共查询到19条相似文献,搜索用时 187 毫秒
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用B3LYP/6-311++G**方法对NO二聚体阳离子(NO)2+进行了研究.几何优化并结合振动分析表明,该复合物存在5种可能的稳定构型.能量最低的是N-N相连的反式异构体,具有C2h对称性.分析了各稳定构型的相对稳定性及成键特征.建立了态态相关并给出异构化过渡态,分析了各构型之间转化的途径. 相似文献
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在B3LYP/6-311++G(d,p)水平上研究了SiC与乙烯的单重态和三重态反应机理,优化得到了反应物、过渡态、中间体和产物的几何构型;通过振动分析对过渡态和中间体构型进行了确认。在CCSD(T)/cc-pVTZ水平上对计算得到的构型进行了能量校正。计算结果表明,SiC+C2H4反应在单重态和三重态条件下均可发生,其中单重态反应为主反应通道,1P5为主产物。 相似文献
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在密度泛函B3LYP/6-31G**水平下,结合金属赝势基组Lanl2dz对14种2-硫代黄嘌呤异构体和Hg2+、Cl-可能形成的47种配合物结构进行了全自由度优化,并计算了键长、键角、零点能、吉布斯自由能、总能量和相对能量等数据。计算结果表明,2-硫代黄嘌呤异构体和Hg2+、Cl-形成的配合物结构中,2-硫代黄嘌呤酮式N(7)H形成的构型较稳定,能量相对较低的5种配合物中,能量由小到大的顺序依次为:2TX(1,3,7)-2<2TX(1,3,7)-3<2TX(1,3,7)-6<2TX(1,3,7)-4<2TX(1,3,7)-5。同时,将实验报道的红外光谱数据进行了归属,实验值和计算值比较吻合,从而说明了异构体的配位形式。 相似文献
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采用两种密度泛函方法对中性单核Ru(CO)n(n=5,4,3)和双核Ru2(CO)n(n=9,8)化合物进行理论计算,优化出16个稳定异构体.研究发现,和Os(CO)5类似,Ru(CO)5存在两个能量接近的最低异构体.Ru(CO)4的能量最低异构体为C2v对称性的单态构型.Ru(CO)3能量最低异构体为G对称性的单态构型.Ru2(c0)。的两个能量接近的最低异构体分别含有单个桥羰基和3个桥羰基.双核不饱和Ru2(CO)8的能量最低异构体为含有两个桥羰基的单态Q构型.通过比较M2(CO)n(M=Fe,Ru,Os;n=9,8)的能量最低构型,发现Fe和Ru倾向于形成含有多个桥配位羰基的构型,而Os则更倾向于形成不含桥配位羰基的构型.对离解能的研究表明,和失去一个羰基生成Ru2(CO)8相比,Ru2(CO)9更容易离解为Ru(CO)5和Ru(CO)4. 相似文献
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本文采用高精度的从头算方法计算了星际分子HC4N的电子结构和势能面。使用MP2/cc-pVTZ方法进行构象优化,共获得23个稳定单重态构型和21个过渡态。其中稳定结构包含线性构型,氢支链构型,以及含三元环,四元环和五元环的构型。进一步的精确单点能量计算在CCSD(T)/cc-pVTZ方法下进行,并采用G3(MP2)方法对比。通过结果分析得到HC4N单重态的5个热力学和动力学都比较稳定的的构型,分别为3个三元环结构R31,R32,R35,一个链状构型C1和一个氢支链构型B1。 相似文献
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二重态的N3O2中性分子作为中间体, 在N3O2阴离子的光解离反应和NO+N2O←→N2+NO2反应中均起重要作用. 在CCSD(T)/6-311G(d,p)//B3LYP/6-311G(d,p)+ZPE的水平上, 对这两个反应进行了理论计算. 结果表明, 在N3O2阴离子的光解离反应中, 该阴离子先在光照下解离为与其具有相同的W构型的中性分子和一个电子, 这个中性分子是一个过渡态, 它将打破C2v构型变成具有Cs对称性的W型中间异构体, 然后再经过一个过渡态, 裂解成N2O+NO两个小分子. 这个裂解过程的能垒非常低(5.96 kJ/mol), 因此在实验中很难检测到W型的中间异构体. 在另一个重要的[N3O2]体系的反应(NO+N2O←→N2+NO2)中, 找到了两条反应通道, 其中不经过中间异构体的一步转化通道更为可行. 相似文献
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类金属P对原子簇Ni_nB_2(n=1~6)性质影响的理论研究 总被引:2,自引:0,他引:2
依据实验事实设计组成可调的系列原子簇 NinBP、NinB2 (n = 1~6)模型, 利用密度泛函(DFT)方法在 B3LYP/Lanl2dz 水平上对所设计构型进行优化,得到各原子簇的最稳定构型,进而研究类金属元素 P 对非晶态合金 Ni-B 性质的影响。结果表明:三元非晶态合金 Ni–B–P 的稳定性强于二元非晶态合金 Ni-B;类金属 P 起到调节金属 Ni 原子 3d 轨道布居数的作用。这些均与实验结果一致,说明模型能反映合金的性质。 相似文献
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Hydrogen sorption properties and some corresponding changes in the crystallization of amorphous TM33Zr67 (TM=Fe, Co, Ni) alloys have been investigated. Relatively large amount of hydrogen was found to dissolve into the amorphous alloys
during electrochemical hydrogen charging. The microstructural evolution during annealing of H-charged Ni33Zr67 was studied as well. The weaker bonded hydrogen desorbs in a large temperature range (440–625 K) before the crystallization
of the amorphous alloys to start. A hydride phase (ZrH2) was found to form during annealing the H-charged amorphous Ni33Zr67 alloy. During heating at constant heating rate the hydride decomposes at about 715 K and formation of Zr2Ni immediately takes place. The final microstructure of the Zr2Ni, crystallized from the H-charged matrix, is noticeably finer compared to the material crystallized from the H-free amorphous
