Assessment of DFT methods for the prediction of detachment energies and electronic structures of complex and multiply charged anions
| Autor: | Xue-Bin Wang, Zhubin Hu, Fufang Wang, Zhenrong Sun, Haitao Sun |
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| Rok vydání: | 2021 |
| Předmět: |
Work (thermodynamics)
010304 chemical physics Chemistry Radius Electronic structure 010402 general chemistry Condensed Matter Physics 01 natural sciences Biochemistry Molecular physics Electron localization function 0104 chemical sciences Ion Delocalized electron 0103 physical sciences Density functional theory Physical and Theoretical Chemistry Adiabatic process |
| Zdroj: | Computational and Theoretical Chemistry. 1202:113295 |
| ISSN: | 2210-271X |
| Popis: | In this work, we assess the ability of different density functional theory methods to reproduce the vertical/adiabatic detachment energies (VDEs/ADEs) of a series of 40 anions, including monoanions versus multiply charged anions (MCAs) and covalent versus noncovalent interaction. The statistical analysis of errors is firstly performed by comparing the theoretical values with the experimental benchmark data obtained from the negative ion photoelectron spectroscopy (NIPES). The proposed optimally tuned range-separated (OTRS) functionals are proved to not only well reproduce the experimental VDEs/ADEs, but also simulate experimental NIPES. The result implies a more serious issue of delocalization error for MCAs and a balanced description of electron-rich/-deficient region of anions is necessary. The radius of the spherically symmetric average electron localization function (ELF) region is demonstrated as a useful descriptor for the characterization of electronic structure of anionic systems and a quasilinear fitting model is proposed to efficiently obtain their OTRS parameters. |
| Databáze: | OpenAIRE |
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