 |
Paul H. WineProfessor Office: 3238 ES&T Phone: 404-894-3425 Fax: 404-894-5638 |
B.S. in Chemistry, University of Michigan, 1968; Ph.D., Physical Chemistry,
Florida State University, 1974.
GTRI Award for Outstanding Performance in Research, 1987. Senior Faculty Best Paper Award, Georgia Tech Chapter of Sigma Xi, 1996; Fellow, American Chemical Society, 2010
Research Interests
Atmospheric chemists attempt to understand the chemical composition of the natural atmosphere, the nature of interactions involving atmospheric gases, liquids, and solids, as well as the Earth surface and biosphere, and the ways that human activity affects the chemical and physical characteristics of the atmosphere. Important environmental issues that are linked to human impacts on atmospheric chemistry include global climate change, stratospheric ozone depletion, acid deposition, and photochemical smog.
Chemical change in the atmosphere is driven largely by reactions of photochemically generated free radicals. Sophisticated experimental techniques (usually associated with physical chemists!) are required to quantitatively characterize important atmospheric photochemical processes as well as the kinetics and mechanisms of the fast free radical reactions, most of which are initiated photochemically. In our laboratory, laser flash photolysis and fast flow techniques are employed to generate reactive intermediates of interest, and a variety of optical and mass spectrometric techniques are employed to probe the time evolution of reactants and products. The experimental results provide needed input into models of atmospheric transport and chemical transformation that are employed to understand the phenomena mentioned in the first paragraph above. Results of our studies also provide fundamental information that is useful for establishing free radical thermochemistry and for refining reaction rate theories. Recent sponsors of our research include the National Science Foundation, the National Aeronautics and Space Administration, and the Camille and Henry Dreyfus Foundation.
There is currently enormous interest in understanding atmospheric sulfur oxidation in order to facilitate (1) our understanding of past climate as interpreted from ice core analyses and (2) our understanding of the role sulfur plays in particle formation and growth in the atmosphere and its resulting impact on current and future climate. Our group is very active in this area of research. Our current effort focuses on elucidating the kinetics and reaction mechanisms which control the atmospheric oxidation of dimethyl sulfide (CH3SCH3, DMS), the most ubiquitous naturally-occurring sulfur compound in the atmosphere, as well as intermediate DMS oxidation products such as CH3S(O), CH3S(O)OH, and CH3SCH2OOH. Both gas phase and aqueous phase chemistry are under investigation, and we are beginning to investigate free radical chemistry of sulfur compounds at the air/water interface.
Although the abundance of ozone in the atmosphere is quite small, i.e.,
3 ozone molecules per 10,000,000 air molecules on average, ozone is
a key atmospheric trace gas. The stratospheric "ozone layer"
protects the biosphere from harmful ultraviolet radiation, thus allowing
the existence of life as we know it. In the lowest regions of the atmosphere,
ozone is a nuisance. It is a powerful oxidant that is harmful to plants
and animals, and it is a key player (both as an initiator and as an
ultimate product) in photochemical smog. The atmospheric chemistry of
ozone is complex, involving numerous catalytic chain reactions. Understanding
this complex chemistry is another focus of our research effort. Our
research in this area involves laboratory studies aimed at quantitatively
characterizing the complex chain reaction sequences via which HOx, NOx,
ClOx, BrOx, and IOx radicals catalytically destroy ozone. The results
of our studies are used in prognostic models that predict the impacts
of anthropogenic activity on future ozone levels, and the resulting
impacts on climate and biological activity.
Another focus of our research effort is on atmospheric chemical processes
that are particularly important in low temperature environments such
as the upper troposphere, lower stratosphere, and polar regions. We
are studying chemical transformations of weakly-bound species that are
only stable in cold environments, and we are also carrying out studies
aimed at quantifying photochemical sources of OH, the atmospheric "cleansing
agent, in cold environments where H2O levels are low.
Recent Publications
"Kinetic and mechanistic study of the reactions of O(1D2) with HCN and CH3CN," R.S. Strekowski, J.M. Nicovich, and P.H. Wine, ChemPhysChem 2010, in press.
"Atmospheric and environmental physical chemistry: Pollutants without borders," P.H. Wine, J. Phys. Chem. Lett. 2010, 1, 1749.
