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Calculations of ionization energies and electron affinities for atoms and molecules: A comparative study with different methods

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Frontiers of Chemistry in China

Abstract

In the present work, we examined the performance of 36 density functionals, including the newly developed doubly hybrid density functional XYG3 (Y. Zhang, X. Xu, and W. A. Goddard III, Proc. Natl. Acad. Sci, USA, 2009, 106, 4963), to calculate ionization energies (IEs) and electron affinities (EAs). We used the well-established G2-1 set as reference, which contains 14 atoms and 24 molecules for IE, along with 7 atoms and 18 molecules for EA. XYG3 leads to mean absolute deviations (MADs) of 0.057 and 0.080 eV for IEs and EAs, respectively, using the basis set of 6-311 + G (3df,2p). In comparison with some other functionals, MADs for IEs are 0.109 (B2PLYP), 0.119 (M06-2X), 0.159 (X3LYP), 0.161 (PBE), 0.162 (B3LYP), 0.165 (PBE0), 0.173 (TPSS), 0.200 (BLYP), and 0.215 eV (LC-BLYP). MADs for EAs are 0.090 (X3LYP), 0.090 (B2PLYP), 0.102 (PBE), 0.103 (M06-2X), 0.104 (TPSS), 0.105 (BLYP), 0.106 (B3LYP), 0.126 (LC-BLYP), and 0.128 eV (PBE0).

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Authors and Affiliations

  1. State Key Laboratory of Physical Chemistry of Solid Surfaces; College for Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China

    Neil Qiang Su, Igor Ying Zhang & Xin Xu

  2. Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials, MOE Laboratory for Computational Physical Science, Department of Chemistry, Fudan University, Shanghai, 200433, China

    Igor Ying Zhang, Jianming Wu & Xin Xu

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  1. Neil Qiang Su
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  2. Igor Ying Zhang
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Correspondence to Jianming Wu.

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Su, N.Q., Zhang, I.Y., Wu, J. et al. Calculations of ionization energies and electron affinities for atoms and molecules: A comparative study with different methods. Front. Chem. China 6, 269–279 (2011). https://doi.org/10.1007/s11458-011-0256-3

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