 Professor, Born 1947
B.S. 1969, Southwestern University
Ph.D. 1974, Cornell University
Room: 4319a
Phone: 608-263-7364
Email: fcrim@chem.wisc.edu
Position: Professor
Time-Resolved Studies of CN Radical Reactions and the Role of Complexes in Solution. Andrew C. Crowther, Stacey L. Carrier, Thomas J. Preston, and F. Fleming Crim, J. Phys. Chem. A 112, 12081 (2008). Reaction Dynamics and Vibrational Spectroscopy of CH3D Molecules with Both C-H and C-D Stretches Excited. Christopher J. Annesley, Andrew E. Berke, and F. Fleming Crim, J. Phys. Chem. A 112, 9448 (2008). Chemical Dynamics of Vibrationally Excited Molecules: Controlling Reactions in Gases and on Surfaces. F. Fleming Crim, Proc. Natl. Acad. Sci. USA 105, 12654 (2008). Vibrationally Mediated Photodissociation of Ammonia: The Influence of N-H Stretching Vibrations on Passage through Conical Intersections, Michael L. Hause, Y. Heidi Yoon, and F. Fleming Crim, J. Chem. Phys. 125, 174309 (2006). Mode- and Bond-selective Reaction of Cl(2P3/2) with CH3D Excited in the C-H Stretch Overtone Region. Robert J. Holiday, Chan-Ho Kwon, Christopher J. Annesley, and F. Fleming Crim, J. Chem. Phys. 125, 133101 (2006). Connecting Chemical Dynamics in Gases and Liquids. Christopher G. Elles and F. Fleming Crim, Annu. Rev. Phys. Chem. 57, 273 (2006). A Time-Resolved Spectroscopic Study of the Reaction Cl + n-C5H12 → HCl + C5H11 in Solution, Leonid Sheps, Andrew C. Crowther, Stacey L. Carrier, and F. Fleming Crim, J. Phys. Chem. A 110, 3087 (2006). Recombination Dynamics and Hydrogen Abstraction Reactions of Chlorine Radicals in Solution. Leonid Sheps, Andrew C. Crowther, Christopher G. Elles, and F. Fleming Crim, J. Phys. Chem. A 109, 4296 (2005). Vibrational Relaxation of CH3I in the Gas Phase and in Solution. Christopher G. Elles, M. Jocelyn Cox, and F. Fleming Crim, J. Chem. Phys. 120, 6973 (2004) The Relative Reactivity of the CH3D molecules with Excited Symmetric and Antisymmetric Stretching Vibrations. Sangwoon Yoon, Robert J. Holiday, Edwin L. Sibert III, and F. Fleming Crim, J. Chem. Phys. 119, 9568 (2003) Competition between Adiabatic and Nonadiabatic Pathways in the Photodissociation of Vibrationally Excited Ammonia. Andreas Bach, J. Matthew Hutchison, Robert J. Holiday, and F. Fleming Crim, J. Phys. Chem A, 107, 10490 (2003). Control of Bimolecular Reactions: Bond-Selected Reaction of Vibrationally Excited CH3D with Cl(2P3/2). Sangwoon Yoon, Robert J. Holiday, and F. Fleming Crim, J. Chem. Phys. 119, 4755 (2003) Vibrational Relaxation of CH2I2 in Solution: Excitation Level Dependence. Christopher G. Elles, Dieter Bingemann, Max M. Heckscher, and F. Fleming Crim, J. Chem. Phys., 118 5587 (2003) Relaxation of the C-H Stretching Fundamental Vibrations of CHI3, CH2I2, and CH3I in Solution. Max M. Heckscher, Leonid Sheps, Dieter Bingemann, and F. Fleming Crim, J. Chem. Phys. 117, 8917 (2002) Transient Electronic Absorption of Vibrationally Excited CH2I2: Watching Energy Flow in Solution. Dieter Bingemann, Andrew M. King, and F. Fleming Crim, J. Chem. Phys. 113, 5018 (2000) Vibrational State Control of Bimolecular Reactions: Discovering and Directing the Chemistry, F. Fleming Crim, Acc. Chem. Res. 32, 877 (1999) Bond-Selected Chemistry: Vibrational State Control of Photodissociation and Bimolecular Reaction, F. Fleming Crim, J. Phys. Chem. 100, 12725 (1996) (Centennial Issue) Vibrationally Mediated Photodissociation: Exploring Excited State Surfaces and Controlling Decomposition Pathways, F. F. Crim, Ann. Rev. Phys. Chem. 44, 397 (1993) Selectively Breaking Either Bond in the Bimolecular Reaction of HOD with Hydrogen Atoms. Ricardo B. Metz, John D. Thoemke, Joann M. Pfeiffer and F. Fleming Crim, J. Chem. Phys. 99, 1744 (1993) Controlling Bimolecular Reactions: Mode and Bond Selected Reaction of Water with Hydrogen Atoms. A. Sinha, M. C. Hsiao, and F. F. Crim, J. Chem. Phys. 94, 4928 (1991) An Experimental and Theoretical Study of the Bond-Selected Photodissociation of HOD. R. L. Vander Wal, J. L. Scott, F. F. Crim, K. Weide, and R. Schinke, J. Chem. Phys. 94, 3548 (1991)
