期刊
JOURNAL OF PHYSICAL CHEMISTRY A
卷 119, 期 22, 页码 5865-5882出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpca.5b03159
关键词
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资金
- National Natural Science Foundation of China [21173082]
- China Scholarship Council [201208310344]
- NIH Grant [GM096678-02]
- DOE Grant [DE-SC0011297]
- Intramural Research Program of the NIH, NHLBI
- U.S. Department of Energy (DOE) [DE-SC0011297] Funding Source: U.S. Department of Energy (DOE)
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 (Lowdin, 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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