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Protocols for Understanding the Redox Behavior of Copper-Containing Systems

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

Authors

Thomas Malcomson

Peter Repiščák

Martin J. Paterson



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.

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

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