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141.
This work presents an experimental and theoretical study to address the chemical reactivity of series of nitroxide radicals. For that purpose two physicochemical properties: the half-wave potential and the hyperfine coupling constants of the nitrogen nuclei, were analyzed. Experimental values are compared with electronic structure calculations at the BHandHLYP/6-311++G(2d,2p) level. E1/2 values were in good agreement with the adiabatic ionization potential when including the solvent effects by the Cramer and Truhlar Solvation Model. Preeliminar experimental electron spin deslocalization studies suggest that structural hindrance plays an important role in their deslocatization mechanism. 相似文献
142.
Joseph Israel Gurti Prof. Xun-Lei Ding Ya-Ya Wang Yan Chen Dr. Wei Li Dr. Xin Wang 《Chemphyschem》2022,23(14):e202200124
The reaction of N2 with trinuclear niobium and tungsten sulfide clusters Nb3Sn and W3Sn (n=0–3) was systematically studied by density functional theory calculations with TPSS functional and Def2-TZVP basis sets. Dissociations of N−N bonds on these clusters are all thermodynamically allowed but with different reactivity in kinetics. The reactivity of Nb3Sn is generally higher than that of W3Sn. In the favorite reaction pathways, the adsorbed N2 changes the adsorption sites from one metal atom to the bridge site of two metal atoms, then on the hollow site of three metal atoms, and at that place, the N−N bond dissociates. As the number of ligand S atoms increases, the reactivity of Nb3Sn decreases because of the hindering effect of S atoms, while W3S and W3S2 have the highest reactivity among four W3Sn clusters. The Mayer bond order, bond length, vibrational frequency, and electronic charges of the adsorbed N2 are analyzed along the reaction pathways to show the activation process of the N−N bond in reactions. The charge transfer from the clusters to the N2 antibonding orbitals plays an essential role in N−N bond activation, which is more significant in Nb3Sn than in W3Sn, leading to the higher reactivity of Nb3Sn. The reaction mechanisms found in this work may provide important theoretical guidance for the further rational design of related catalytic systems for nitrogen reduction reactions (NRR). 相似文献
143.
Dr. Jia Wang Xuhui Liu Dr. Chunxu Wang Wanyi Zhang Prof. Zhengkun Qin 《ChemistryOpen》2022,11(2):e202100208
The spin polarization of carbon nanomaterials is crucial to design spintronic devices. In this paper, the first-principles is used to study the electronic properties of two defect asymmetric structures, Cap-(9, 0)-Def [6, 6] and Cap-(9, 0)-Def [5, 6]. We found that the ground state of Cap-(9, 0)-Def [6, 6] is sextet and the ground state of Cap-(9, 0)-Def [5, 6] is quartet, and the former has a lower energy. In addition, compared with Cap-(9, 0) CNTs, the C adatom on C30 causes spin polarization phenomenon and Cap-(9, 0)-Def [6, 6] has more spin electrons than Cap-(9, 0)-Def [5, 6] structure. Moreover, different adsorb defects reveal different electron accumulation. This finding shows that spin polarization of the asymmetric structure can be adjusted by introducing adatom defects. 相似文献
144.
Brønsted acid-catalyzed inverse-electron demand (IED) aza-Diels-Alder reactions between 2-aza-dienes and ethylene were studied using quantum chemical calculations. The computed activation energy systematically decreases as the basic sites of the diene progressively become protonated. Our activation strain and Kohn-Sham molecular orbital analyses traced the origin of this enhanced reactivity to i) “Pauli-lowering catalysis” for mono-protonated 2-aza-dienes due to the induction of an asynchronous, but still concerted, reaction pathway that reduces the Pauli repulsion between the reactants; and ii) “LUMO-lowering catalysis” for multi-protonated 2-aza-dienes due to their highly stabilized LUMO(s) and more concerted synchronous reaction path that facilitates more efficient orbital overlaps in IED interactions. In all, we illustrate how the novel concept of “Pauli-lowering catalysis” can be overruled by the traditional concept of “LUMO-lowering catalysis” when the degree of LUMO stabilization is extreme as in the case of multi-protonated 2-aza-dienes. 相似文献
145.
Hristo Rasheev Prof. Dr. Radostina Stoyanova Prof. Dr. Alia Tadjer 《Chemphyschem》2021,22(11):1110-1123
The construction of hybrid metal-ion batteries faces a plethora of challenges. A critical one is to unveil the solvation/desolvation processes at the molecular level in electrolytes that ensure efficient transfer of several types of charge carriers. This study reports first results on simulations of mixed-ion electrolytes. All combinations of homo- and hetero-binuclear complexes of Li+, Na+ and Mg2+, solvated with varying number of ethylene carbonate (EC) molecules are modeled in non-polar and polar environment by means of first principles calculations and compared to the mononuclear analogues in terms of stability, spatial organization, charge distribution and solvation/desolvation behavior. The used PF6− counterion is shown to have minor impact on the geometry of the complexes. The desolvation energy penalty of binuclear complexes can be lowered by the fluoride ions, emerging upon the PF6− decay. These model investigations could be extended to rationalize the solvation structure and ionic mobility in dual-ion electrolytes. 相似文献
146.
