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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Bibliographic Details
Main Authors: Blobner, Florian (Author) , Zharnikov, Michael (Author)
Format: Article (Journal)
Language:English
Published: January 17, 2012
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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Summary: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.
Item Description:Gesehen am 10.10.2018
Physical Description:Online Resource
ISSN:1948-7185
DOI:10.1021/jz2015567