极性分子键角与键偶极矩的关系-北京大学.PDF

物理化学学报(Wuli Huaxue Xuebao) July Acta Phys. -Chim. Sin. 2016, 32 (7), 1639－1648 1639 [Article] doi: 10.3866/PKU.WHXB201604062 极性分子键角与键偶极矩的关系 曹静思 韦美菊 陈飞武* (北京科技大学化学与生物工程学院化学与化学工程系，功能分子与晶态材料科学与应用北京市重点实验室，北京100083) 摘要：研究了基态极性分子的键角和键偶极矩之间的关系。我们采用原子偶极矩校正的Hirshfeld (ADCH) 电 荷来计算键偶极矩，利用电子的局域函数和键临界点处的局域函数值来分析键的电子结构。通过对IVA 族 (IVA = C, Si, Ge)、VA 族(VA = N, P, As )、VIA 族(VIA = O, S, Se)和VIIA 族(VIIA = F, Cl, Br)元素形成的系列共 价型基态分子，以及环状基态分子的键角和键偶极矩数据进行分析，发现在键的电子结构类似的情况下，由 于键偶极矩的排斥作用，这些分子的键角随键偶极矩的增加而增大。这一发现有助于加深我们对分子几何结 构的认识。 关键词：极性分子；键角；键偶极矩；原子电荷；电子局域函数 中图分类号：O641 Relationship between the Bond Dipole Moment and Bond Angle of Polar Molecules CAO Jing-Si WEI Mei-Ju CHEN Fei-Wu* (Department of Chemistry and Chemical Engineering, School of Chemistry and Biological Engineering, University of Science and Technology Beijing; Beijing Key Laboratory for Science and Application of Functional Molecular and Crystalline Materials, Beijing 100083, P. R. China) Abstract: The relationship between the bond angle and bond dipole moment is investigated. The atomic dipole moment corrected Hirshfeld (ADCH) charges are used to calculate the bond dipole moment. The electron localizationfunctionanditsvaluesatthebondcriticalpointsareexploitedtoanalyzethebond′selectronic structures. Through analyzing the data of a series of covalent compounds formed by the IVA (IVA = C, Si, Ge), VA (VA = N, P, As), VIA (VIA = O, S, Se) and VIIA (VIIA = F, Cl, Br) group elements, it is found that, owing to the repulsion of bond dipole moments, the