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Modeling such chemistry requires electronic structure methods capable of the accurate prediction of ionization energies (IEs) for compounds including copper in different oxidation states and supported by various ligands. Herein, we estimate IEs for 12 mononuclear Cu species previously reported in the literature by using 21 modern density functionals and the DLPNO\u2010CCSD(T) wave function theory model; we consider extrapolated values of the latter to provide reference values of acceptable accuracy. Our results reveal a considerable diversity in functional performance. Although there is nearly always at least one functional that performs well for any given species, there are none that do so for every member of the test set, and certain cases are particularly pathological. Over the entire test set, the SOGGA11\u2010X functional performs best with a mean unsigned error (<jats:italic>MUE<\/jats:italic>) of 0.22\u2005eV. PBE0, \u03c9B97X\u2010D, CAM\u2010B3LYP, M11\u2010L, B3LYP, and M11 exhibit <jats:italic>MUE<\/jats:italic>s ranging between 0.23 and 0.34\u2005eV. When including relativistic effects with the zero\u2010order regular approximation, \u03c9B97X\u2010D, CAM\u2010B3LYP, and PBE0 are found to provide the best accuracy.<\/jats:p>","DOI":"10.1002\/cphc.201701334","type":"journal-article","created":{"date-parts":[[2017,12,16]],"date-time":"2017-12-16T17:14:52Z","timestamp":1513444492000},"page":"959-966","update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":21,"title":["Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory"],"prefix":"10.1002","volume":"19","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-9247-0848","authenticated-orcid":false,"given":"B\u00fcsra","family":"Dereli","sequence":"first","affiliation":[{"name":"Department of Chemistry Supercomputing Institute and Chemical Theory Center University of Minnesota  207 Pleasant St. SE Minneapolis MN 55455-0431 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