| Research Description
Our group is studying the dynamics of reaction and photodissociation with the goal of understanding the essential features of chemistry in both gases and liquids. The unifying theme of our research is connecting chemical reaction dynamics occurring in gases to those in liquids. We use both high resolution lasers and ultrafast lasers, and the key to all of our experiments is preparing molecules in vibrationally excited states and spectroscopically monitoring their subsequent behavior.
Vibrational excitation is crucial in many chemical reactions because motion of the atoms relative to each other carries the system through the transition state that lies atop the barrier to reaction. Because laser excitation is a particularly attractive means of preparing molecules in specific internal states, our strategy is to excite molecules with a laser pulse and use time-resolved spectroscopy to follow their subsequent behavior. We use high resolution lasers in some experiments and ultrafast lasers, which produce pulses of less than 100 fs duration, in others. The two approaches often provide complementary information and allow us to study some of the same reactions in isolated molecules and in liquids.  In the former case, laser excitation prepares a molecular eigenstate that does not evolve in time and whose properties we exploit to control the course of a chemical reaction. In the later case, the short laser pulse prepares a state that does evolve in time and that we intercept at different points in its evolution. This good time resolution allows us to observe processes that occur during a time that is comparable to the interval between the interactions in solution.
We use a variety of excitation and detection techniques, such as resonant multiphoton ionization with ion imaging in molecular beams and time-resolved transient absorption or non-linear spectroscopy in liquids. The molecular beam experiments provide an extremely detailed view of the chemical dynamics of isolated, well-characterized molecules. We have exploited our understanding of the behavior of vibrationally excited molecules to control the course of a chemical reaction, and we have used laser excitation to cleave a particular bond selectively in both photodissociation and bimolecular reaction. The ultrafast laser techniques now allow us to follow the flow of energy within a molecule directly and to study vibrationally driven reactions in liquids. Discovering the controlling aspects of chemical reactions at a fundamental level is the focus of our research. The attached list gives a few representative publications. There is a current list of all publications at our group website, http://www.chem.wisc.edu/~crim/
Last updated February 8, 2010
Hilldale Award in the Physical Sciences, 2010 ACS Fellow, Inaugural class, 2009 Silver Medal and Centenary Lectureship, Royal Society of Chemistry, London, 2008 Irving Langmuir Award in Chemical Physics, American Chemical Society, 2006 Member, National Academy of Sciences, 2001 Earl K. Plyler Prize for Molecular Spectroscopy, American Physical Society, 1998 Fellow, American Academy of Arts and Sciences, 1998 Fellow, Japan Society for the Promotion of Science, 1995 Fellow, American Association for the Advancement of Science, 1995 Max Planck Research Award (with Juergen Troe), 1993 Upjohn Teaching Award, Department of Chemistry, University of Wisconsin, 1992 Chancellor's Award for Excellence in Teaching, University of Wisconsin, 1991 Fellow, American Physical Society, 1989 Alexander von Humboldt Senior U.S. Scientist Award, 1986 Camille and Henry Dreyfus Teacher-Scholar, 1982 Alfred P. Sloan Research Fellow, 1981-83
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