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31.
Explicitly correlated MBPT-R12 and coupled cluster [up to CCSD(T)-R12] methods have been used in calculations of various
(vibrationless) electrical properties for the LiH molecule, including the dipole and quadrupole moments, dipole and quadrupole
polarizability tensors, dipole hyperpolarizability tensors, and the second dipole hyperpolarizability tensors. Generally,
with extension of the basis set the R12 method did not lead to faster convergence for the calculated properties towards the
basis limit. Nevertheless, R12 calculations serve as useful indicators to judge the reliability of the results, and substantially
help in determining the accuracy. Results obtained with the 11s8p6d5f/9s8p6d5f basis and CCSD(T)-R12 calculated within this work should be close to the basis set limit.
Received: 8 June 1998 / Accepted: 23 July 1998 / Published online: 7 October 1998 相似文献
32.
Gerhard Schmid 《Journal of membrane science》1998,150(2):151-157
In capillary systems with narrow pores the Helmholtz electrochemical double layer located at the pore wall extends over the entire cross section of the pores. It loses its character as the “charge on the wall”. It will be shown that not only the electrokinetic phenomena but also the electrical conductivity and the dialysis potential of membranes with narrow pores can be understood from the same point of view, namely: the electrolyte solution in the pores of a membrane with narrow pores is considered to be an approximately homogeneous solution in contact with immobilised charges located at the pore wall. In this case the electrochemical equations contain the fixed ion concentration as a parameter instead of the ζ potential. This makes it possible to describe quantitatively to a good approximation data on the electroosmosis, the electrical conductivity, the streaming potential and the dialysis potential taken from the literature, as well as results of our own measurements, by using a single membrane constant. 相似文献
33.
H. Dhaouadi H. Marouani M. Rzaigui A. Madani 《Phosphorus, sulfur, and silicon and the related elements》2013,188(8):1801-1814
Chemical preparation, crystal structure, thermogravimetric and differential analysis, solid state 31P MAS NMR characterization, and IR spectroscopic investigations are given for a new organic cation dihydrogenmonophosphate, (2-CH3OC6H4CH2NH3)H2PO4. This compound is monoclinic C2/c, with unit cell parameters a = 27.740(8), b = 4.827(2), c = 16.435(3) Å, β = 93.79(2)°, V = 2196 (1) Å3, Z = 8, and ρ = 1.422 g · cm?3. The crystal structure has been determined and refined to R = 0.046 (Rw = 0.056), using 1,746 independent reflections with I > 3σ (I). Its atomic arrangement can be described by infinite polyanions [H2PO4] n n ?, organized in ribbons alternating with organic cations. Strong hydrogen bonds connect the different components. Electrical conductivity measurements show that the [2-CH3OC6H4CH2NH3]H2PO4 has a low ionic conductivity value at 403 K. 相似文献
34.
35.
利用粗粒化分子动力学模拟研究了电场作用下离子型聚合物复合囊泡形变与破裂的过程.定量分析了囊泡破裂过程中的结构变化,包括囊泡的形变程度、破裂速度、组分分布以及破裂后的结构.研究表明,电场强度较弱时,囊泡表面所吸附的聚电解质首先脱落,囊泡由球形结构转变为椭球结构.随着电场强度增大,离聚物的离子侧基发生重新排布,囊泡表面电荷的有序结构被破坏,导致囊泡的结构无法维持而破裂,囊泡塌缩,分裂形成离聚物团簇,并进一步破裂为小尺寸的离聚物聚集体,均匀分散于溶液中.本文利用分子动力学模拟明确了电场中离子型高分子复合囊泡破裂过程的分子机理,为药物释放技术的优化及发展提供了理论支持. 相似文献
36.
Dr. Liping Liu Dr. Haibing Meng Dr. Yongqiang Chai Dr. Xianjie Chen Dr. Jingyi Xu Dr. Xiaolong Liu Dr. Weixu Liu Prof. Dirk M. Guldi Prof. Yongfa Zhu 《Angewandte Chemie (International ed. in English)》2023,62(11):e202217897
High-efficiency photocatalysts based on metal-organic frameworks (MOFs) are often limited by poor charge separation and slow charge-transfer kinetics. Herein, a novel MOF photocatalyst is successfully constructed by encapsulating C60 into a nano-sized zirconium-based MOF, NU-901. By virtue of host-guest interactions and uneven charge distribution, a substantial electrostatic potential difference is set-up in C60@NU-901. The direct consequence is a robust built-in electric field, which tends to be 10.7 times higher in C60@NU-901 than that found in NU-901. In the catalyst, photogenerated charge carriers are efficiently separated and transported to the surface. For example, photocatalytic hydrogen evolution reaches 22.3 mmol g−1 h−1 for C60@NU-901, which is among the highest values for MOFs. Our concept of enhancing charge separation by harnessing host-guest interactions constitutes a promising strategy to design photocatalysts for efficient solar-to-chemical energy conversion. 相似文献
37.
