Simple and accurate correlation of experimental redox potentials and DFT-calculated HOMO/LUMO energies of polycyclic aromatic hydrocarbons

Dalvin D. Méndez-Hernández, Pilarisetty Tarakeshwar, Devens Gust, Thomas A. Moore, Ana L. Moore, Vladimiro Mujica

Research output: Contribution to journalArticle

49 Citations (Scopus)


The ability to accurately predict the oxidation and reduction potentials of molecules is very useful in various fields and applications. Quantum mechanical calculations can be used to access this information, yet sometimes the usefulness of these calculations can be limited because of the computational requirements for large systems. Methodologies that yield strong linear correlations between calculations and experimental data have been reported, however the balance between accuracy and computational cost is always a major issue. In this work, linear correlations (with an R2 value of up to 0.9990) between DFT-calculated HOMO/LUMO energies and 70 redox potentials from a series of 51 polycyclic aromatic hydrocarbons (obtained from the literature) are presented. The results are compared to previously reported linear correlations that were obtained with a more expensive computational methodology based on a Born-Haber thermodynamic cycle. It is shown in this article that similar or better correlations can be obtained with a simple and cheaper calculation.

Original languageEnglish
Pages (from-to)2845-2848
Number of pages4
JournalJournal of Molecular Modeling
Issue number7
Publication statusPublished - Jul 1 2013



  • HOMO
  • LUMO
  • Linear correlation
  • Oxidation
  • Reduction

ASJC Scopus subject areas

  • Catalysis
  • Computer Science Applications
  • Physical and Theoretical Chemistry
  • Organic Chemistry
  • Computational Theory and Mathematics
  • Inorganic Chemistry

Cite this