Hot Hole Hopping in a Polyoxotitanate Cluster Terminated with Catechol Electron Donors
| Autor: | Jianhua Bao, Jason B. Benedict, Zhihao Yu, Lars Gundlach, Robert C. Snoeberger, Piotr Piotrowiak, Victor S. Batista, Philip Coppens |
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| Rok vydání: | 2016 |
| Předmět: |
Catechol
Quantum dynamics Exciton 02 engineering and technology Electron 010402 general chemistry 021001 nanoscience & nanotechnology 01 natural sciences Molecular physics 0104 chemical sciences Surfaces Coatings and Films Electronic Optical and Magnetic Materials chemistry.chemical_compound General Energy chemistry Cluster (physics) Physical and Theoretical Chemistry Atomic physics 0210 nano-technology Spectroscopy HOMO/LUMO Excitation |
| Zdroj: | The Journal of Physical Chemistry C. 120:20006-20015 |
| ISSN: | 1932-7455 1932-7447 |
| Popis: | Fast hole hopping in Ti17cat4, a 1 nm diameter molecular polyoxotitanate cluster bearing four catechol ligands (Ti17(μ4-O)4(μ3-O)16(μ2-O)4(cat)4(OPri)16), was investigated by ultrafast spectroscopy and quantum dynamics simulations. The catechol moieties coupled to the TiO2 core of the cluster give rise to a charge-transfer band, the excitation of which promotes an electron from the highest occupied molecular orbital of the ligand to the inorganic core, resulting in the formation of {cat+•,Ti3+}, a vibrationally hot polaronic exciton. Dynamic depolarization measurements indicate that within less than 100 fs the Franck–Condon polaronic state formed at the interface evolves into a fully charge-separated state and the injected electron delocalizes over the quasi conduction band of the cluster. The positive charge (hole) resulting from the injection does not remain static either. The initial hole hopping between the catechol sites occurs with the rate of ∼5 × 1011 s–1 or more and competes with the intramolecul... |
| Databáze: | OpenAIRE |
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