"Reactive and non-reactive quenching of O(1D) by the potent greenhouse gases SO<sub>2</sub>F<sub>2</sub>, NF<sub>3</sub>, and SF<sub>5</sub>CF<sub>3</sub>, Z. Zhao, P.L. Laine, J.M. Nicovich, and P.H. Wine, Proc. Natl. Acad. Sci. USA 2010, 107, 6610.
Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation No.16, S.P. Sander, J. Abbatt, J.R. Barker, J.B. Burkholder, R.R. Friedl, D.M. Golden, R.E. Huie, C.E. Kolb, M.J. Kurylo, G.K. Moortgat, V.L. Orkin, and P.H. Wine, JPL Publication 09-31, Jet Propulsion Laboratory, Pasadena CA, 2009.
"Experimental and theoretical study of the carbon-13 and deuterium kinetic isotope effects in the Cl and OH reactions of CH<sub>3</sub>F," M. Marinkovic, M. Gruber-Stadler, J. M. Nicovich, R. Soller, M. Mulhauser, P.H. Wine, L. Bache-Andreassen, and C.J. Nielsen, J. Phys. Chem. A 2008, 112, 12416.
"Spectroscopic and kinetic study of the gas-phase CH3I−Cl and C2H5I−Cl adducts," V. Dookwah-Roberts, J.M. Nicovich, and P.H. Wine, J. Phys. Chem. A 2008, 112, 9535.
"Temperature-dependent kinetics study of the gas phase reactions of atomic chlorine with acetone, 2-butanone, and 3-pentanone," Z. Zhao, D.T. Huskey, J.M. Nicovich, and P.H. Wine, Int. J. Chem. Kinet. 2008, 40, 259.
"Kinetics, mechanism, and thermochemistry of the gas-phase reaction of atomic chlorine with pyridine," Z. Zhao, D.T. Huskey, K.J. Olsen, J.M. Nicovich, M.L. McKee and P.H. Wine, Phys. Chem. Chem. Phys. 2007, 9, 4383.
"Spectroscopy and kinetics of the gas-phase addition complex of atomic chlorine with dimethylsulfoxide," K. M. Kleissas, J. M. Nicovich, P. H. Wine, J. Photochem. Photobiol. A: Chem. 2007, 187, 1.
Chemical Kinetics and Photochemical Data for Use in Atmospheric Studies, Evaluation No. 15, S.P. Sander, B.J. Finlayson-Pitts, R.R. Friedl, D.M. Golden, R.E. Huie, H. Keller-Rudek, C.E. Kolb, M.J. Kurylo, M.J. Molina, G.K. Moortgat, V.L. Orkin, A.R.Ravishankara, and P.H. Wine, JPL Publication 06−2, Jet Propulsion Laboratory, Pasadena CA., 2006. Web access: http://jpldataeval.jpl.nasa.gov/.
"On the stratospheric chemistry of hydrogen cyanide," A. Kleinbohl, G. C. Toon, B. Sen, J. -F. L. Blavier, D. K. Weisenstein, R. S. Strekowski, J. M. Nicovich, P. H. Wine, P. O. Wennberg, Geophys. Res. Lett., 2006, 33, L11806, doi:10.1029/2006GL026015.
"Kinetics, mechanism, and thermochemistry of the gas phase reaction of atomic chlorine with dimethyl sulfoxide," J.M. Nicovich, S. Parthasarathy, F.D. Pope, A.T. Pegus, M.L. McKee, and P.H. Wine, J. Phys. Chem. A 2006, 110, 6874.
"Effects of aqueous organo-sulfur chemistry on speciation and particulate MS-to-NSS ratios," L. Zhu, A. Nenes, P.H. Wine, and J.M. Nicovich, J. Geophys. Res. 2006, 111, D05316, doi:10.1029/2005JD006326.
"Spectroscopic and kinetic study of the gas-phase CS2-Cl adduct," V. Dookwah-Roberts, R. Soller, J.M. Nicovich, and P.H. Wine, J. Photochem. Photobiol. A: Chem 2005 176, 114.
