Accurate Electron Affinities and Orbital Energies of Anions from a Nonempirically Tuned Range-Separated Density Functional Theory Approach

作者：Anderson Lindsey N; Oviedo M Belen; Wong Bryan M^*

来源：Journal of Chemical Theory and Computation, 2017, 13(4): 1656-1666.

DOI：10.1021/acs.jctc.6b01249

The treatment of atomic anions with Kohn Sham density functional theory (DFT) has long been controversial because the highest occupied molecular orbital (HOMO) energy, EHOMO, is often calculated to be positive with most approximate density functionals. We assess the accuracy of orbital energies and electron affinities for all three rows of elements in the periodic table (H-Ar) using a variety of theoretical approaches and customized basis sets. Among all of the theoretical methods studied here, we find that a nonempirically tuned range-separated approach (constructed to satisfy DFT-Koopmans' theorem for the anionic electron system) provides the best accuracy for a variety of basis sets, even for small basis sets where most functionals typically fail. Previous approaches to solve this conundrum of positive E-HOMO values have utilized non-self-consistent methods; however, electronic properties, such as electronic couplings/gradients (which require a self-consistent potential and energy), become ill-defined with these approaches. In contrast, the nonempirically tuned range-separated procedure used here yields well-defined electronic couplings/gradients and correct E-HOMO values because both the potential and resulting electronic energy are computed self-consistently. Orbital energies and electron affinities are further analyzed in the context of the electronic energy as a function of electronic number (including fractional numbers of electrons) to provide a stringent assessment of self-interaction errors for these complex anion systems.

• 出版日期2017-4