Green function theory of charge transfer processes in solution

Journal Article · Fri Apr 01 04:00:00 EST 1988 · J. Chem. Phys.; (United States)

DOI:https://doi.org/10.1063/1.453804· OSTI ID:5287106

Newton, M D; Friedman, H L

By using a Green function Q to characterize the linear response of a dielectric body to electric charges, we obtain a theory for the solvent dielectric contribution to relaxation along the reaction coordinate RC(t) in an electron transfer process. For an electron transfer reaction model, in which the ions are embedded in a dielectric continuum, the theory gives, at t = 0, the reorganization free energy derived by Marcus in 1956. For the same model the characteristic time tau/sub Q/ associated with RC(t) is evaluated in terms of the dielectric function epsilon/sub ..omega../ of the medium. How the rate constant k/sub et/ for an electron transfer process depends on tau/sub Q/ is illustrated for both high-barrier and low-barrier cases by approximating RC(t) as a Smoluchowski process on a potential surface. Applying the theory to a molecular model (charged hard sphere ions in a dipolar hard sphere solvent), treated in the mean spherical approximation for the response at any frequency (Wolynes, 1987), indicates that the effects of the molecular structure of the solvent on tau/sub Q/ are large even if the ion is several times larger than a solvent molecule.

• Research Organization: Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973
• OSTI ID: 5287106
• Journal Information: J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 88:7; ISSN JCPSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
CHARGE EXCHANGE
CHEMICAL REACTION KINETICS
DISPERSIONS
ELECTRON TRANSFER
FUNCTIONS
GREEN FUNCTION
KINETICS
MIXTURES
POLARIZATION
REACTION KINETICS
SOLUTIONS
SOLVENTS