"Rate and mechanism for the reaction of chlorine atoms with iodoethane and 2-iodopropane," J. J. Orlando, C. A. Piety, J. M. Nicovich, M. L. McKee, and P. H. Wine, J. Phys. Chem. A 2005 109,6659.
"Kinetics studies of aqueous phase reactions of Cl atoms and Cl2- radicals with organic sulfur compounds of atmospheric interest," L. Zhu, J. M. Nicovich, and P. H. Wine, J. Phys. Chem. A 2005 109, 3903.
"Temperature-dependent kinetics study of the reactions of O(1D2) with N2 and O2," R. S. Strekowski, J. M. Nicovich, and P .H. Wine, Phys. Chem. Chem. Phys. 2004, 6, 2145.
"Temperature-dependent quantum yields for O(3P) and O(1D) production from photolysis of O3 at 248 nm," E. J. Dunlea, A. R. Ravishankara, R. S. Strekowski, J. M. Nicovich, and P. H. Wine, Phys. Chem. Chem. Phys.2004, 6, 5484.
"Temperature-dependent kinetics studies of aqueous phase reactions of hydroxyl radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate," L. Zhu, J. M. Nicovich, and P. H. Wine, Aquatic Sciences 2003, 65, 425.
"Temperature-dependent kinetics studies of aqueous phase reactions of SO4- radicals with dimethylsulfoxide, dimethylsulfone, and methanesulfonate," L. Zhu, J. M. Nicovich, and P. H. Wine, J. Photochem. Photobiol. A: Chem 2003, 157, 311.
"Bromine nitrate photochemistry: Quantum yields for O, Br, and BrO over the wavelength range 248-355 nm," R. Soller, J. M. Nicovich, and P. H. Wine, J. Phys. Chem. A 2002, 106, 8378.
"Redetermination of the rate coefficient for the reaction of O(1D) with N2," A. R. Ravishankara, E. J. Dunlea, M. A. Blitz, T. J. Dillon, D. E. Heard, M. J. Pilling, R. S. Strekowski, J. M. Nicovich, and P. H. Wine, Geophys. Res. Lett. 2002, 29 (15), 10.1029/2002GL014850.
"Investigation of N2O production from 266 and 532 nm laser flash photolysis of O3/N2/O2 mixtures," E. G. Estupinan, J. M. Nicovich, J. Li, D. M. Cunnold, and P. H. Wine, J. Phys. Chem. A 2002, 106, 5880.
"A temperature-dependent kinetics study of the reaction of O(3PJ) with (CH3)2SO," F. D. Pope, J. M. Nicovich, and P. H. Wine, Int. J. Chem. Kinet. 2002, 34, 156.
"Factors controlling tropospheric O3, OH, NOx, and SO2 over the tropical Pacific during PEM-Tropics B," Y. Wang, S. C. Liu, P. H. Wine, D. D. Davis, S. T. Sandholm, E. L. Atlas, M. A. Avery, D. R. Blake, N. J. Blake, W. H. Brune, B. G. Heikes, G. W. Sachse, R. E. Shetter, H. B. Singh, R. W. Talbot, and D. Tan, J. Geophys. Res. 2001, 106, 32733.
"A temperature-dependent kinetics study of the important stratospheric reaction O(3P) + NO2 -> NO + O2," E. G. Estupinan, J. M. Nicovich, and P. H. Wine, J. Phys. Chem. A 2001, 105, 9697.
"Kinetic and mechanistic study of the reaction of O(1D) with CF2HBr," R.S. Strekowski, J.M. Nicovich, and P.H. Wine, Int. J. Chem. Kinet. 2001, 33, 262.
"Temperature-dependent rate coefficients for the reactions of Br(2P3/2), Cl(2P3/2), and O(3PJ) with BrONO2," R. Soller, J.M. Nicovich, and P.H. Wine, J. Phys. Chem. A 2001, 105, 1416.
"Ab-initio study of the atmospheric oxidation of CS2," M. L. McKee and P. H. Wine, J. Am. Chem. Soc. 2001, 123, 2344.
"An investigation of N2O production from quenching of OH(A2Σ+) by N2," E. G. Estupinan, R. E. Stickel, and P. H. Wine, Chem. Phys. Lett. 2001, 336, 109.