Solvent reorganization entropy of electron transfer in polar solvents.
We report the results of molecular dynamics simulations of the solvent reorganization energy of intramolecular electron transfer in a charge-transfer molecule dissolved in water and acetonitrile at varying temperatures. The simulations confirm the prediction of microscopic solvation theories of a positive reorganization entropy in polar solvents. The results of simulations are analyzed in terms of the splitting of the reorganization entropy into the contributions from the solute-solvent interaction and from the alteration of the solvent structure induced by the solute. These two contributions mutually cancel each other, resulting in the reorganization entropy amounting to only a fraction of each component.
Ghorai
Pradip K
PK
Department of Chemistry and Biochemistry and the Center for the Early Events in Photosynthesis, Arizona State University, PO Box 871604, Tempe, Arizona 85287-1604, USA.
Matyushov
Dmitry V
DV