biostudies-literatureUnknown7(49)Malcomson TSuitability of single-reference density functional theory (DFT) methods for the calculation of redox potentials of copper-containing macrocycle complexes was confirmed by the use of <i>T</i> ₁ diagnostics along with a verification of negligible spin contamination or wave function instability. When examining the effect of improvement in the cc-pV<i>n</i>Z basis set series on calculated redox potentials, the results readily converged at the cc-pVTZ level. The all-electron Def2-TZVPP basis set is shown to be a suitable choice of a basis set for the calculation of redox potentials when utilizing a cc-pVTZ geometry. The best-performing model chemistries are determined to be the M06/polarizable continuum model (PCM); therefore, a scheme for redox potential calculations of copper macrocycles using either M06/cc-pVTZ with PCM solvation is proposed to reliably reproduce experimental trends.ACS omega45057-45066https://www.ebi.ac.uk/biostudies/studies/S-EPMC9753522biostudies-literatureProtocols for Understanding the Redox Behavior of Copper-Containing Systems.PMC9753522Malcomson TRepiscak PErhardt SPaterson MJfalseProtocols for Understanding the Redox Behavior of Copper-Containing Systems.Suitability of single-reference density functional theory (DFT) methods for the calculation of redox potentials of copper-containing macrocycle complexes was confirmed by the use of <i>T</i> ₁ diagnostics along with a verification of negligible spin contamination or wave function instability. When examining the effect of improvement in the cc-pV<i>n</i>Z basis set series on calculated redox potentials, the results readily converged at the cc-pVTZ level. The all-electron Def2-TZVPP basis set is shown to be a suitable choice of a basis set for the calculation of redox potentials when utilizing a cc-pVTZ geometry. The best-performing model chemistries are determined to be the M06/polarizable continuum model (PCM); therefore, a scheme for redox potential calculations of copper macrocycles using either M06/cc-pVTZ with PCM solvation is proposed to reliably reproduce experimental trends.2022-01-01T00:00:00Z2022 Dec2025-04-18T16:31:19.196Z2025-04-07T03:46:56.129ZS-EPMC97535223653029910.1021/acsomega.2c05484