γ射线辐照等技术研究了纳米微晶对CO的催化选择性能。结果表明,纳米微晶对CO的催化选择性明显高于一般粉料对CO的选择性;纳米微晶对CO的选择性与掺杂量有关;未辐照的纳米微晶,当掺杂量x=06时,其对CO的选择性为最高,辐照后的纳米微晶,当掺杂量x=04时,其对CO的选择性为最高 相似文献
977.
合成了E,E-1,4-二[2′,2″-(苯并(口恶)唑基乙烯基)]苯及衍生物共14种,测定了它们的熔点、红外光谱、核磁共振氢谱、紫外吸收光谱和荧光发射光谱、荧光量子产率及激光性能。 相似文献
978.
979.
The conformational preference of calix[4]pyrrole and its fluoride and chloride anion-binding properties have been investigated by density functional theory calculations. Geometries were optimized by the BLYP/3-21G and BLYP/6-31G methods, and energies were evaluated with the BLYP/6-31+G method. To model the effect of medium, the SCIPCM solvent model was also employed. Four typical conformations of the parent substituent-free calix[4]pyrrole were studied. Both in the gas phase and in CH(2)Cl(2) solution, the stability sequence is predicted to be 1,3-alternate > partial cone > 1,2-alternate > cone. The cone conformation is predicted to be about 16.0 and 11.4 kcal/mol less stable in the gas phase and CH(2)Cl(2) solution, respectively. This is mainly due to electrostatic repulsions arising from the all-syn pyrrole/pyrrole/pyrrole/pyrrole arrangement present in this conformer. The existence of possible 1:1 and 1:2 anion-binding modes were explored in the case of fluoride anion, and the factors favoring the 1:1 binding mode are discussed. The calculated binding energy for fluoride anion is about 15 kcal/mol larger than that for chloride anion. The calculated binding energy for chloride anion agrees with the experimental value very well. The presence of meso-alkyl substituents destabilizes the cone conformer with respect to the 1,3-alternate conformer and, therefore, reduces the anion-binding affinity by 3-4 kcal/mol. The strength of N-H- - -anion hydrogen bonds in the various structures subject to study were estimated on the basis of the calculated anion-binding energies and the predicted structural deformation energies of substituent-free calix[4]pyrrole. 相似文献
980.
The structure and stability of endohedral X@Si20H20 complexes (X = Li0/+, Na0/+, K0/+, Be0/2+, Mg0/2+, Ca0/2+) have been studied at the B3LYP/6-31G* level of density functional theory. It is found that complexes with X = Na0/+, K0/+, Mg and Ca0/2+ are energy minimum structures with X at the cage center in Ih symmetry, while those with X = Li0/+, Be0/2+, Mg2+ have off-centered structures with X towards one pentagon face in C5v symmetry. Large electron or charge transfer between the Si20H20 cage and the encapsulated X has been observed. 相似文献