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Cited by 18Advanced Chemical Physics StudiesFree Radicals and AntioxidantsPhysical Organic Chemistry and Reaction Kinetics

The DOI matches its Crossref record; 42 of the 42 references it cites were found in a registry or an index.

DFT benchmark study of the O–O bond dissociation energy in peroxides validated with high-level ab initio calculations

Open access
Carmona, Danilo J., Jaque, Pablo, Vöhringer-Martinez, Esteban·2020·Theoretical Chemistry Accounts
DOI 10.1007/s00214-020-02607-x

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Abstract

Peroxides play a central role in many chemical and biological processes such as the Fenton reaction. The relevance of these compounds lies in the low stability of the O–O bond which upon dissociation results in radical species able to initiate various chemical or biological processes. In this work, a set of 64 DFT functional-basis set combinations has been validated in terms of their capability to describe bond dissociation energies (BDE) for the O–O bond in a database of 14 ROOH peroxides for which experimental values of BDE are available. Moreover, the electronic contributions to the BDE were obtained for four of the peroxides and the anion H2O2-\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\hbox {H}_2\hbox {O}_2^-$$\end{document} at the CBS limit at CCSD(T) level with Dunning’s basis sets up to triple-ζ\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\zeta$$\end{document} quality providing a reference value for the hydrogen peroxide anion as a model. Almost all the functionals considered here yielded mean absolute deviations around 5.0kcalmol-1\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$5.0\hbox { kcal mol}^{-1}$$\end{document}. The smallest values were observed for the ω\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\omega$$\end{document}B97 family and the Minnesota M11 functional with a marked basis set dependence. Despite the mean deviation, order relations among BDE experimental values of peroxides were also considered. The ω\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$$\omega$$\end{document}B97 family was able to reproduce the relations correctly whereas other functionals presented a marked dependence on the chemical nature of the R group. Interestingly, M11 functional did not show a very good agreement with the established order despite its good performance in the mean error. The obtained results support the use of similar validation strategies for proper prediction of BDE or other molecular properties by DFT methods in subsequent related studies.

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Research works printed but not linked: 1

  1. Frisch MJ, Trucks GW, Schlegel HB, Scuseria GE, Robb MA, Cheeseman JR, Scalmani G, Barone V, Mennucci B, Petersson GA, Nakatsuji H, Caricato M, Li X, Hratchian HP, Izmaylov AF, Bloino J, Zheng G, Sonnenberg JL, Hada M, Ehara M, Toyota K, Fukuda R, Hasegawa J, Ishida M, Nakajima T, Honda Y, Kitao O, Nakai H, Vreven T, Montgomery JA Jr, Peralta JE, Ogliaro F, Bearpark M, Heyd JJ, Brothers E, Kudin KN, Staroverov VN, Kobayashi R, Normand J, Raghavachari K, Rendell A, Burant JC, Iyengar SS, Tomasi J, Cossi M, Rega N, Millam JM, Klene M, Knox JE, Cross JB, Bakken V, Adamo C, Jaramillo J, Gomperts R, Stratmann RE, Yazyev O, Austin AJ, Cammi R, Pomelli C, Ochterski JW, Martin RL, Morokuma K, Zakrzewski VG, Voth GA, Salvador P, Dannenberg JJ, Dapprich S, Daniels AD, Farkas Ã, Foresman JB, Ortiz JV, Cioslowski J, Fox DJ (2009) Gaussian 09 revision E.01. Gaussian Inc., Wallingford

Metadata

Authors
Carmona, D. J., Jaque, P., & Vöhringer-Martinez, E.
Affiliations
  • University of Concepción (CL)
  • University of Chile (CL)
ORCID
Venue
Theoretical Chemistry Accounts
Publisher
Springer Science and Business Media LLC
Published
2020-06-04
Volume
139
Issue
7
ISSN
  • 1432-2234 (ISSN-L)
  • 1432-881X
DOI
10.1007/s00214-020-02607-x
OpenAlex
W3033093533
Cited by
18
References
42
Citations by year
2026: 3 · 2025: 6 · 2024: 4 · 2023: 1 · 2022: 2 · 2021: 2
FWCI
0.51
Type
journal article
Language
en
Open access
Licence
Locations
  • Theoretical Chemistry Accounts (publishedVersion)
  • ChemRxiv (acceptedVersion, cc-by-nc-nd)
  • Royal College of Surgeons in Ireland (submittedVersion, cc-by-nc-nd)
  • Universidad de Chile (submittedVersion, cc-by-nc-nd)
Funders
  • Fondo Nacional de Desarrollo Científico y Tecnológico (1160197, 1181914)
  • Conicyt (21131021)
Topics
  • Physical Sciences › Physics and Astronomy › Atomic and Molecular Physics, and Optics › Advanced Chemical Physics Studies
  • Physical Sciences › Chemistry › Organic Chemistry › Free Radicals and Antioxidants
  • Physical Sciences › Chemistry › Organic Chemistry › Physical Organic Chemistry and Reaction Kinetics
Keywords
peroxides, DFT functional benchmarking, basis set effects, Fenton reaction, radical formation

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