Protocols for Understanding the Redox Behavior of Copper-Containing Systems

Malcomson, Thomas; Repiščák, Peter; Erhardt, Stefan; Paterson, Martin J.

Abstract

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 T 1 diagnostics along with a verification of negligible spin contamination or wave function instability. When examining the effect of improvement in the cc-pVnZ 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.

Citation

Malcomson, T., Repiščák, P., Erhardt, S., & Paterson, M. J. (2022). Protocols for Understanding the Redox Behavior of Copper-Containing Systems. ACS Omega, 7(49), 45057-45066. https://doi.org/10.1021/acsomega.2c05484

• Journal Article Type: Article
• Acceptance Date: Nov 9, 2022
• Online Publication Date: Nov 30, 2022
• Publication Date: 2022-12
• Deposit Date: Jan 9, 2023
• Publicly Available Date: Jan 9, 2023
• Journal: ACS Omega
• Print ISSN: 2470-1343
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 7
• Issue: 49
• Pages: 45057-45066
• DOI: https://doi.org/10.1021/acsomega.2c05484
• Public URL: http://researchrepository.napier.ac.uk/Output/2984462