高等学校化学学报

高等学校化学学报

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一些密度泛函方法预测电子亲和势

丁秀丽, 吴剑鸣, 徐昕   

  1. 厦门大学固体表面物理化学国家重点实验室, 化学化工学院, 厦门 361005
  • 收稿日期:2007-11-15 修回日期:1900-01-01 出版日期:2008-02-10 发布日期:2008-02-10
  • 通讯作者: 吴剑鸣

Performance of Some Density Functional Methods in the Prediction of the Adiabatic Electron Affinities

DING Xiu-Li, WU Jian-Ming*, XU Xin   

  1. State Key Laboratory for Physical Chemistry of Solid Surfaces, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China
  • Received:2007-11-15 Revised:1900-01-01 Online:2008-02-10 Published:2008-02-10
  • Contact: WU Jian-Ming

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被引次数

6

摘要： 选取了杂化泛函B3LYP, B3PW91, O3LYP, PBE0, 以及与之相对应的GGA泛函BLYP, BPW91, OLYP和PBE, 还选取了能更好地兼顾强相互作用和弱相互作用的X3LYP泛函和在预测NMR的化学位移有较好表现的OPBE泛函, 以及两种meta-GGA泛函VSXC和TPSS, 共12种泛函, 详细地考察了这些泛函在预测EA方面的准确性.

关键词: 密度泛函理论, 电子亲和势, B3LYP, X3LYP

Abstract: In this paper, we examined the performance of 12 density functionals(B3LYP, X3LYP, O3LYP, PBE0, B3PW91, BLYP, OLYP, OPBE, PBE, BPW91,VSXC and TPSS), combined with two basis sets[DZP++ and 6-311+G(3df,2p)] in the prediction of the adiabatic electron affinities against a set of 91 well-established experimental values. We have reached a conclusion that all these modern functionals are ge-nerally good, giving a mean absolute deviation(MAD) less than 0.24 eV. B3LYP and X3LYP are among the most reliable methods for this test set. When the DZP++ basis set is adopted, X3LYP is the best with a MAD of 0.14 eV, while B3LYP leads to a MAD of 0.16 eV. When the basis set is extended to 6-311+G(3df,2p), B3LYP improves its MAD to 0.13 eV, while the MAD of X3LYP remains to be 0.14 eV. Most hybrid functionals outperform the corresponding GGA functinals, with the exception of PBE0. The meta-GGA functionals(VSXC and TPSS) are not necessarily better than the GGA functionals. Our calculations also reveal that there are flaws associated with the OPTX exchange functional in the calculations of EA.

Key words: Density functional theory, Electron affinity, B3LYP, X3LYP

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