1 research outputs found
Corresponding Orbitals Derived from Periodic Bloch States for Electron Transfer Calculations of Transition Metal Oxides
An
approach for modeling electron transfer in solids and at surfaces
of iron-(oxyhydr)Âoxides and other redox active solids has been developed
for electronic structure methods (i.e., plane-wave density functional
theory) capable of performing calculations with periodic cells and
large system sizes efficiently while at the same time being accurate
enough to be used in the estimation of the electron-transfer coupling
matrix element, <i>V</i><sub><i>AB</i></sub>,
and the electron transfer transmission factor, κ<sub>el</sub>. This method is an extension of the valence bond theory electron
transfer method for molecules and clusters implemented by Dupuis and
others and used extensively by Rosso and co-workers in which scaled
corresponding orbitals derived from the Bloch states are used to calculate
the off-diagonal matrix elements <i>H</i><sub><i>AB</i></sub> and <i>S</i><sub><i>AB</i></sub>. A key
development of the present work is the formulation of algorithms to
improve the accuracy of the integration of the exact exchange integral
in periodic boundary conditions. This method is demonstrated on model
systems for electron small polaron transfer in iron-(oxyhydr)Âoxides,
including bare Fe<sup>2+</sup>–Fe<sup>3+</sup> ions, and in
[Fe<sup>3+</sup>(OH<sub>2</sub>)<sub>2</sub> (OH<sup>–</sup>)<sub>2</sub>)]<sub><i>n</i></sub><sup><i>n</i>+</sup> chains representing the
common edge-sharing Fe octahedral motif in these materials