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81.
Romanescu C Sergeeva AP Li WL Boldyrev AI Wang LS 《Journal of the American Chemical Society》2011,133(22):8646-8653
Small boron clusters have been shown to be planar from a series of combined photoelectron spectroscopy and theoretical studies. However, a number of boron clusters are quasiplanar, such as B(7)(-) and B(12)(-). To elucidate the nature of the nonplanarity in these clusters, we have investigated the electronic structure and chemical bonding of two isoelectronic Al-doped boron clusters, AlB(6)(-) and AlB(11)(-). Vibrationally resolved photoelectron spectra were obtained for AlB(6)(-), resulting in an accurate electron affinity (EA) for AlB(6) of 2.49 ± 0.03 eV. The photoelectron spectra of AlB(11)(-) revealed the presence of two isomers with EAs of 2.16 ± 0.03 and 2.33 ± 0.03 eV, respectively. Global minimum structures of both AlB(6)(-) and AlB(11)(-) were established from unbiased searches and comparison with the experimental data. The global minimum of AlB(6)(-) is nearly planar with a central B atom and an AlB(5) six membered ring, in contrast to that of B(7)(-), which possesses a C(2v) structure with a large distortion from planarity. Two nearly degenerate structures were found for AlB(11)(-) competing for the global minimum, in agreement with the experimental observation. One of these isomers with the lower EA can be viewed as substituting a peripheral B atom by Al in B(12)(-), which has a bowl shape with a B(9) outer ring and an out-of-plane inner B(3) triangle. The second isomer of AlB(11)(-) can be viewed as an Al atom interacting with a B(11)(-) cluster. Both isomers of AlB(11)(-) are perfectly planar. It is shown that Al substitution of a peripheral B atom in B(7)(-) and B(12)(-) induces planarization by slightly expanding the outer ring due to the larger size of Al. 相似文献
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A new one-dimensional polymeric complex [Cd(SCN)2(H2O)]L (L = N,N?-bis(furan- 2-ylmethylene)hydrazine) has been synthesized and characterized by IR, UV spectra, TG-DTA technique and single-crystal X-ray diffraction analysis. It crystallizes in triclinic, pace group P1 with a = 5.9268(8), b = 10.8678(15), c = 13.3671(19) , α = 109.295(2), β = 95.092(2), γ = 97.8580(10)°, V = 796.70(19) 3, Z = 2, C12H10CdN4O3S2, Mr = 434.76, μ = 1.648 mm–1, Dc = 1.812 g/cm3, F(000) = 428, R = 0.0308 and wR = 0.0769. The crystal structure reveals that the structure of [Cd(SCN)2(H2O)]n features di-μ-1,3-thiocyante bridges and 1D chains. The octahedrally coordinated Cd atom is surrounded by one oxygen atom from water molecule, three S atoms and two Natoms from five di-μ-1,3 thiocyanato bridges. The Cd atoms are connected by two di-μ-1,3 thiocyanato bridges with the Cd(1)…Cd(1A) separation of 4.239(1) and Cd(1)…Cd(1B) of 5.852(1). In addition, the one-dimensional straight chain structure is further connected by multiform intermolecular N-H…O hydrogen bonds and π…π interactions to form a three-dimensional supramolecular structure. 相似文献
85.
