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本文利用环聚合分子动力学方法对C(1D)+H2反应开展了详细的理论研究. 计算中使用了最近构建的Zhang-Ma-Bian(ZMB)从头算势能面,该势能面对锥形交叉附近区域以及范德华区域均有精确的描述. 环聚合分子动力学计算得到的热反应速率常数与最新实验值吻合很好. 与前人计算结果比较,发现在?1A′电子基态的ZMB-a势能面上获得的反应速率常数远大于前人构建的RKHS势能面上的结果,这是由于ZMB势能面上的范德华鞍具有与之前势能面上的范德华阱完全不同的动态学作用,表明环聚合分子动力学方法能够处理范德华作用引起的势能面拓扑结构所导致的动态学效应. 本文还揭示了b1A′′电子激发态ZMB-b势能面以及量子效应对反应的重要性. 相似文献
3.
Structural stability in terms of the decomposition temperature in LiMn2O4 was systematically investigated by a series of high-temperature and high-pressure experiments.LiMn2O4 was found to have structural stability up to 5 GPa at room temperature.Under ambient pressure,the compound decomposed at 1300℃.The decomposition temperature decreased with increasing pressure,yielding more complex decomposed products.Below the decomposition temperature,the crystal structure of LiMn2O4 varied with pressure.The presented results in this study offer new insights into the thermal and pressure stability of LiMn2O4 materials as a cathode for lithium-ion batteries that can operate under extreme conditions.Therefore,these findings may serve as a useful guide for future work for improving lithium-ion batteries. 相似文献
4.
Cross-section measurements of (n, 2n) and (n, p) reactions on 124,126,128,130,131,132Xe in the 14 MeV region and theoretical calculations of their excitation functions 下载免费PDF全文
Junhua Luo Li Jiang Juncheng Liang Fei Tuo Long He Liang Zhou 《中国物理C(英文版)》2022,46(4):044001-044001-13
The reaction cross-sections of 124Xe(n, 2n)123Xe, 126Xe(n, 2n)125Xe, 128Xe(n, 2n)127Xe, 130Xe(n, 2n)129mXe, 132Xe(n, 2n)131mXe, 130Xe(n, p)130I, 131Xe(n, p)131I, and 132Xe(n, p)132I were measured at the 13.5, 13.8, 14.1, 14.4, and 14.8 MeV neutron energies. The monoenergetic neutrons were generated via the 3H(d,n)4He reaction at the China Academy of Engineering Physics using the K-400 Neutron Generator with a solid 3H-Ti target. A high-purity germanium detector was employed to measure the activities of the product. The reactions 93Nb(n, 2n)92mNb and 27Al(n, α)24Na were adopted for neutron flux calibration. The cross sections of the (n, 2n) and (n, p) reactions of the xenon isotopes were obtained within the 13–15 MeV neutron energy range. These cross-sections were then compared with the IAEA-exchange format (EXFOR) database-derived experimental data, together with the evaluation results of the CENDL-3, ENDF/B-VIII.0, JENDL-4.0, RUSFOND, and JEFF-3.3 data libraries, as well as the theoretical excitation function obtained using the TALYS-1.95 code. The cross-sections of the reactions (except for the 124Xe(n, 2n)123Xe and 132Xe(n, p)132I) at 13.5, 13.8, and 14.1 MeV are reported for the first time in this study. The obtained results are beneficial in providing better cross-section constraints for the reactions in the 13–15 MeV region, thus improving the quality of the corresponding database. Meanwhile, these data can also be used for the verification of relevant nuclear reaction model parameters. 相似文献
5.
