Khoudiakov, Mikhail and Parise, Alejandro R. and Brunschwig, Bruce S. (2003) Interfacial Electron Transfer in Fe^(II)(CN)_6^(4-)−Sensitized TiO_2 Nanoparticles: A Study of Direct Charge Injection by Electroabsorption Spectroscopy. Journal of the American Chemical Society, 125 (15). pp. 4637-4642. ISSN 0002-7863. doi:10.1021/ja0299607. https://resolver.caltech.edu/CaltechAUTHORS:20170421-152324583
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Abstract
Electroabsorption (Stark) spectroscopy has been used to study the dye sensitized interfacial electron transfer in an Fe^(II)(CN)_6^(4-) donor complex bound to a TiO_2 nanoparticle. The average charge-transfer distance determined from the Stark spectra is 5.3 Å. This value is similar to the estimated distance between the Fe^(II) center of the complex and the Ti^(IV) surface site coordinated to the nitrogen end of a bridging CN ligand in (CN)_5Fe^(II)−CN−Ti^(IV)(particle). This finding suggests that the electron injection is to either an individual titanium surface site or a small number of Ti centers localized around the point of ferrocyanide coordination to the particle and not into a conduction band orbital delocalized over the nanoparticle. The polarizability change, Tr(Δα), between the ground and the excited states of the Fe^(II)(CN)_6^(4-)−TiO_2(particle) system is ∼3 time larger than normally observed in mixed-valence dinuclear metal complexes. It is proposed that the large polarizability of the excited state increases the dipole-moment changes measured by Stark spectroscopy.
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| Additional Information: | © 2003 American Chemical Society. Received December 30, 2002. Publication Date (Web): March 19, 2003. The authors would like to thank Dr. Jonathan Hanson for obtaining X-ray powder diffraction data, Dr. Janet Petroski for help with TEM studies and Dr. Norman Sutin for helpful discussions. The work was supported by the U.S. Department of Energy, Division of Chemical Sciences, under Contract No. DE-AC02-98CH10886. | |||||||||
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| Issue or Number: | 15 | |||||||||
| DOI: | 10.1021/ja0299607 | |||||||||
| Record Number: | CaltechAUTHORS:20170421-152324583 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20170421-152324583 | |||||||||
| Official Citation: | Interfacial Electron Transfer in FeII(CN)64-−Sensitized TiO2 Nanoparticles: A Study of Direct Charge Injection by Electroabsorption Spectroscopy Mikhail Khoudiakov, Alejandro R. Parise, and Bruce S. Brunschwig Journal of the American Chemical Society 2003 125 (15), 4637-4642 DOI: 10.1021/ja0299607 | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 76829 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Tony Diaz | |||||||||
| Deposited On: | 24 Apr 2017 14:37 | |||||||||
| Last Modified: | 15 Nov 2021 17:03 |
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