Taking Advantage of a Systematic Energy Non-linearity Error in Density Functional Theory for the Calculation of Electronic Energy Levels.

Abstract

We present an approximate approach for the calculation of ionization potential (IP) and electron affinity (EA) by exploiting the complementary energy non-linearity errors for a species M and its one-electron-ionized counterpart (M+). Reasonable IPs and EAs are thus obtained by averaging the orbital energies of M and M+, even with a low-level method such as BLYP/6-31G(d). By combining the corrected IPs and EAs, we can further obtain reasonable excitation energies. The errors in uncorrected valence IPs and uncorrected virtual-orbital energies show systematic trends. These characteristics provide a convenient and computationally efficient avenue for qualitative estimation of these properties with single corrections for multiple IPs and excitation energies.