UNIVERSITY OF ARIZONA, TUCSON, ARIZONA UNIVERSITY OF ARIZONA, DEPT OF CHEMISTRY
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Dennis L. Lichtenberger
B.S. 1969, Indiana University, Bloomington
Ph.D. 1974, University of Wisconsin, Madison

office CSML 342
email dlichten@u.arizona.edu
phone (520) 621-4749
fax (520) 626-8065

PRINCIPLES OF STRUCTURE AND BONDING IN CHEMICAL REACTIVITY, CATALYSIS, MATERIALS, AND BIOLOGY.

All chemical behavior involves movement of electrons.

A special feature of this research program is the use of photoelectron spectroscopy to obtain an experimental measure of the energies required to remove electrons from large molecules. These energies and other features of the photoionization process reveal much about the factors of electron movement that determine chemical behavior.

Because of the special capabilities in our laboratory and the direct significance of the information we obtain to many important chemical processes, exciting discoveries are being made in several areas. Examples of chemical systems studied in this research program are shown below:

 

Chemical reactivity and catalysis depend on mechanisms that move electrons from existing bonds in starting materials to new bonds in desired products. Movement of electrons in materials is important to electrical conductivity and optical properties for technological applications. In biology, electron transfer involving active metal sites is central to many life processes. This research provides fundamental information for understanding all of these processes. Students choose the area and projects in which they are most interested.

We are particularly interested in the study of molecules with unusual electronic structure and bonding modes. These molecules offer opportunities for unique properties and new applications.  For instance, our discovery of an unusual metal-metal bonded molecule that requires less energy to give up an electron than any atom in the periodic table and any other molecule previously known opens a new realm of behavior with many potential applications.

The figure above depicts some of the activities in our laboratory. We have developed instrumentation for gas-phase photoelectron spectroscopy of large molecules that is not matched elsewhere.  As a consequence, we are often the only source of this information for other researchers. In order to serve the needs for this information, we have established a user facility for gas-phase electron spectroscopy directed by Dr. Nadine Gruhn. We have numerous rewarding collaborations and often share students with other research groups, both within this Department and in other institutions.

In addition to gas-phase photoelectron spectroscopy, the research incorporates special chemical and material preparations, theory and molecular modeling, and many other modern chemical and physical techniques. Intermolecular interactions are investigated by preparation of thin condensed films of molecules in ultrahigh vacuum, and characterized by electron spectroscopy, scanning probe microscopy, and other surface science techniques.


SELECTED PUBLICATIONS

Joshi, H. K.; Cooney, J. A.; Inscore, F. E.; Gruhn, N. E.; Lichtenberger, D. L.; Enemark, J. H. "Investigation of Metal-Dithiolate Fold Angle Effects by Gas-Phase Photoelectron Spectroscopy and Density Functional Calculations: Implications for Molybdenum Enzymes." Proc. Natl. Acad. Sci. U.S.A. 2003, 100 (7), 3719-3724.

Lichtenberger, D. "The Electron Distribution, Bonding, and J(Si-H) NMR Coupling Constant in (05-C5H5)(CO)2MnHSiCl3: The Molecular Orbital View." Organometallics 2003, 22 (8), 1599-1602.

Lichtenberger, D. L.; Fan, H. -J.; Gruhn, N. E. "Ligand-Mediated Metal-Metal Interactions and Localized versus Delocalized Mixed-Valence Cation States of Biferrocene and Bis(-fulvalenediyl)diiron Characterized in the Gas Phase by Valence Photoelectron Spectroscopy." J. Organomet. Chem. 2003, 666, 75-85.

Cotton, F. A.; Gruhn, N. E.; Gu, J.; Huang, P.; Lichtenberger, D. L.; Murrillo, C. A.; Van Dorn, L. O.; Wilkinson, C. C. "Closed-Shell Molecules that Ionize More Readily than Cesium." Science 2002, 298, 1971-1974.

Lichtenberger, D. L.; Gruhn, N. E.; Rai-Chaudhuri, A.; Renshaw, S. K.; Gladysz, J. A.; Jiao, H.; Seyler, J.; Igau, A. "How do the Electronic Structures of Low-Symmetry Metal-Hydride and -Alkyl Complexes Compare? Photoelectron Spectroscopy and Computational Studies of (05-C5R5)Re(NO)(L)R' [L = CO, P(C6H5)3; R, R' = H, CH3)]." J. Am. Chem. Soc. 2002, 21, 5494-5504.

Amashukeli, X.; Winkler, J. R.; Gray, H. B.; Gruhn, N. E.; Lichtenberger, D. L. "Electron-Transfer Reorganization Energies of Isolated Organic Molecules." J. Phys. Chem. 2002, 106, 7593-7598.

Lichtenberger, D. L.; Gruhn, N. E.; Rai-Chaudhuri, A.; Renshaw, S. K.; Gladysz, J. A.; Jiao, H.; Seyler, J.; Igau, A. "Vibrational Progressions in the Valence Ionizations of Transition Metal Hydrides: Evaluation of Metal-Hydride Bonding and Vibrations in (05-C5R5)Re(NO)(CO)H [R = H, CH3]." J. Am. Chem. Soc. 2002, 124, 1417-1423.

Westcott, B. L.; Gruhn, N. E.; Michelsen, L. J.; Lichtenberger, D. L. "Experimental Observation of Non-Aufbau Behavior: The Photoelectron Spectrum of Vanadyloctaethylporphyrinate and Vanadylphthalocyanine." J. Am. Chem. Soc. 2000, 122, 8083-8084.


UNIVERSITY OF ARIZONA CHEMISTRY HOMEPAGE SITE CONTACT
chemweb@arizona.edu
LAST MODIFIED
date: Mon, 16 Sep 2002 17:21:54 GMT
time: Mon, 16 Sep 2002 17:21:54 GMT