极化率
偶极子
各向同性
各向异性
穆利肯种群分析
电荷(物理)
化学
电场
人口
密度泛函理论
分子物理学
分子
原子物理学
计算化学
物理
量子力学
人口学
有机化学
社会学
作者
Mei Ye,Andrew C. Simmonett,Frank C. Pickard,Robert A. DiStasio,Bernard R. Brooks,Yihan Shao
标识
DOI:10.1021/acs.jpca.5b03159
摘要
In order to carry out a detailed analysis of the molecular static polarizability, which is the response of the molecule to a uniform external electric field, the molecular polarizability was computed using the finite-difference method for 21 small molecules, using density functional theory. Within nine charge population schemes (Löwdin, Mulliken, Becke, Hirshfeld, CM5, Hirshfeld-I, NPA, CHELPG, MK-ESP) in common use, the charge fluctuation contribution is found to dominate the molecular polarizability, with its ratio ranging from 59.9% with the Hirshfeld or CM5 scheme to 96.2% with the Mulliken scheme. The Hirshfeld-I scheme is also used to compute the other contribution to the molecular polarizability coming from the induced atomic dipoles, and the atomic polarizabilities in eight small molecules and water pentamer are found to be highly anisotropic for most atoms. Overall, the results suggest that (a) more emphasis probably should be placed on the charge fluctuation terms in future polarizable force field development and (b) an anisotropic polarizability might be more suitable than an isotropic one in polarizable force fields based entirely or partially on the induced atomic dipoles.
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