Dynamic salt effect on intramolecular charge-transfer reactions.
The dynamic salt effect in charge-transfer reactions is investigated theoretically in this paper. Free-energy surfaces are derived based on a nonequilibrium free-energy functional. Reaction coordinates are clearly defined. The solution of the reaction-diffusion equation leads to a rate constant depending on the time correlation function of the reaction coordinates. The time correlation function of the ion-atmosphere coordinate is derived from the solution of the Debye-Falkenhagen equation. It is shown that the dynamic salt effect plays an important role in controlling the rate of charge-transfer reactions in the narrow-window limit but is balanced by the energetics and the dynamics of the polar-solvent coordinate. The simplest version of the theory is compared with an experiment, and the agreement is fairly good. The theory can also be extended to charge-transfer in the class of electrolytes that has come to be called "ionic fluids."
Zhu
Jianjun
J
Department of Chemistry, Henan Normal University, Xin Xiang, Henan 453002, People's Republic of China. zhuji01@ca.com
Ma
Rong
R
Lu
Yan
Y
Stell
George
G
D002627:Chemistry, Physical / Q000379:methods*; D004058:Diffusion; D004583:Electrons; D005583:Fourier Analysis; D007477:Ions; D008024:Ligands; D008956:Models, Chemical; D015233:Models, Statistical; D008968:Molecular Conformation; D012492:Salts / Q000737:chemistry*; D012997:Solvents; D013696:Temperature; D013816:Thermodynamics
D007477:Ions; D008024:Ligands; D012492:Salts; D012997:Solvents