Yu Wang Bochun Liang Jiaxiong Zhu Geng Li Qing Li Ruquan Ye Jun Fan Chunyi Zhi 《Angewandte Chemie (International ed. in English)》2023,62(23):e202302583
Constructing a reliable solid-electrolyte interphase (SEI) is imperative for enabling highly reversible zinc metal (Zn0) electrodes. Contrary to conventional “bulk solvation” mechanism, we found the SEI structure is dominated by electric double layer (EDL) adsorption. We manipulate the EDL adsorption and Zn2+ solvation with ether additives (i.e. 15-crown-5, 12-crown-4, and triglyme). The 12-crown-4 with medium adsorption on EDL leads to a layer-structured SEI with inner inorganic ZnFx/ZnSx and outer organic C−O−C components. This structure endows SEI with high rigidness and strong toughness enabling the 100 cm2 Zn||Zn pouch cell to exhibit a cumulative capacity of 4250 mAh cm−2 at areal-capacity of 10 mAh cm−2. More importantly, a 2.3 Ah Zn||Zn0.25V2O5⋅n H2O pouch cell delivers a recorded energy density of 104 Wh Lcell−1 and runs for >70 days under the harsh conditions of low negative/positive electrode ratio (2.2 : 1), lean electrolyte (8 g Ah−1), and high-areal-capacity (≈13 mAh cm−2). 相似文献
38.
Qiuyue Ge Yangyang Liu Kejian Li Lifang Xie Xuejun Ruan Wei Wang Longqian Wang Tao Wang Wenbo You Liwu Zhang 《Angewandte Chemie (International ed. in English)》2023,62(27):e202304189
Solar-driven CO2 reduction reaction (CO2RR) is largely constrained by the sluggish mass transfer and fast combination of photogenerated charge carriers. Herein, we find that the photocatalytic CO2RR efficiency at the abundant gas-liquid interface provided by microdroplets is two orders of magnitude higher than that of the corresponding bulk phase reaction. Even in the absence of sacrificial agents, the production rates of HCOOH over WO3 ⋅ 0.33H2O mediated by microdroplets reaches 2536 μmol h−1 g−1 (vs. 13 μmol h−1 g−1 in bulk phase), which is significantly superior to the previously reported photocatalytic CO2RR in bulk phase reaction condition. Beyond the efficient delivery of CO2 to photocatalyst surfaces within microdroplets, we reveal that the strong electric field at the gas-liquid interface of microdroplets essentially promotes the separation of photogenerated electron-hole pairs. This study provides a deep understanding of ultrafast reaction kinetics promoted by the gas-liquid interface of microdroplets and a novel way of addressing the low efficiency of photocatalytic CO2 reduction to fuel. 相似文献
39.
Chao Wang Jialu Li Tianyu Shao Dongsheng Zhang Yuanqiang Mai Prof. Dr. Yongwang Li Prof. Dr. Flemming Besenbacher Prof. Dr. Hans Niemantsverdriet Prof. Dr. Federico Rosei Prof. Dr. Jun Zhong Prof. Dr. Ren Su 《Angewandte Chemie (International ed. in English)》2023,62(51):e202313313
Heterogeneous catalytic ammoxidation provides an eco-friendly route for the cyanide-free synthesis of nitrile compounds, which are important precursors for synthetic chemistry and pharmaceutical applications. However, in general such a process requires high pressures of molecular oxygen at elevated temperatures to accelerate the oxygen reduction and imine dehydrogenation steps, which is highly risky in practical applications. Here, we report an electric field enhanced ammoxidation system using a supported Fe clusters catalyst (Fe/NC), which enables efficient synthesis of nitriles from the corresponding aldehydes under ambient air pressure at room temperature (RT). A synergistic effect between the external electric field and the Fe/NC catalyst promotes the ammonia activation and the dehydrogenation of the generated imine intermediates and avoids the unwanted backwards reaction to aldehydes. This electric field enhanced ammoxidation system presents high efficiency and selectivity for the conversion of a series of aldehydes under mild conditions with high durability, rendering it an attractive process for the green synthesis of nitriles with fragile functional groups. 相似文献
40.
双电层相互重叠时蒙脱胶体表面阴离子的负吸附 总被引:2,自引:0,他引:2
本文用Ag-AgCl电极判断平衡,测定双电层处于不同重叠程度下肢体表面阴离子的负吸附量Γ.结果表明,胶体表面双电层相互重叠程度可由两胶体表面间的中点电位φd与外Helmhotz面处的电位φd之比表征;阴离子负吸附随双电层重叠程度和电解质浓度的增加而显著减小. 相似文献