Limiting factors in the accuracy of DFT calculation for redox potentials

Abstract In the present study, we have investigated factors affecting the accuracy of computational chemistry calculation of redox potentials, namely the gas‐phase ionization energy (IE) and electron affinity (EA), and the continuum solvation effect. In general, double‐hybrid density functional theory methods yield IEs and EAs that are on average within ~0.1 eV of our high‐level W3X‐L benchmark, with the best performing method being DSD‐BLYP/ma‐def2‐QZVPP. For lower‐cost methods, the average errors are ~0.2–0.3 eV, with ω B97X‐3c being the most accurate (~0.15 eV). For the solvation component, essentially all methods have an average error of ~0.3 eV, which shows the limitation of the continuum solvation model. Curiously, the directly calculated redox potentials show errors of ~0.3 eV for all methods. These errors are notably smaller than what can be expected from error propagation with the two components (IE and EA, and solvation effect). Such a discrepancy can be attributed to the cancellation of errors, with the lowest‐cost GFN2‐xTB method benefiting the most, and the most accurate ω B97X‐3c method benefiting the least. For organometallic species, the redox potentials show large deviations exceeding ~0.5 eV even for DSD‐BLYP. The large errors are attributed to those for the gas‐phase IEs and EAs, which represents a major barrier to the accurate calculation of redox potentials for such systems.