alloy, most probably due to the higher temperature of Zr2Ni formation in the H-charged amorphous alloy than in the H-free sample. 相似文献
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Majid Tavoosi 《Journal of Thermal Analysis and Calorimetry》2018,131(2):917-924
The crystallization behavior of amorphous Fe–Cr–B–Si alloys in the presence of Ni and Nb elements was the goal of this study. In this regard, four different amorphous–nanocrystalline Fe40Cr20Si15B15M10 (M=Fe, Nb, Ni, Ni0.5Nb0.5) alloys were prepared using mechanical alloying technique up to 20 h. Based on the achieved results, in contrast to Fe50Cr20Si15B15 alloy, the amorphous phase can be successfully prepared in the presence of Ni and Nb in composition. Although the crystallization mechanism of prepared amorphous phase in different alloys was the same, the Fe40Cr20Si15B15Nb10 alloy showed higher thermal stability in comparison with other samples. The crystallization activation energy of this amorphous alloy was estimated about 410 kJ mol?1 which was much higher than Fe40Cr20Si15B15Ni10 (195.5 kJ mol?1) and Fe40Cr20Si15B15Ni5Nb5 (360 kJ mol?1) samples. The calculated values of Avrami exponent (1.5 < n < 2.2) indicated that the crystallization process in different alloying systems is the same and to be governed by a three-dimensional diffusion-controlled growth. 相似文献
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本文研究了稀土元素对Ti0.26Zr0.07V0.24Mn0.1Ni0.33合金的微观结构和电化学性能的影响。结果表明,Ti0.26Zr0.07V0.24-xMn0.10Ni0.33REx(RE=Ce,Nd,Gd;x=0.01)合金均有V基固溶体相和C14型Laves相两相组成。合金中两相的晶格参数随加入稀土元素的不同而发生变化。稀土元素部分取代可改善合金电极的活化性能。然而,对合金电极的其他性能影响因元素种类不同而各异。Ce取代增大了合金电极的最大放电容量,Nd元素可以有效改善合金的高倍率放电性能。工作温度对合金电极的放电容量影响较大,Nd和Gd在333 K最大放电容量可达426和465 mAh.g-1。过高的温度使其循环容量衰减加剧。 相似文献
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Skeletal Ni Catalysts Prepared from Amorphous Ni–Zr Alloys: Enhanced Catalytic Performance for Hydrogen Generation from Ammonia Borane 下载免费PDF全文
Ai Nozaki Yasutomo Tanihara Dr. Yasutaka Kuwahara Tetsutaro Ohmichi Dr. Kohsuke Mori Dr. Takeshi Nagase Prof. Dr. Hiroyuki Y. Yasuda Prof. Dr. Hiromi Yamashita 《Chemphyschem》2016,17(3):412-417
Skeletal Ni catalysts were prepared from Ni–Zr alloys, which possess different chemical composition and atomic arrangements, by a combination of thermal treatment and treatment with aqueous HF. Hydrogen generation from ammonia borane over the skeletal Ni catalysts proceeded efficiently, whereas the amorphous Ni–Zr alloy was inactive. Skeletal Ni prepared from amorphous Ni30Zr70 alloy had a higher catalytic activity than that prepared from amorphous Ni40Zr60 and Ni50Zr50 alloys. The atomic arrangement of the Ni–Zr alloy also strongly affected the surface structure and catalytic activities. Thermal treatment of the amorphous Ni–Zr alloys at a temperature slightly lower than the crystallization temperature led to an increase of the number of surface‐exposed Ni atoms and an enhancement of the catalytic activities for hydrogen generation from ammonia borane. The skeletal Ni catalysts also showed excellent durability and recyclability. 相似文献
