2005/08/03 by Pradip K. Ghorai, Pradip Kumar Ghorai, Ghorai, Pradip K. +2
Chemistry · Materials Science · Physics and Astronomy · #Adsorption, diffusion, and thermodynamic properties of materials #FOS: Physical sciences #Glass properties and applications #Photochemistry and Electron Transfer Studies #Soft Condensed Matter (cond-mat.soft) #Statistical Mechanics (cond-mat.stat-mech) #cond-mat.soft #cond-mat.stat-mech
paper · pdf · doi:10.48550/arxiv.cond-mat/0508109
5 pages, 4 figures; submitted to J. Phys. Chem. B
arxiv created 2005/08/03 · openalex publication_date 2005/08/03 · arxiv updated 2009/12/01 · openalex created_date 2025/10/10 · openalex updated_date 2026/07/28
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.