QuardokusRC042013D.pdf (37.91 MB)
Scanning Tunneling Microscopy Observations of Neutral and Mixed-Valence Organometallic Complexes
thesis
posted on 2013-04-08, 00:00 authored by Rebecca Carole QuardokusLow-temperature ultra-high-vacuum scanning tunneling microscopy (STM) is used to study di- and trinuclear iron-based organometallic molecules. Chemical oxidation of these molecules leads to mixed-valence species with interesting intramolecular charge-transfer properties. STM images of neutral molecules show symmetrical distribution of electron density across the metal centers because the metal centers are present in the same oxidation state. STM images of mixed-valence molecules show an asymmetric distribution of the electron density, indicating that the metal centers are present in different oxidation states. I have found that the intramolecular charge-transfer rates depend on the geometry of the organic linker between the metal centers, and that these mixed-valence compounds retain their electronic properties when placed on a metal surface in the absence of bulk solvent. Comparison with theoretical STM images derived from constrained-density-functional theory (CDFT) calculations leads to the conclusion that the observed features in the STM images are electronic in nature. Investigation of mixed-valence dinuclear organometallic molecules with asymmetric electron state density may open up the possibility for their use in molecularly based electronic devices.
History
Date Modified
2017-06-02Defense Date
2013-04-04Research Director(s)
Prof. S. Alex KandelCommittee Members
Prof. J. Daniel Gezelter Prof. Prashant Kamat Prof. Marya LiebermanDegree
- Doctor of Philosophy
Degree Level
- Doctoral Dissertation
Language
- English
Alternate Identifier
etd-04082013-105353Publisher
University of Notre DameProgram Name
- Chemistry and Biochemistry
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