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Steven Adelman
Professor—Physical/Theoretical Chemistry
Email: saa@purdue.edu
Phone: 765-494-5277
Office: WTHR 228
For Professor Adelman's individual Home Page click here.
Our group has developed a general statistical mechanical theory of the solvent effect on the dynamics of chemical reactions in solution. Such reactions represent a new and non-traditional problem in the theory of irreversible dynamics. Because realistic potential surfaces produce forces (~1 e.v./Å) of tremendous accelerating power on the reactive solute, reactions are characterized by solute motional times which are short compared to solvent relaxation times. Consequently, during reactive events, the solvent following of the solute motions is highly imperfect and severe breakdowns of thermodynamic equilibrium occur. 
Solution reactions, and related phenomena such as solute vibrational energy relaxation (VER), thus represent a new type of condensed phase dynamics which is qualitatively different from Brownian or diffusive dynamics. This new type of dynamics is dominated by forces which work to restore thermodynamic equilibrium.
We next turn to an application of the theory to solute VER. The principle of imperfect following leads to picture of vibrational dynamics in which, in zeroth order, the solute normal mode vibrates with liquid phase frequency TR in a hypothetical non-responding solvent. In first order, the normal mode probes the liquid at frequency TR leading to weak solvent response. This gives rise to VER with relaxation time T1 = ß-1(T R), where ß(T) is the friction kernel of the normal mode. Within the Gaussian model for the fluctuating force autocorrelation function, our expression for T1 becomes Equation 1. The quantities in Equation 1 have been computed for molecular bromine in liquid argon at T = 295 K (BR295) from solute-solvent pair correlation functions. In Fig. 1 we compare rates computed for BR295 from Eq. (1) (solid line) with isolated binary collision rates (dashed line) and with a low density extrapolation (dotted line).
Education
B.S., 1967, Illinois Institute of Technology; Ph.D. 1972, Harvard University; Postdoctoral Fellow, Massachusetts Institute of Technology, 1972-74; Postdoctoral Fellow, University of Chicago, 1974-75Recognitions
- Fellow of the American Physical Society, 1991
- Guggenheim Fellow, 1983
- Sloan Research Fellow, 1976
Selected Publications
- Adelman S. A., Comparison of Two Simple Models for High Frequency Friction: Exponential versus Gaussian Wings . Journal of Physical Chemistry B 2009 , 113 , 5528-5536.
- Gutman G. A.;Chandy, K. G.;Adelman, J. P.;Aiyar, J.;Bayliss, D. A.;Clapham, D. E.;Covarriubias, M.;Desir, G. V.;Furuichi, K.;Ganetzky, B.;Garcia, M. L.;Grissmer, S.;Jan, L. Y.;Karschin, A.;Kim, D.;Kuperschmidt, S.;Kurachi, Y.;Lazdunski, M.;Lesage, F.;Les, International Union of Pharmacology. XLI. Compendium of voltage-gated ion channels: Potassium channels . Pharmacol. Rev. 2003 , 55 , 583-586.
- Miller D. W.;Adelman, S. A., Time correlation function approach to liquid phase vibrational energy relaxation: Dihalogen solutes in rare gas solvents . J. Chem. Phys. 2002 , 117 , 2672-2687.