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E. Kuzmann A. Pákozdi A. Vértes Gy. Láng L. Kiss J. Ensling I. A. Novochatskii L. A. Ianov 《Journal of Radioanalytical and Nuclear Chemistry》1990,146(3):159-168
Electrochemical measurements and Mössbauer spectroscopy were used to study a rapidly quenched Ni80
57Fe1P19 amorphous alloy solution treated between 920 and 1500 °C. Different short range orderings were shown in amorphous alloys solution treated at different temperatures. This finding can be associated with phase separation occurring in the liquid state. This phase separation can be inherited in slightly relaxed amorphous state. 相似文献
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基于尖晶石晶体结构信息,本文采用热力学三亚晶格模型,将材料热力学计算和第一性原理计算相结合,研究了ZnxMn1-x Fe2O4和NixMn1-xFe2O4立方相中的Zn2+、Ni2+、Mn2+以及Fe3+在8a和16d亚晶格上的占位有序化行为。结果表明:在锰铁氧体中,室温下Mn2+完全占据在8a亚晶格上,Fe3+完全占据在16d亚晶格上,属于正尖晶石结构;随着热处理温度升高,在1 273 K达到热处理平衡时的占位构型为(Fe0.093+Mn0.912+)[Fe1.913+Mn0.092+]O4,在热处理温度升至1 473 K时,达到热处理平衡时的占位构型为(Fe0.113+ Mn0.892+)[Fe1.893+Mn0.112+]O4,均与实验结果符合较好。在锌铁氧体中,室温下Zn2+完全占据在8a亚晶格上,Fe3+完全占据在16d亚晶格上,属于正尖晶石结构;在热处理温度较高时,Zn2+和Fe3+发生部分置换,符合实验结果。在镍铁氧体中,半数的Fe3+在室温下占据在8a亚晶格上,Ni2+与剩下另一半的Fe3+共同占据在16d亚晶格上,仅在热处理温度较高的时候发生微弱变化,亦与已有的实验结果吻合。在此基础上,本文进一步通过热力学预测建立了立方相尖晶石结构的ZnxMn1-xFe2O4、NixMn1-xFe2O4复合体系中阳离子占位行为与热处理温度对占位的影响。 相似文献
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Novel magnetic composites (Ni0.5Zn0.5Fe2O4-MWCNTs) of multi-walled carbon nanotubes (MWCNTs) coated with Ni0.5Zn0.5Fe2O4 nanocrystals were synthesized by chemical precipitation-hydrothermal process. The composites were characterized by X-ray powder diffractometer (XRD), X-ray photoelectron spectrometer (XPS), Fourier transform infrared spectroscopy (FTIR), Mössbauer spectroscopy (MS), transmission electron microscopy (TEM), and selected area electron diffraction (SAED), etc. A temperature of about 200 °C was identified to be an appropriate hydrothermal condition to obtain Ni0.5Zn0.5Fe2O4-MWCNTs, being lower than the synthesis temperature of a single-phase Ni0.5Zn0.5Fe2O4 nanocrystals. The sizes of Ni0.5Zn0.5Fe2O4 in the composites were smaller than those of Ni0.5Zn0.5Fe2O4 nanocrystals in single phase. The composites exhibited more superparamagnetic than Ni0.5Zn0.5Fe2O4 nanocrystals in their relaxation behaviors. The magnetic properties measured by a vibrating sample magnetometer showed that the composites had a high coercive field of 386.0 Oe at room temperature, higher than those of MWCNT and Ni0.5Zn0.5Fe2O4 nanocrystals. 相似文献
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完全还原的NixCu1-xFe2O4(x=0.25,0.5,0.75)可用来分解CO2。采用共沉淀法制备了NixCu1-xFe2O4(x=0.25,0.5,0.75)系列铁酸盐的纳米微粒,利用H2-TG数据分析NixCu1-xFe2O4(x=0.25,0.5,0.75)中Cu2+的还原反应动力学数据,得出表观活化能Ea并不是单纯随着Ni2+或Cu2+含量的变化而变化,当x=0.25时反应活化能具有最大值。通过CO2-TG比较不同样品经H2完全还原后分解CO2的活性,得出Ni0.5Cu0.5Fe2O4具有最低的起始反应温度和最大的分解活性,并采用XRDRietveld拟合方法对Ni0.5Cu0.5Fe2O4的完全还原产物和分解CO2产物进行物相分析。 相似文献