Dr. Hang-Yu Zhou Yu Ou Shuai-Shuai Yan Dr. Jin Xie Pan Zhou Lei Wan Zi-Ang Xu Dr. Feng-Xiang Liu Dr. Wei-Li Zhang Dr. Yin-Chun Xia Prof. Kai Liu 《Angewandte Chemie (International ed. in English)》2023,62(35):e202306948
Improved durability, enhanced interfacial stability, and room temperature applicability are desirable properties for all-solid-state lithium metal batteries (ASSLMBs), yet these desired properties are rarely achieved simultaneously. Here, in this work, it is noticed that the huge resistance at Li metal/electrolyte interface dominantly impeded the normal cycling of ASSLMBs especially at around room temperature (<30 °C). Accordingly, a supramolecular polymer ion conductor (SPC) with “weak solvation” of Li+ was prepared. Benefiting from the halogen-bonding interaction between the electron-deficient iodine atom (on 1,4-diiodotetrafluorobenzene) and electron-rich oxygen atoms (on ethylene oxide), the O-Li+ coordination was significantly weakened. Therefore, the SPC achieves rapid Li+ transport with high Li+ transference number, and importantly, derives a unique Li2O-rich SEI with low interfacial resistance on lithium metal surface, therefore enabling stable cycling of ASSLMBs even down to 10 °C. This work is a new exploration of halogen-bonding chemistry in solid polymer electrolyte and highlights the importance of “weak solvation” of Li+ in the solid-state electrolyte for room temperature ASSLMBs. 相似文献
86.
采用SIMPLE算法对二维流体力学基本方程组进行了数值模拟,研究了Poiseuille-Rayleigh-Bénard流动中对流斑图的分区、成长及水平流动对不同斑图特征物理量的影响.结果表明,上下临界雷诺数Re_u,Re_l将流动分成三个区域,即行波区、局部行波区、水平流区.Re_u和Re_l随着相对瑞利数r的增大而增大.在对流斑图的成长阶段,三种斑图随时间的成长过程是不同的,但对流圈都是从下游区开始成长;特征物理量随着时间的变化也是不同的,行波对流和局部行波对流的最大垂直流速wmax和努塞尔数Nu经过指数增长阶段后进入周期变化的稳定阶段;水平流斑图的w_(max)和Nu经过缓慢增长后又缓慢降到稳定值.三种斑图的w_(max)和Nu随雷诺数Re增大而减小,不同斑图区域有不同的变化规律.本文给出了Re_u和Re_l随r的变化关系式及不同斑图的w_(max)和Nu随着Re的变化关系式. 相似文献
87.
Jian Wu Dan-Dan Xie Wei-Li Shan Yong-Hui Zhao Wei Zhang Baoan Song Song Yang Juan Ma 《Chemical Papers》2015,69(7):993-1003
A series of anthranilic diamides with a hydrazone substructure was synthesised and characterised using 1HNMR, 13C NMR, IR and elemental analyses. The in vitro insecticidal activity of all the compounds was tested against Plutella xylostella. The results showed the synthesised compounds to possess good insecticidal activity. The LC50 values of compounds VIIg, VIIl, VIIm, VIIn exhibited excellent insecticidal activities, with the LC50 affording 7.92 mg L?1, 12.01 mg L?1, 0.62 mg L?1 and 10.71 mg L?1, respectively. These may prove to be useful as potential insecticidal agents. 相似文献
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89.
Li WL Romanescu C Galeev TR Wang LS Boldyrev AI 《The journal of physical chemistry. A》2011,115(38):10391-10397
The structures and the electronic properties of two Al-doped boron clusters, AlB(9)(-) and AlB(10)(-), were investigated via joint photoelectron spectroscopy and high-level ab initio study. The photoelectron spectra of both anions are relatively broad and have no vibrational structure. The geometrical structures were established by unbiased global minimum searches using the Coalescence Kick method and comparison between the experimental and calculated vertical electron detachment energies. The results show that both clusters have quasi-planar structures and that the Al atom is located at the periphery. Chemical bonding analysis revealed that the global minimum structures of both anions can be described as doubly (σ- and π-) aromatic systems. The nona-coordinated wheel-type structure of AlB(9)(-) was found to be a relatively high-lying isomer, while a similar structure for the neutral AlB(9) cluster was previously shown to be either a global minimum or a low-lying isomer. 相似文献
90.
H2Bn- (n = 7—12) clusters are generated by laser vaporization of an isotopically enriched 11B target with helium containing 5% D2 as the carrier gas. 相似文献