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Breakdown of Onsager's conjecture on distance dependent polarization relaxation in solvation dynamics

American Institute of Physics
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  • Solid State & Structural Chemistry Unit


Onsager's conjecture that the polarization relaxation of solvent mols. closer to a newly created ion occurs slower than those which are far away was examd. by using a mol. theory. Although Onsager's conjecture is correct when only the rotational diffusion mechanism of polarization relaxation is considered, it breaks down completely for a significant translational contribution to polarization relaxation. The consequences of this result in solvation dynamics of ions and dipoles are discussed.

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