期刊
JOURNAL OF PHYSICAL CHEMISTRY C
卷 121, 期 3, 页码 1498-1506出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpcc.6b11133
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资金
- UK Engineering and Physical Sciences Research Council (EPSRC) [EP/1004424/1, EP/N004884/1]
- EPSRC [EP/L000202/1]
- EPSRC National Centre for Computational Chemistry Software (NCCCS)
- EPSRC [EP/I004424/1, EP/L000202/1, EP/N004884/1] Funding Source: UKRI
- Engineering and Physical Sciences Research Council [EP/I004424/1, EP/L000202/1, EP/N004884/1] Funding Source: researchfish
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 Delta DFT approach to those measured experimentally. For solid-state potentials, 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 Delta B3LYP 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 Delta B3LYP 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.
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