Based on the isospin-dependent Boltzmann–Langevin model, the dynamical fluctuations in the fragmentation reaction of 112Sn+112Sn are investigated. The quadrupole moment and octupole moment with zero magnetic quantum number have large fluctuations in the early time of the collisions. The dynamical fluctuations in momentum space show a strong dependence on the incident energy. The effects of using different fluctuations on the fragment cross sections are also studied in the fragmentation reactions. The results by using Q20 + Q30 fluctuation have a better agreement with the experimental data. Calculations using Q20 + Q30 fluctuation produce more proton-rich and neutron-rich nuclei than those using Q20 fluctuation only. Besides, the difference between the production cross sections of fragments calculated by using Q20 and Q20 + Q30 fluctuations is larger in the vicinity of the projectile. These results present that the dynamical fluctuations may affect the whole dynamical process of fragmentation reactions including the production of fragments, due to the nonlinear nature of the Boltzmann–Langevin equation. 相似文献
6.
SHANG Anqi ZHAO Lele LI Zhenhua CHENG Zhuang JIN Haixu FENG Zijun CHEN Zhijun ZHANG Haiquan LU Ping 《高等学校化学研究》2022,38(6):1461-1466
Near-infrared(NIR) fluorescent materials with high photoluminescent quantum yields(PLQYs) have wide application prospects. Therefore, we design and synthesize a D-A type NIR organic molecule, TPATHCNE, in which triphenylamine and thiophene are utilized as the donors and fumaronitrile is applied as the acceptor. We systematically investigate its molecular structure and photophysical property. TPATHCNE shows high Tgof 110℃ and Td of 385℃ and displays an aggregation-induced emission(AIE) property. A narrow optical bandgap of 1.65 eV is obtained. The non-doped film of TPATHCNE exhibits a high PLQY of 40.3% with an emission peak at 732 nm, which is among the best values of NIR emitters. When TPATHCNE is applied in organic light-emitting diode(OLED), the electroluminescent peak is located at 716 nm with a maximum external quantum efficiency of 0.83%. With the potential in cell imaging, the polystyrene maleic anhydride(PMSA) modified TPATHCNE nanoparticles(NPs) emit strong fluorescence when labeling HeLa cancer cells, suggesting that TPATHCNE can be used as a fluorescent carrier for specific staining or drug delivery for cellular imaging. TPATHCNE NPs fabricated by bovine serum protein(BSA) are cultivated with mononuclear yeast cells, and the intense intracellular red fluorescence indicates that it can be adopted as a specific stain for imaging. 相似文献
7.
Lydia A. Panther Dr. Daniel P. Guest Dr. Andrew McGown Hugo Emerit Dr. Raysa Khan Tareque Dr. Arathy Jose Mr. Chris M. Dadswell Dr. Simon J. Coles Dr. Graham J. Tizzard Dr. Ramón González-Méndez Dr. Charles A. I. Goodall Prof. Mark C. Bagley Prof. John Spencer Dr. Barnaby W. Greenland 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(49):e202201444
Solvent-free synthesis by using a vibratory ball mill (VBM) offers the chance to access new chemical reactivity, whilst reducing solvent waste and minimising reaction times. Herein, we report the core functionalisation of N,N’-bis(2-ethylhexyl)-2,6-dibromo-1,4,5,8-naphthalenetetracarboxylic acid (Br2-NDI) by using Suzuki, Sonogashira and Buchwald–Hartwig coupling reactions. The products of these reactions are important building blocks in many areas of organic electronics including organic light-emitting diodes (OLEDs), organic field-effect transistors (OFETs) and organic photovoltaic cells (OPVCs). The reactions proceed in as little as 1 h, use commercially available palladium sources (frequently Pd(OAc)2) and are tolerant to air and atmospheric moisture. Furthermore, the real-world potential of this green VBM protocol is demonstrated by the double Suzuki coupling of a monobromo(NDI) residue to a bis(thiophene) pinacol ester. The resulting dimeric NDI species has been demonstrated to behave as an electron acceptor in functioning OPVCs. 相似文献
8.
