Ionization Energies and Aqueous Redox Potentials of Organic Molecules: Comparison of DFT, Correlated ab Initio Theory and Pair Natural Orbital Approaches

Miho Isegawa, Frank Neese, Dimitrios A. Pantazis

Research output: Contribution to journalArticle

40 Citations (Scopus)

Abstract

The calculation of redox potentials involves large energetic terms arising from gas phase ionization energies, thermodynamic contributions, and solvation energies of the reduced and oxidized species. In this work we study the performance of a wide range of wave function and density functional theory methods for the prediction of ionization energies and aqueous one-electron oxidation potentials of a set of 19 organic molecules. Emphasis is placed on evaluating methods that employ the computationally efficient local pair natural orbital (LPNO) approach, as well as several implementations of coupled cluster theory and explicitly correlated F12 methods. The electronic energies are combined with implicit solvation models for the solvation energies. With the exception of MP2 and its variants, which suffer from enormous errors arising at least partially from the poor Hartree-Fock reference, ionization energies can be systematically predicted with average errors below 0.1 eV for most of the correlated wave function based methods studies here, provided basis set extrapolation is performed. LPNO methods are the most efficient way to achieve this type of accuracy. DFT methods show in general larger errors and suffer from inconsistent behavior. The only exception is the M06-2X functional which is found to be competitive with the best LPNO-based approaches for ionization energies. Importantly, the limiting factor for the calculation of accurate redox potentials is the solvation energy. The errors in the predicted solvation energies by all continuum solvation models tested in this work dominate the final computed reduction potential, resulting in average errors typically in excess of 0.3 V and hence obscuring the gains that arise from choosing a more accurate electronic structure method.

Original languageEnglish
Pages (from-to)2272-2284
Number of pages13
JournalJournal of Chemical Theory and Computation
Volume12
Issue number5
DOIs
Publication statusPublished - May 10 2016

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Ionization potential
Solvation
Discrete Fourier transforms
ionization
orbitals
Molecules
solvation
molecules
Wave functions
energy
Extrapolation
wave functions
Electronic structure
Density functional theory
Oxidation-Reduction
Gases
Thermodynamics
Oxidation
Electrons
extrapolation

All Science Journal Classification (ASJC) codes

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

Ionization Energies and Aqueous Redox Potentials of Organic Molecules : Comparison of DFT, Correlated ab Initio Theory and Pair Natural Orbital Approaches. / Isegawa, Miho; Neese, Frank; Pantazis, Dimitrios A.

In: Journal of Chemical Theory and Computation, Vol. 12, No. 5, 10.05.2016, p. 2272-2284.

Research output: Contribution to journalArticle

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