Isotope effects in electron transfer across the electrode-electrolyte interface: a measure of solvent mode quantization
Article Abstract:
The free energy of electron transfer has been computed for the Fe2+/Fe3+ reaction with a Pt electrode through path integral molecular dynamics and path integral quantum transition state theory. The study focuses on the quantum mechanical manifestations of the solvent. There is only a small isotope effect on the free energy barrier when D2O is substituted for H2O because the solvent free energy barrier does not depend on the mass. Results show that a significant inverse isotope effect due to the better solvation of the ion by the quantum water instead of D2O.
Publication Name: Journal of Physical Chemistry B
Subject: Chemicals, plastics and rubber industries
ISSN: 1520-6106
Year: 1998
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Classical and quantum simulatio of electron transfer through a polypeptide
Article Abstract:
Electron transfer mediated by a solvated polypeptide was investigated using quantum rate theory, molecular dynamics simulations and semiempirical electronic structure. The nonadiabatic electron-transfer rate constant was calculated from the nuclear free energies and the electronic coupling between the initial and final states using a stationary-phase approximation. The calculations indicated that electron transfer in a significant range of conformations linking the polypeptide to the acceptor may contribute to the overall rate constant.
Publication Name: Journal of Physical Chemistry B
Subject: Chemicals, plastics and rubber industries
ISSN: 1520-6106
Year: 1999
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Multistate empirical valence bond model for proton transport in water
Article Abstract:
Research was conducted to examine proton-transfer reactions in aqueous systems. A multistate empirical valence bond model for describing proton transport in aqueous systems is proposed. The electrostatic interaction of the solvent water molecules with an exchange charge distribution is explicitly involved in the off-diagonal elements of the empirical valence bond Hamiltonian. Computational results are in good agreement with high-level ab initio calculations.
Publication Name: Journal of Physical Chemistry B
Subject: Chemicals, plastics and rubber industries
ISSN: 1520-6106
Year: 1998
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