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基于从晶体锗确立的多体展开势能函数, 本文通过坐标完全优化, 发现小的锗原子簇分子(Ge~2~Ge~14)倾向于形成密堆积结构, 表面原子分布以蝶形四元环(D~2d)为主; 常见立方晶体“微观晶体碎片”的分层优化结果表明, 在Ge~15~Ge~100范围内, 多数壳层的原子到分子中心的距离均受到压缩, 且以畸变的简单立方、面心立方及体心立方较为稳定; 在这些畸变密堆积结构中, 表面原子向内压缩最为严重, 使整个分子趋于球形化。较为开放的金刚石类层状原子族只有当所含原子数达数百以上时才可能相对更为稳定。 相似文献
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本文首次提出了化学反应过程中几何可能性的定量研究.在下列条件下:(1)反应过程中,惰性配位体的键长,立体角系数等参数保持不变;(2)惰性配位体的压缩性很小;(3)在不压缩其它配位体的条件下,某一配位体在配位球面漂移所需的活化能低于这一配位体所形成的化学键断裂时所需的相应能量.我们提出动态堆积模型.以此来模拟反应过程中各个配位体间的相对位置和运动、配位体之间间隙的大小与受压缩的程度,并计算在反应中间过程中能够容纳新的配位体的最大空缺.考虑到使惰性配位体压缩将产生很大的空间势垒,以UCp3X为例说明了Lewis碱的配合与解离;金属-碳σ键的热分解以及一氧化碳插入反应的可能性. 相似文献
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本文用RHF/STO-3G解析梯度方法研究了亚烷基卡宾XYC=C:(X, Y=Cl, H, Me和F)的重排反应, 给出了平衡态与过渡态构型. 对该组体系的计算发现: 基团的迁移活性顺序为Cl>H>Me>F; 迁移性小的基团增大迁移基团的迁移活性; 取代基不同一般比取代基相同的卡宾稳定性低; 基团的迁移活性顺序与电负性顺序不一致; 中心原子与C=C双键夹角小的基团优先迁移. 相似文献
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本文讨论了不同的预处理对Pt电极 pH 响应的影响 。经阴极 极 化或火焰上红热后, Pt电极以Pt(OH)2+Ze-Pt+2OH响应溶液的pH。而经+1.5V(vs.SCE)阳极极化后, 由于Pt电极表面PtO2的快速分解,电极的电位值很快下降, 并逐渐达到稳定值, 稳定后的Pt电极仍以上式响应溶液的pH。用KMnO4溶液浸泡后, Pt电极表面有MnO~2沉积, 并以MnO2+4H^++Ze-Mn^2^++2H2O(PH2-7)ZMnO2+2H^++Ze-Mn2O3+H2O(PH8-12)响应溶液的pH。 相似文献
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动态核磁共振(dynamic nuclear magnetic resonance,DNMR)是研究分子运动现象,获得活化参数的有力工具.有关酰胺类化合物的内旋转势垒已有多人用DNMR方法作过研究.本文用DNMR多重合并方法(multicoalescence)测得N,N-二甲基苯甲酰胺(DMB)及N,N-二乙基苯甲酰胺(DEB)绕C—N键旋转势垒的活化自由能△G~≠.为进一步讨论内旋转势垒的机制,除测量在不同溶剂中的活化参数外,还测定了在相应溶剂中的~(15)N化学位移δ_(16N).线性回归法计算表明,内旋转势垒的活化自由能△G~≠、~(15)N的化学位移δ_(16N)与溶剂性质参数E_T(30)有良好的线性关系.从不同温度下的谱图看出,随着温度升高,交换增快,出现谱线增宽、合并现象(图1). 相似文献
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胺丶醇丶醚类化合物气相碱性的CNDO/2计算 总被引:1,自引:0,他引:1
The gas-phase basicities of compounds can be measured by their proton affinities. In this paper we he calculated the gas-phase basicities of about seventy compounds containing N or O by means of the method CNDO/2. For the alkylamines, alcohols, ethers and carbonyl compounds, computational results agree qualitatively with the experimental values. The sequences of gas-phase basicities for the series of these compounds are as follows: Et2NH>Me3N>t-BuNH2>Me2NH>i-PrNH2>n-BuNH2>n-PrNH2>EtNH2>MeNH2>NH3; Et2O>EtOMe>t-BuOH>Me2O>i-PrOH>n-BuOH>n-PrOH>EtOH>MeOH>H2O; n-PrCHO>EtCHO>MeCHO>HCHO; n-BuCO2H>n-PrCO2H>EtCO2H>MeCO2H>HCO2H; HCO2Bu-n>HCO2Pr-N>HCO2Et>HCO2Me>HCO2H Obviously, alkyl substitution plays a role to increase the gas-phase basicities. The squence of increasing effectiveness is t-Bu>i-Pr>n-Bu>n-Pr>Et>Me For the amines containing heteroatoms investigated here, the gas-phase basicities have the following order repectively: CH3NH2>NH2NH2>NH2OH>NH2F>NHF2>NF3 The gas-phase basicities of these compounds change regularly with various substitutents. For the aliphatic compounds, the gas-phase basicity increases with thosizo and the degree of branching of the alkyl groups. For the amines containing heteroatoms, the gas-phase basicity decreases with increasing of the electro-negativity of the substitutent. For the relationship between the gas-phase basksity and the charge distribution and the ionization potentials, the conclusions are as follows: (1) The gas-phase basicities of the homologous compounds are proportional to the electron density of the atom N or O, but those of Rn NH3-n and Rn OH2-n are inversely proportional to the electron denisty of atom N or O. This shows that the base strength of the molecule cannot be determined solely by the electron density of the individual atom. (2) In the protonation reaction the alkyl groups spread the charges from the charged center. This effect enables protonated cations to become more stable because of the charge distribution av 相似文献