密度泛函算法中基组效应对SiOSi链节的结构、能量和非共价键作用的影响(英文)

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以二硅氧烷(H3SiOSiH3)为聚硅氧烷中SiOSi骨架的模型分子,以它与水分子形成1∶1氢键复合物作为SiOSi骨架参与非共价相互作用的模型分子,对二重裂分基组6-31G和三重裂分基组6-311G与不同极化函数和弥散函数组合下对二硅氧烷的几何结构、SiOSi线性化能垒及其非键相互作用的预测能力进行了测评.以B3LYP算法来测试基组效应对几何结构和SiOSi线性化能垒的影响,以PBE1PBE算法来考查基组对非共价相互作用的影响.结果表明:1)二硅氧烷的几何结构与线性化能垒对角动量的依赖性较强,至少要使用(3df,p)以上的角动量才会达到收敛;2)二硅氧烷的非共价相互作用同样也要使用(3df,p)以上的角动量才会达到收敛,同时需要包含零点校正能才能得到合理的结合能,但基组叠加效应对结合能的影响则可忽略. In this paper, siliconyl (H3SiOSiH3) is used as a model molecule of SiOSi skeleton in polysiloxane, which forms a 1: 1 hydrogen bond complex with water molecules as SiOSi framework to participate in noncovalent interaction model molecules, Subbase group 6-31G and triplet subgroup 6-311G were combined with different polarizations and dispersion functions to predict the geometries of disiloxane, the SiOSi linearized barrier and the prediction of their non-bond interactions The B3LYP algorithm was used to test the effect of the basis set effect on the geometrical structure and the SiOSi linear barrier, and PBE1PBE algorithm was used to examine the effect of the basis set on the non-covalent interaction.The results showed that: 1) Which is strongly dependent on the diagonal momentum of the linear energy barrier. At least the angular momentum above (3df, p) should be used to reach convergence. 2) The non-covalent interactions of disiloxanes should also be used (3df, p) above the angular momentum will reach the convergence, at the same time need to include zero correction in order to get a reasonable binding energy, but the effect of the superposition of the base effect on the binding energy can be ignored.
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