Journal
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA
Volume 107, Issue 11, Pages 4830-4833Publisher
NATL ACAD SCIENCES
DOI: 10.1073/pnas.0913277107
Keywords
density functional theory; molecular dynamics simulations; photovoltaics; solid/liquid interfaces; statistical mechanics
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Funding
- Swiss National Science Foundation [200020-111895]
- Swiss National Supercomputer Center for computer resources
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A highly efficient mechanism for the regeneration of the cis-bis(isothiocyanato) bis(2,2'-bipyridyl-4,4'-dicarboxylato)-ruthenium (II) sensitizing dye (N3) by I- in acetonitrile has been identified by using molecular dynamics simulation based on density functional theory. Barrier-free complex formation of the oxidized dye with both I- and I-2(-), and facile dissociation of I-2(-) and I-3(-) from the reduced dye are key steps in this process. In situ vibrational spectroscopy confirms the reversible binding of I-2 to the thiocyanate group. Additionally, simulations of the electrolyte near the interface suggest that acetonitrile is able to cover the (101) surface of anatase with a passivating layer that inhibits direct contact of the redox mediator with the oxide, and that the solvent structure specifically enhances the concentration of I- at a distance which further favors rapid dye regeneration.
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