Guiglion, P;
Monti, A;
Zwijnenburg, MA;
(2017)
Validating a Density Functional Theory Approach for Predicting the Redox Potentials Associated with Charge Carriers and Excitons in Polymeric Photocatalysts.
Journal of Physical Chemistry C
, 121
(3)
pp. 1498-1506.
10.1021/acs.jpcc.6b11133.
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Abstract
We compare, for a range of conjugated polymers relevant to water-splitting photocatalysis, the predictions for the redox potentials associated with charge carriers and excitons by a total-energy ΔDFT approach to those measured experimentally. For solid-state potentials, of the different classes of potentials available experimentally for conjugated polymers, the class measured under conditions which are the most similar to those during water splitting, we find a good fit between the ionization potentials predicted using ΔB3LYP and those measured experimentally using photoemission spectroscopy (PES). We also observe a reasonable fit to the more limited data sets of excited-state ionization potentials, obtained from two-photon PES, and electron affinities, measured by inverse PES, respectively. Through a comparison of solid-state potentials with gas phase and solution potentials for a range of oligomers, we demonstrate how the quality of the fit to experimental solid-state data is probably the result of benign error cancellation. We discuss that the good fit for solid-state potentials in vacuum suggests that a similar accuracy can be expected for calculations on solid-state polymers interfaced with water. We also analyze the quality of approximating the ΔB3LYP potentials by orbital energies. Finally, we discuss what a comparison between experimental and predicted potentials teaches us about conjugated polymers as photocatalysts, focusing specifically on the large exciton-binding energy in these systems and the mechanism of free charge carrier generation.
| Type: | Article |
|---|---|
| Title: | Validating a Density Functional Theory Approach for Predicting the Redox Potentials Associated with Charge Carriers and Excitons in Polymeric Photocatalysts |
| Open access status: | An open access version is available from UCL Discovery |
| DOI: | 10.1021/acs.jpcc.6b11133 |
| Language: | English |
| Additional information: | This is an open access article published under a Creative Commons Attribution (CC-BY) License, which permits unrestricted use, distribution and reproduction in any medium, provided the author and source are cited. |
| Keywords: | Science & Technology, Physical Sciences, Technology, Chemistry, Physical, Nanoscience & Nanotechnology, Materials Science, Multidisciplinary, Chemistry, Science & Technology - Other Topics, Materials Science, GRAPHITIC CARBON NITRIDE, DRIVEN HYDROGEN EVOLUTION, ULTRAVIOLET PHOTOELECTRON-SPECTROSCOPY, ACCURATE IONIZATION-POTENTIALS, VISIBLE-LIGHT, RATIONAL DESIGN, ELECTRON-AFFINITIES, GEOMETRIC STRUCTURES, CONJUGATED POLYMERS, THIN-FILMS |
| UCL classification: | UCL UCL > Provost and Vice Provost Offices > UCL BEAMS UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences UCL > Provost and Vice Provost Offices > UCL BEAMS > Faculty of Maths and Physical Sciences > Dept of Chemistry |
| URI: | https://discovery.ucl.ac.uk/id/eprint/1550539 |
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