Accurate density functional prediction of molecular electron affinity with the scaling corrected Kohn-Sham frontier orbital energies

作者：Zhang, DaDi; Yang, Xiaolong; Zheng, Xiao^*; Yang, Weitao^*

来源：Molecular Physics, 2018, 116(7-8): 927-934.

DOI：10.1080/00268976.2017.1382738

• Density functional theory
• scaling correction approach
• electron affinity
• Kohn-Sham frontier orbital energy
• orbital relaxation

Electron affinity (EA) is the energy released when an additional electron is attached to an atom or a molecule. EA is a fundamental thermochemical property, and it is closely pertinent to other important properties such as electronegativity and hardness. However, accurate prediction of EA is difficult with density functional theory methods. The somewhat large error of the calculated EAs originates mainly from the intrinsic delocalisation error associated with the approximate exchange--correlation functional. In this work, we employ a previously developed non-empirical global scaling correction approach, which explicitly imposes the Perdew-Parr-Levy-Balduz condition to the approximate functional, and achieve a substantially improved accuracy for the calculated EAs. In our approach, the EA is given by the scaling corrected Kohn-Sham lowest unoccupied molecular orbital energy of the neutral molecule, without the need to carry out the self-consistent-field calculation for the anion.

• 出版日期2018
• 单位中国科学技术大学