Piao He Jian‐Guo Zhang Kun Wang Xin Yin Tong‐Lai Zhang 《Journal of Physical Organic Chemistry》2016,29(1):29-34
Two novel energetic nitrogen‐rich compounds 1,4‐diaminotetrazol‐5‐one ( DATO ) and 1,4‐dinitrotetrazol‐5‐one ( DNTO ) were proposed first and studied by quantum chemistry method with B3LYP/6‐31G* level of theory. The optimized geometry, IR predicted spectrum and thermochemical parameters, frontier molecular orbitals and molecular electrostatic potential were calculated for inspecting the electronic structure, molecular stability and chemical reactivity. The important macroscopic properties including density, enthalpy of formation, detonation parameters and impact sensitivity have been predicted as well. As a result, two designed compounds DATO and DNTO possess positive enthalpy of formation (395.79 and 342.77 kJ/mol), impressive detonation parameters (D = 8.80 km/s, P = 33.69 GPa; D = 8.89 km/s, P = 34.98 GPa) superior to the remarkable explosive RDX, acceptable sensitivities and might be promising candidates of energetic materials. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
147.
Transient spectroscopic characterization of the ring‐opening reaction of tetrahydrochromeno[2,3‐dimethyl]indole 下载免费PDF全文
Ariel S. Marshall Robert A. Rogers Joseph W. Perry W. J. Brittain 《Journal of Physical Organic Chemistry》2016,29(5):221-226
Tetrahydrochromeno is a structural variant of spiropyran that undergoes a reversible ring‐opening to generate a colored nitrophenolate intermediate. Earlier work confirmed this intermediate through trimethylsilyl cyanide trapping under continuous irradiation. We have performed transient absorption spectroscopy to further characterize the mechanism of the ring‐opening reaction. Excitation at 355 nm produced a transient species with an absorption maximum at 445 nm, which we assign to the nitrophenolate unit of the ring‐opened product. The transient absorption decays after ~970 ns with small optical density changes corresponding to a 0.15 quantum yield. Exposure to oxygen did not exhibit a significant deleterious effect on the photoisomerization of the chromeno dye. Time‐dependent density functional theory corroborated spectroscopic assignments of the starting chromeno and the putative ring‐opened intermediate. The excited state behavior of this system parallels the structurally similar oxazine system reported by Raymo and coworkers. The one significant difference is the longer lifetime of the photochemically generated intermediate from chromeno. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
148.
本文研究了无线传感网络( Wireless Sensor Network,WSNs)的节点定位问题,并针对APIT由于锚节点在低密度环境下的节点误判和节点失效等问题给出了改进,在APICT定位算法的基础提出了联合分步定位算法UNION-APICT(Union Approximate Point-In-Circumcircle Test),该算法是结合连通性的测距技术,RSSI测距技术以及质心定位和APICT等技术,来联合解决对未知节点定位问题。通过仿真实验结果表明,改进后的UNION-APICT在APICT算法的基础之上平均定位误差减少了10%-25%,定位性能有了明显的提升;随着通信半径R和最大探测距离rmax的增加,定位误差也在逐渐减小,该算法较APIT和APICT定位算法在锚节点密度、节点覆盖率和定位精度上都有所提高。 相似文献
149.
A. L. Vikharev A. M. Gorbachev M. A. Lobaev A. B. Muchnikov D. B. Radishev V. A. Isaev V. V. Chernov S. A. Bogdanov M. N. Drozdov J. E. Butler 《固体物理学:研究快报》2016,10(4):324-327
We report on building a novel chemical vapor deposition (CVD) reactor for diamond delta‐doping. The main features of our reactor are: a) the use of rapid gas switching system, (b) the reactor design providing the laminar gas flow. These features provide the creation of ultra‐sharp interfaces between doped and undoped material and minimize the prolonged ”tails” formation in the doping profile. It is proved by optical emission spectroscopy that gas switching time is not more than 10 seconds. Using the novel reactor we have grown the nanometer‐thin layers of boron doped diamond. The FWHM of boron concentration profile is about 2 nm which is proved by SIMS. It is shown that the both single delta‐layer and multiple delta‐layers could be grown using the novel CVD reactor. In principle, the reactor could be used for diamond delta doping with other dopants, like nitrogen, phosphorus etc. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
150.
Structure and physical properties of BiF3 doped with M=Cr, Cu, Fe, Mn, Ni, Ti, V and Co are calculated by the DFT+U method. Effect of metal doping on the electronic structure and optical response of host materials BiF3 is investigated systematically. New energy levels are formed and located within the band gap, which could decrease the recombination rate of e−/h+ pairs. Furthermore, transition metal doping extends the optical absorption of BiF3 to the visible spectral region. 相似文献