Orbital-symmetry-dependent electron transfer through molecules assembled on metal substrates
Femtosecond charge-transfer dynamics in self-assembled monolayers of cyano-terminated ethane-thiolate on gold substrates was investigated with the core hole clock method. By exploiting symmetry selection rules rather than energetic selection, electrons from the nitrogen K-shell are state-selectively...
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| Main Authors: | , |
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| Format: | Article (Journal) |
| Language: | English |
| Published: |
January 17, 2012
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| In: |
The journal of physical chemistry letters
Year: 2012, Volume: 3, Issue: 3, Pages: 436-440 |
| ISSN: | 1948-7185 |
| DOI: | 10.1021/jz2015567 |
| Online Access: | Verlag, Volltext: http://dx.doi.org/10.1021/jz2015567 Verlag, Volltext: https://doi.org/10.1021/jz2015567 
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| Author Notes: | Florian Blobner, Pedro B. Coto, Francesco Allegretti, Michel Bockstedte, Oscar Rubio-Pons, Haobin Wang, David L. Allara, Michael Zharnikov, Michael Thoss, and Peter Feulner |
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| 520 | |a Femtosecond charge-transfer dynamics in self-assembled monolayers of cyano-terminated ethane-thiolate on gold substrates was investigated with the core hole clock method. By exploiting symmetry selection rules rather than energetic selection, electrons from the nitrogen K-shell are state-selectively excited into the two symmetry-split π* orbitals of the cyano end group with X-ray photons of well-defined polarization. The charge-transfer times from these temporarily occupied orbitals to the metal substrate differ significantly. Theoretical calculations show that these two π* orbitals extend differently onto the alkane backbone and the anchoring sulfur atom, thus causing the observed dependence of the electron-transfer dynamics on the symmetry of the orbital. | ||
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