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

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

Research output: Contribution to journalArticle

41 Citations (Scopus)

Abstract

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 (US)
Pages (from-to)2845-2848
Number of pages4
JournalJournal of Molecular Modeling
Volume19
Issue number7
DOIs
StatePublished - Jul 2013

Fingerprint

Polycyclic Aromatic Hydrocarbons
polycyclic aromatic hydrocarbons
Polycyclic aromatic hydrocarbons
Discrete Fourier transforms
methodology
thermodynamic cycles
energy
Thermodynamics
costs
Oxidation
requirements
oxidation
Molecules
Oxidation-Reduction
Costs
molecules

Keywords

  • HOMO
  • Linear correlation
  • LUMO
  • Oxidation
  • Reduction

ASJC Scopus subject areas

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

Cite this

@article{5d223fe018424fca9bffe229849e921d,
title = "Simple and accurate correlation of experimental redox potentials and DFT-calculated HOMO/LUMO energies of polycyclic aromatic hydrocarbons",
abstract = "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.",
keywords = "HOMO, Linear correlation, LUMO, Oxidation, Reduction",
author = "M{\'e}ndez-Hern{\'a}ndez, {Dalvin D.} and Tarakeshwar Pilarisetty and Devens Gust and Thomas Moore and Ana Moore and Vladimiro Mujica",
year = "2013",
month = "7",
doi = "10.1007/s00894-012-1694-7",
language = "English (US)",
volume = "19",
pages = "2845--2848",
journal = "Journal of Molecular Modeling",
issn = "1610-2940",
publisher = "Springer Verlag",
number = "7",

}

TY - JOUR

T1 - Simple and accurate correlation of experimental redox potentials and DFT-calculated HOMO/LUMO energies of polycyclic aromatic hydrocarbons

AU - Méndez-Hernández, Dalvin D.

AU - Pilarisetty, Tarakeshwar

AU - Gust, Devens

AU - Moore, Thomas

AU - Moore, Ana

AU - Mujica, Vladimiro

PY - 2013/7

Y1 - 2013/7

N2 - 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.

AB - 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.

KW - HOMO

KW - Linear correlation

KW - LUMO

KW - Oxidation

KW - Reduction

UR - http://www.scopus.com/inward/record.url?scp=84879788532&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84879788532&partnerID=8YFLogxK

U2 - 10.1007/s00894-012-1694-7

DO - 10.1007/s00894-012-1694-7

M3 - Article

VL - 19

SP - 2845

EP - 2848

JO - Journal of Molecular Modeling

JF - Journal of Molecular Modeling

SN - 1610-2940

IS - 7

ER -