Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids

Holroyd, Richard A.; Miller, John R.

doi:10.1021/acs.jpcb.9b07845

Title: Rate versus Free Energy Change for Attaching Highly Mobile Electrons to Molecules in Nonpolar Liquids

Journal Article · Tue Oct 08 00:00:00 EDT 2019 · Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry

DOI:https://doi.org/10.1021/acs.jpcb.9b07845· OSTI ID:1572366

Holroyd, Richard A. ^[1];

^[1]

Brookhaven National Lab. (BNL), Upton, NY (United States)

The inverted region of the Marcus theory, usually absent for bimolecular electron transfer reactions, is clearly observed for electron attachment reactions to molecules in nonpolar fluids. Application of pressure increased the energies of the solvated electron reactants letting us continuously adjust the free energy change. Inverted behavior is enabled by the very high mobilities of the solvated electrons which raise the diffusion-controlled encounter rates so high that they do not limit the reaction rates. The nonpolar media used in these experiments reduce reorganization energies, enhancing inverted behavior. Still, for every case showing an inverted region, the presence of low-lying excited states in the product radical anions led to regions of increasing rate constants that began at the energies of excited states of –0.54 to –1.2 eV. Here, while continuum models predict no solvent reorganization energy in nonpolar liquids, fits to the data found solvent reorganization energies of 0.05–0.4 eV supporting ideas advanced in theories of Matyushov.

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Research Organization:: Brookhaven National Lab. (BNL), Upton, NY (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0012704

OSTI ID:: 1572366

Report Number(s):: BNL-212236-2019-JAAM; TRN: US2001321

Journal Information:: Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry, Vol. 123, Issue 43; ISSN 1520-6106

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 10 works

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