Dynamical arrest of electron transfer reorganization in super-cooled water.
This paper reports the results of Molecular Dynamics (MD) simulations of the solvent reorganization energy of electron transfer (ET) reactions in low-temperature solvents. Simulations are carried out for a model charge-transfer optical dye (p-nitroaniline) in SPC/E water in a range of temperatures down to the point of solvent ideal glass transition. We show a significant departure of the solvent reorganization energy, measured on a given time window, from its thermodynamic limit obtained by averaging over long simulation trajectories. Our results thus indicate that optical solvatochromism and activation parameters of ET reactions measured in viscous solvents will be significantly affected by the dynamical arrest of nuclear solvation when the experimental time scale becomes comparable to the characteristic relaxation time of the solvent.
Ghorai
Pradip K
PK
Department of Chemistry and Biochemistry and the Center for the Study of Early Events in Photosynthesis, Arizona State University, PO Box 871604, Tempe, Arizona 85287-1604, USA.
Matyushov
Dmitry V
DV