二甲基亚砜团簇生长行为中氢键协同效应的密度泛函理论研究
Density functional theory study on the dihydrogen bond cooperativity in the growth behavior of dimethyl sulfoxide clusters
摘要：
本文采用密度泛函理论对DMSO团簇的结构进行了研究，并利用分子静电势和分子中原子的量子理论（QTAIM）对团簇的结构和稳定性进行了分析。DMSO团簇的基态几何构型更倾向于以衔尾蛇的形式存在。两两相互作用能的计算表明，相邻的DMSO分子的甲基之间的相互作用和不稳定是由甲基，这是彼此远离。分子静电势分析表明，在奇数簇上存在空穴，这有助于它们的高度定向生长。QTAIM分析表明，分子间存在两个氢键，SOC型氢键和甲基CHC型氢键。计算值和Laplacian值均为正的分子间键，支持非共价相互作用的存在。计算得到的氢键椭圆率大于2，证实了电子的离域性，主要是由于甲基的氢-氢相互作用。总氢键能与所观察到的总局域电子密度的关系曲线显示出线性关系，相关系数接近1，这表明分子间二氢HH键的协同效应。
英文摘要：
We have carried out a density functional theory study on the structures of DMSO clusters and analysed the structure and their stability using molecular electrostatic potential and quantum theory of atoms-in-molecules (QTAIM). The ground state geometry of the DMSO clusters, prefer to exist in ouroboros shape. Pair wise interaction energy calculation show the interaction between methyl groups of adjacent DMSO molecules and a destabilization is is created by the methyl groups which are away from each other. Molecular electrostatic potential analysis shows the existence of hole on the odd numbered clusters, which helps in their highly directional growth. QTAIM analysis show the existence of two intermolecular hydrogen bonds, of type SOC hydrogen bonds and methyl CHC dihydrogen bonds. The computed and Laplacian values were all positive for the intermolecular bonds, supporting the existence of noncovalent interactions. The computed ellipticity for the dihydrogen bonds have values > 2, which confirms the delocalization of electron, are mainly due to the hydrogen-hydrogen interactions of methyl groups. A plot of total hydrogen bonding energy vs the observed total local electron density shows linearity with correlation coefficient of near unity, which indicates the cooperative effects of intermolecular dihydrogen HH bonds.
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