Dr. Edward L. Quitevis
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Title: |
Professor |
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Education: |
Ph.D., Harvard University, 1981; Postdoctoral Fellow, University of Toronto, 1981-1984 |
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Research Area: |
Physical Chemistry/Chemical Physics |
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Office: |
Chemistry 035 |
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Principal Research Interests
- Ultrafast Nonlinear Optical Spectroscopy of Liquids
- Dynamics of Complex Fluids
- Physical Chemistry of Ionic Liquids
- Supercooled Liquids and the Glass Transition
The research of Professor Quitevis is directed toward understanding liquid-state dynamics. The focus of our current research is on the dynamics of complex fluids, in particular, room temperature ionic liquids and supercooled liquids.
The main technique used in my laboratory is optical heterodyne-detected Raman-induced Kerr effect spectroscopy (OHD-RIKES). OHD-RIKES is an ultrafast nonlinear optical time-domain technique that measures the collective polarizability anisotropy dynamics of a liquid. By use of a Fourier-transform deconvolution procedure, the OHD-RIKES transient can be converted to a reduced spectral density or optical Kerr effect (OKE) spectrum, which is directly related to the depolarized Raman spectrum of the liquid and contains information about the low-frequency intermolecular modes of the liquid.
Ionic Liquids: Room temperature ionic liquids (ILs) are commonly defined as salts with melting points below 373K. An IL is composed of a bulky organic cation and one of a range of common anions, which might be either organic or inorganic, and possesses negligible vapour pressure, low flammability, and a wide liquid range. The vast number of potential ILs (over a million simple ones and over a trillion ternary systems) means that ILs can be designed specifically with tuneable physicochemical properties, leading to their description as “designer” solvents. Because they offer unique sets of properties not achievable with other materials, there is increasing interest in applications beyond solvents in such wide ranging fields as energetic materials, biotechnology, and nanoscience. Despite the great success of this application-driven research, a fundamental understanding of the structure, dynamics, and interactions in these complex fluids is still lacking. A particularly important feature of ILs is that they are structured liquids characterized by nanoscopic polar and nonpolar domains. Understanding the relationship between this nanostructural organization and the intermolecular dynamics in ILs is one of the main themes guiding research in my group.
Supercooled Liquids: The dramatic viscous slow down that accompanies the formation of glasses upon cooling supercooled liquids to below the glass transition temperature Tg is one of the oldest and most extensively studied problems in condensed matter physics and chemistry. The microscopic causes of the viscous slow down responsible for the glass transition however remain an unsolved problem. We are currently studying translational and rotational diffusion in glass-forming liquids above and below Tg. The goal of this research is to further understand the decoupling between translational and rotational diffusion that occurs as Tg is approached from above in the supercooled state and the processes that underlie physical aging when the glass-former is quenched from a temperature above Tg to the glassy state. Current theories of the glass transition are based on the existence of dynamic heterogeneity near Tg. Experiments in my laboratory are aimed at revealing the relationship between decoupling, physical aging, and dynamic heterogeneity. Fluorescence recovery after photobleaching (FRAP) techniques are being used to measure the ultraslow translational and rotational diffusion near Tg.
Representative Publications
- "Effect of Cation Symmetry and Alkyl Chain Length on the Structure and Intermolecular Dynamics of 1,3-Dialkylimidazolium Bis(trifluoromethanesulfonyl)amide Ionic Liquids," D. Xiao, L. G. Hines, Jr., S. Li, R. A. Bartsch, E. L. Quitevis, O. Russina, A. Triolo, J. Phys. Chem. B 2009, 113, 6426-6433.
- "Intermolecular Vibrational Motions of Solute Molecules Confined in Nonpolar Domains of Ionic Liquids," D. Xiao, L. G. Hines, Jr., R. A. Bartsch, E. L. Quitevis, J. Phys. Chem. B 2009, 113, 4544-4548.
- "Nanostructural Organization and the Anion Effects in the Optical Kerr Effect Spectra of Binary Ionic Liquid Mixtures," D. Xiao, J. R. Rajian, L. G. Hines, Jr., S. Li, R. A. Bartsch, and E. L. Quitevis, J. Phys. Chem. B 2008, 112, 13316-13325.
- "Translational Diffusion in Sucrose Benzoate Near the Glass Transition: Probe Size Dependence in the Breakdown of the Stokes-Einstein Equation," Rajian, J. R.; Quitevis, E. L. J. Chem. Phys. 2007, 126 , 224506(1)-224506(10).
- "Nanostructural Organization and Anion Effect on the Temperature Dependence of the Optical Kerr Effect Spectra of Ionic Liquids," Xiao, D.; Rajian, J. R.; Cady, A.; Li, S.; Bartsch, R. A.; Quitevis, E. L. J. Phys. Chem. B 2007, 111, 4669 – 4677. (Part of special issue “Physical Chemistry of Ionic Liquids”.)
- "Additivity of the Optical Kerr Effect Spectra in Binary Ionic Liquid Mixtures: Implications for Nanostructural Organization," Xiao, D.; Rajian, J. R.; Li, S.; Bartsch, R. A.; Quitevis, E. L. J. Phys. Chem. B 2006, 110, 16174-16178.
- "Enhanced Translational Diffusion of Rubrene in Sucrose Benzoate," Rajian, J. R.; Huang, W.; Richert, R.; Quitevis, E. L. J. Chem. Phys. 2006, 124, 014510(1)-014510(7).
- "Intermolecular Spectrum of Liquid Biphenyl Studied by Optical Kerr Effect Spectroscopy," Rajian, J. R., Hyun, B.-Y., Quitevis, E. L. J. Phys. Chem. A 2004, 108, 10107-10115.
- "Temperature-Dependence of the Low-Frequency Spectrum of 3-Pentyl-1-methylimidazolium Bis(trifluoromethanesulfonyl)imide Studied by Optical Kerr Effect Spectroscopy," Rajian, J.R.; Li, S.; Bartsch, R.A.; Quitevis, E.L. Chem. Phys. Lett, 2004, 393, 372-377.
- "Relaxation of the Methylene Blue Monomer-Dimer Equilibrium in Supercooled Glycerol near the Glass Transition," Weaver, F.W.; Quitevis, E.L. Chem. Phys. Lett. 2003, 378, 135-141.
- "Low-frequency Spectrum of Homeotropically-aligned Liquid Crystals: Optical Heterodyne-detected Raman-induced Kerr Effect Spectroscopy of 4-Octyl-4’-cyanobiphenyl," Hyun, B.-R.; Quitevis, E.L., Chem. Phys. Lett. 2003, 370, 725-732.
