Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory

Büsra Dereli, Manuel A. Ortuño, Chris Cramer

Research output: Contribution to journalArticle

1 Citation (Scopus)

Abstract

Copper is ubiquitous and its one-electron redox chemistry is central to many catalytic processes. 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-CCSD(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-X functional performs best with a mean unsigned error (MUE) of 0.22 eV. PBE0, ωB97X-D, CAM-B3LYP, M11-L, B3LYP, and M11 exhibit MUEs ranging between 0.23 and 0.34 eV. When including relativistic effects with the zero-order regular approximation, ωB97X-D, CAM-B3LYP, and PBE0 are found to provide the best accuracy.

Original languageEnglish (US)
Pages (from-to)959-966
Number of pages8
JournalChemPhysChem
Volume19
Issue number8
DOIs
StatePublished - Apr 17 2018

Fingerprint

computer aided manufacturing
Ionization potential
Computer aided manufacturing
Density functional theory
Copper
Copper compounds
chemistry
copper compounds
density functional theory
ionization
copper
relativistic effects
Wave functions
functionals
Electronic structure
wave functions
electronic structure
Ligands
Oxidation
ligands

Keywords

  • copper
  • density functional calculations
  • ionization energy
  • relativistic effects
  • wave function theory

PubMed: MeSH publication types

  • Journal Article
  • Research Support, U.S. Gov't, Non-P.H.S.

Cite this

Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory. / Dereli, Büsra; Ortuño, Manuel A.; Cramer, Chris.

In: ChemPhysChem, Vol. 19, No. 8, 17.04.2018, p. 959-966.

Research output: Contribution to journalArticle

@article{4b7201bfdbd84e21887cd7b8b750bd8f,
title = "Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory",
abstract = "Copper is ubiquitous and its one-electron redox chemistry is central to many catalytic processes. 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-CCSD(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-X functional performs best with a mean unsigned error (MUE) of 0.22 eV. PBE0, ωB97X-D, CAM-B3LYP, M11-L, B3LYP, and M11 exhibit MUEs ranging between 0.23 and 0.34 eV. When including relativistic effects with the zero-order regular approximation, ωB97X-D, CAM-B3LYP, and PBE0 are found to provide the best accuracy.",
keywords = "copper, density functional calculations, ionization energy, relativistic effects, wave function theory",
author = "B{\"u}sra Dereli and Ortu{\~n}o, {Manuel A.} and Chris Cramer",
year = "2018",
month = "4",
day = "17",
doi = "10.1002/cphc.201701334",
language = "English (US)",
volume = "19",
pages = "959--966",
journal = "ChemPhysChem",
issn = "1439-4235",
publisher = "Wiley-VCH Verlag",
number = "8",

}

TY - JOUR

T1 - Accurate Ionization Energies for Mononuclear Copper Complexes Remain a Challenge for Density Functional Theory

AU - Dereli, Büsra

AU - Ortuño, Manuel A.

AU - Cramer, Chris

PY - 2018/4/17

Y1 - 2018/4/17

N2 - Copper is ubiquitous and its one-electron redox chemistry is central to many catalytic processes. 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-CCSD(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-X functional performs best with a mean unsigned error (MUE) of 0.22 eV. PBE0, ωB97X-D, CAM-B3LYP, M11-L, B3LYP, and M11 exhibit MUEs ranging between 0.23 and 0.34 eV. When including relativistic effects with the zero-order regular approximation, ωB97X-D, CAM-B3LYP, and PBE0 are found to provide the best accuracy.

AB - Copper is ubiquitous and its one-electron redox chemistry is central to many catalytic processes. 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-CCSD(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-X functional performs best with a mean unsigned error (MUE) of 0.22 eV. PBE0, ωB97X-D, CAM-B3LYP, M11-L, B3LYP, and M11 exhibit MUEs ranging between 0.23 and 0.34 eV. When including relativistic effects with the zero-order regular approximation, ωB97X-D, CAM-B3LYP, and PBE0 are found to provide the best accuracy.

KW - copper

KW - density functional calculations

KW - ionization energy

KW - relativistic effects

KW - wave function theory

UR - http://www.scopus.com/inward/record.url?scp=85042353128&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85042353128&partnerID=8YFLogxK

U2 - 10.1002/cphc.201701334

DO - 10.1002/cphc.201701334

M3 - Article

VL - 19

SP - 959

EP - 966

JO - ChemPhysChem

JF - ChemPhysChem

SN - 1439-4235

IS - 8

ER -