Electronic Couplings in Organic Mixed-Valence Compounds: The Contribution of Photoelectron Spectroscopy
- 7 February 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Journal of the American Chemical Society
- Vol. 126 (9) , 2727-2731
- https://doi.org/10.1021/ja039263u
Abstract
We show that the electronic coupling in strongly coupled organic mixed-valence systems can be effectively probed by means of gas-phase ultraviolet photoelectron spectroscopy (UPS). Taking six diamines as examples, the UPS estimates for the electronic couplings Hab are compared with the corresponding values determined from the intervalence charge-transfer absorption bands and from electronic structure calculations. Similar trends are observed for the Hab values estimated from UPS and optical spectra; this provides support for the applicability of Hush theory to strongly coupled organic mixed-valence systems. The UPS electronic couplings are found to be somewhat smaller than those from optical spectroscopy, which is attributed to the role of vibronic coupling to symmetrical modes; when corrected for this vibronic coupling, the UPS Hab estimates confirm that triarylamine-based mixed-valence systems are close to the class-II/class-III borderline.This publication has 54 references indexed in Scilit:
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