Taking Advantage of a Systematic Energy Non-linearity Error in Density Functional Theory for the Calculation of Electronic Energy Levels
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Updated: Oct 11, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry
Published on: April 8, 2020
Bun Chan1, William Dawson2, Takahito Nakajima2
1Graduate School of Engineering, Nagasaki University, Bunkyo 1-14, Nagasaki 852-8521, Japan.
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.
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