title: Block-Localized Wavefunction (BLW) Based Two-State Approach for Charge Transfers between Phenyl Rings.
abstract: The block-localized wave function (BLW) method is the simplest and most efficient variant of ab initio valence bond (VB) theory which defines electron-localized resonance states following the conventional VB concepts. Here, a BLW-based two-state approach is proposed to probe the charge/hole transfer reactions within the Marcus-Hush model. With this approach, both the electronic coupling and reorganization energies can be derived at the ab initio level. Pilot applications to the electron/hole transfers between two phenyl rings are presented. Good exponential correlation between the electronic coupling energy and the donor-acceptor distance is shown, whereas the inner-sphere reorganization shows little geometric dependency. Computations also support the assumption in Marcus theory that the thermal electron transfer barrier (ΔG*), which is a sum of the reaction barrier (ΔEa) for electron/hole transfer and the coupling energy (VAB), is a quarter of the reorganization energy (λ).
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan 49008, United States.
authors.forename: Yirong
authors.initials: Y
authors.lastname: Mo
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan 49008, United States.
authors.forename: Lingchun
authors.initials: L
authors.lastname: Song
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan 49008, United States.
authors.forename: Yuchun
authors.initials: Y
authors.lastname: Lin
authors.affiliation: Department of Chemistry, Western Michigan University, Kalamazoo, Michigan 49008, United States.
authors.forename: Minghong
authors.initials: M
authors.lastname: Liu
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
authors.forename: Zexing
authors.initials: Z
authors.lastname: Cao
authors.affiliation: The State Key Laboratory of Physical Chemistry of Solid Surfaces, Fujian Provincial Key Laboratory of Theoretical and Computational Chemistry, and College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005, China.
authors.forename: Wei
authors.initials: W
authors.lastname: Wu