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11.
Alkynes cycloaddition reactions are powerful tools for constructing cyclic molecules with optimal atom efficiency, but these reactions cannot proceed at ambient temperature without transition-metal catalysts. In this work, a heterobimetallic complex featuring an Nb–Fe triple bond, Nb(iPrNPMe2)3Fe–PMe3, has been evaluated as the potential catalyst for acetylene cycloaddition, using density functional theory. The calculated results show that the singlet-state (i.e. ground-state) Nb(iPrNPMe2)3Fe–PMe3 can be applied to benzene synthesis, but is not suitable for cyclobutadiene. Benzene can be obtained easily at room temperature and is the unique product on the singlet potential surface. The irradiation of infrared-red light can drive the excitation of singlet Nb(iPrNPMe2)3Fe–PMe3 to its triplet state. Both benzene and cyclobutadiene can be formed on the triplet reaction potential surface due to their low energy barriers. Therefore, Nb(iPrNPMe2)3Fe–PMe3 is a potential high reactivity heterobimetallic catalyst for the cyclotrimerization of alkynes. In the reaction process, the catalytic active site of Nb(iPrNPMe2)3Fe–PMe3 moves from niobium to iron. 相似文献
12.
Dr. Si-Yong Qin Yan Jiang Dr. Han Sun Han Liu Prof. Ai-Qing Zhang Prof. Xinxiang Lei 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17245-17251
Residual dipolar coupling (RDC), a robust anisotropic NMR parameter for structural elucidation of organic molecules, is only accessible in an anisotropic environment. Herein, we introduce a novel alignment medium based on the molecular self-assembly of oligopeptide amphiphile (OPA). This medium is compatible with different intermediate and polar solvent systems, such as CD3OD, [D6]DMSO, and D2O. The preparation of the OPA-based medium is simple and rapid, while only very weak background signals were observed from OPAs. Furthermore, we show that the purity of OPA has only a minor influence on the quality of the RDC data. These advantages allow RDC measurements of organic molecules with different polarities and solubilities with high efficiency and accuracy. 相似文献
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用密耦方法计算了非对称同位素替代分子与氦原子碰撞(He-HD,HT,DT)转动激发,当入射能量E=0.3 eV时,得到了上述碰撞体系的微分散射截面或角分布.基于上述理论计算,讨论了原子与双原子分子碰撞的同位素效应. 相似文献
15.
应用不可约张量理论构造了三角对称晶场中3d2/3d8态离子的45阶可完全对角化的微扰哈密顿矩阵,研究了CsNiCl3晶体的光谱精细结构、晶体结构、零场分裂参量、Jahn-Telller效应以及自旋单重态对Ni2+离子基态能级的影响,理论与实验相符合.在此基础上,进一步研究了以前工作中被忽略的自旋-自旋耦合作用和Trees修正对CsNiCl3晶体的光谱精细结构和零场分裂参量的影响,发现有四种机理会影响零场分裂参量:1)自旋-轨道耦合机理,2)自旋-自旋耦合机理;3)自旋-轨道与自旋-自旋联合耦合机理;4)自旋-轨道与Trees修正联合耦合机理,其中自旋-轨道耦合机理是最主要的,其他三种机理也是不可忽略的.
关键词:
基态能级
精细结构
零场分裂
自旋-自旋耦合 相似文献
16.
在长距离无线光通信中,接收点光功率密度与光束发散角平方呈反比关系,为了获得小的发散角和大的功率耦合效率,要求准直系统有较大的数值孔径(NA),但数值孔径过大会增加像差,因此合理设计功率耦合效率与准直系统的数值孔径就非常重要。该文对半导体激光器光束准直系统中功率耦合效率进行了研究,给出了半导体激光器光束功率耦合效率与k(孔径半径与孔径处等效光束半径之比)的关系表达式,并结合激光器光束准直系统,给出了半导体激光器光束功率耦合效率与准直系统数值孔径的关系表达式。该研究结论对于半导体激光器光束准直系统设计具有参考作用。 相似文献
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19.
High-temperature series expansions of the susceptibility and second moment to 15th order are calculated for zero external field on the linear chain (LC), plane square (PSQ), simple cubic (SC), and body-centered cubic (BCC) lattices. Checks for specific models against pertinent work in the literature are detailed. 相似文献
20.
《Magnetic resonance in chemistry : MRC》2003,41(6):417-430
A systematic study of the one‐bond and long‐range J(C,C), J(C,H) and J(H,H) in the series of nine bicycloalkanes was performed at the SOPPA level with special emphasis on the coupling transmission mechanisms at bridgeheads. Many unknown couplings were predicted with high reliability. Further refinement of SOPPA computational scheme adjusted for better performance was carried out using bicyclo[1.1.1]pentane as a benchmark to investigate the influence of geometry, basis set and electronic correlation. The calculations performed demonstrated that classical ab initio SOPPA applied with the locally dense Dunning's sets augmented with inner core s‐functions used for coupled carbons and Sauer's sets augmented with tight s‐functions used for coupled hydrogens performs perfectly well in reproducing experimental values of different types of coupling constants (the estimated reliability is ca 1–2 Hz) in relatively large organic molecules of up to 11 carbon atoms. Additive coupling increments were derived for J(C,C), J(C,H) and J(H,H) based on the calculated values of coupling constants within SOPPA in the model bicycloalkanes, in reasonably good agreement with the known values obtained earlier on pure empirical grounds. Most of the bridgehead couplings in all but one bicycloalkane appeared to be essentially additive within ca 2–3 Hz while bicyclo[1.1.1]pentane demonstrated dramatic non‐additivity of ?14.5 Hz for J(C,C), +16.6 Hz for J(H,H) and ?5.5 Hz for J(C,H), in line with previous findings. Non‐additivity effects in the latter compound established at the SOPPA level should be attributed to the through‐space non‐bonded interactions at bridgeheads due to the essential overlapping of the bridgehead rear lobes which provides an additional and effective non‐bonding coupling path for the bridgehead carbons and their protons in the bicyclopentane framework. Copyright © 2003 John Wiley & Sons, Ltd. 相似文献