Reorganization energy of electron transfer at the solvent glass transition

Details Reorganization energy of electron transfer at the solvent glass transition Reorganization energy of electron transfer at the solvent glass transition

2005-08-03

arxiv.org/abs/cond-mat/0508109v1

Physics

Condensed Matter

Soft Condensed Matter

5 pages, 4 figures; submitted to J. Phys. Chem. B

Scientific paper

We present a molecular-dynamics study of the solvent reorganization energy of electron transfer in supercooled water. We observe a sharp decrease of the reorganization energy at a temperature identified as the temperature of structural arrest due to cage effect as discussed by the mode coupling theory. Both the heat capacity and dielectric susceptibility of the pure water show sharp drops at about the same temperature. This temperature also marks the onset of the enhancement of translational diffusion relative to rotational relaxation signaling the break-down of the Stokes-Einstein relation. The change in the reorganization energy at the transition temperature reflects the dynamical arrest of the slow, collective relaxation of the solvent related to Debye relaxation of the solvent dipolar polarization.

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