2019
DOI: 10.1149/2.0241905jes
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Practical Aspects of Cyclic Voltammetry: How to Estimate Reduction Potentials When Irreversibility Prevails

Abstract: What is the best approach for estimating standard electrochemical potentials, E (0) , from voltammograms that exhibit chemical irreversibility? The lifetimes of the oxidized or reduced forms of the majority of known redox species are considerably shorter than the voltammetry acquisition times, resulting in irreversibility and making the answer to this question of outmost importance. Halfwave potentials, E (1/2) , provide the best experimentally obtainable representation of E (0) . Due to irreversible oxidati… Show more

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Cited by 200 publications
(206 citation statements)
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“…In line with best practice, energy levels were estimated from E 1/2 (when reversibility is observed) or E i (when irreversibility is observed), where E 1/2 is the half‐wave potential and E i is the inflection‐point potential. [ 47 ] HOMO = −( E 1/2 or i + 4.8) eV and LUMO = −( E 1/2 or i + 4.8) eV for oxidation and reduction respectively, with the ferrocene/ferrocenium reference redox system at 4.8 eV below the vacuum level. Electrochemical data for IDT‐di(O) were reanalyzed by the above method to ensure a reliable comparison.…”
Section: Resultsmentioning
confidence: 99%
“…In line with best practice, energy levels were estimated from E 1/2 (when reversibility is observed) or E i (when irreversibility is observed), where E 1/2 is the half‐wave potential and E i is the inflection‐point potential. [ 47 ] HOMO = −( E 1/2 or i + 4.8) eV and LUMO = −( E 1/2 or i + 4.8) eV for oxidation and reduction respectively, with the ferrocene/ferrocenium reference redox system at 4.8 eV below the vacuum level. Electrochemical data for IDT‐di(O) were reanalyzed by the above method to ensure a reliable comparison.…”
Section: Resultsmentioning
confidence: 99%
“…Steady‐state optical spectroscopy provided a means for estimating the excitation energies and testing for solvatochromic behavior of the chromophores . Cyclic voltammetry and spectroelectrochemistry allowed for determining the reduction potentials (needed for estimating the driving forces), and the absorption spectra of the radical ions (needed for the assignments of the TA features of the CT states) …”
Section: Methodsmentioning
confidence: 99%
“…For irreversible oxidations, the half-peak potentials (E (p/2) ) were used to estimate the thermodynamic oxidation potential (E(S + /S)). 48 For DPP dye , an irreversible oxidation is observed with a potential of +1.22 V vs. normal hydrogen electrode (NHE) in DMF solution and of +1.29 V vs. NHE for the mITO|DPP dye electrode in MeCN (Fig. S8 †).…”
Section: Electrochemical Propertiesmentioning
confidence: 98%