Superatoms are atomic clusters with tailored size and composition that mimic the chemistry of atoms in the periodic table. However, unlike the atoms whose chemistry is governed by their valence electron orbitals, the chemistry of superatoms is governed by their highest occupied molecular orbitals. In addition, due to their large size and non-spherical geometry, superatoms can promote unusual reactions and serve as the building blocks of cluster assembled materials with properties very different from conventional materials. This perspective highlights the unique role of superatoms in chemical and material sciences by focusing on superhalogens, which not only possess electron affinities larger than those of halogens but also can be stable when multiply charged. We discuss how these unique features of superhalogens enable noble gas atoms like argon to form chemical bonds at room temperature and zinc to exhibit an oxidation state of +3. The advantages of using superhalogens in the synthesis of water-resistant materials for solar cells, halogen-free electrolytes for solid-state batteries, and multiferroic materials are also discussed. 相似文献
9.
Dr. Thomas Hansen Dr. Alba Nin-Hill Prof. Dr. Jeroen D. C. Codée Dr. Trevor A. Hamlin Prof. Dr. Carme Rovira 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(60):e202201649
The development of small-molecule covalent inhibitors and probes continuously pushes the rapidly evolving field of chemical biology forward. A key element in these molecular tool compounds is the “electrophilic trap” that allows a covalent linkage with the target enzyme. The reactivity of this entity needs to be well balanced to effectively trap the desired enzyme, while not being attacked by off-target nucleophiles. Here we investigate the intrinsic reactivity of substrates containing a class of widely used electrophilic traps, the three-membered heterocycles with a nitrogen (aziridine), phosphorus (phosphirane), oxygen (epoxide) or sulfur atom (thiirane) as heteroatom. Using quantum chemical approaches, we studied the conformational flexibility and nucleophilic ring opening of a series of model substrates, in which these electrophilic traps are mounted on a cyclohexene scaffold (C6H10Y with Y=NH, PH, O, S). It was revealed that the activation energy of the ring opening does not necessarily follow the trend that is expected from C−Y leaving-group bond strength, but steeply decreases from Y=NH, to PH, to O, to S. We illustrate that the HOMONu–LUMOSubstrate interaction is an all-important factor for the observed reactivity. In addition, we show that the activation energy of aziridines and phosphiranes can be tuned far below that of the corresponding epoxides and thiiranes by the addition of proper electron-withdrawing ring substituents. Our results provide mechanistic insights to rationally tune the reactivity of this class of popular electrophilic traps and can guide the experimental design of covalent inhibitors and probes for enzymatic activity. 相似文献
10.
Palladium nanoparticles/wool keratin-assisted carbon composite-modified flexible and disposable electrochemical solid-state pH sensor 下载免费PDF全文
张文立 刘笑天 林友辉 马利芸 孔令庆 闵光宗 吴荣辉 Sharwari K.Mengane 杨丽坤 Aniruddha B.Patil 刘向阳 《中国物理 B》2022,31(2):28201-028201
Several p H-dependent processes and reactions take place in the human body;hence,the p H of body fluids is the best indicator of disturbed health conditions.However,accurate and real-time diagnosis of the p H of body fluids is complicated because of limited commercially available p H sensors.Hence,we aimed to prepare a flexible,transparent,disposable,userfriendly,and economic strip-based solid-state p H sensor using palladium nanoparticles(Pd NPs)/N-doped carbon(NC)composite material.The Pd NPs/NC composite material was synthesized using wool keratin(WK)as a precursor.The insitu prepared Pd NPs played a key role in the controlled switching of protein structure to the N-doped carbon skeleton withπ–πarrangement at the mesoscale level,which mimics the A–B type polymeric structure,and hence,is highly susceptible to H+ions.The optimized carbonization condition in the presence of Pd NPs showed that the material obtained using a modified Ag/Ag Cl reference electrode had the highest p H sensitivity with excellent stability and durability.The optimized p H sensor showed high specificity and selectivity with a sensitivity of 55 m V/p H unit and a relative standard deviation of 0.79%.This study is the first to synthesize Pd NPs using WK as a stabilizing and reducing agent.The applicability of the sensor was investigated for biological samples,namely,saliva and gastric juices.The proposed protocol and material have implications in solid-state chemistry,where biological material will be the best choice for the synthesis of materials with anticipated performance. 相似文献