Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling

Abstract

We describe a new computer implementation of electron transfer (ET) theory in extended systems treated by periodic density functional theory (DFT), including the calculation of the electronic coupling transition element V_AB. In particular, the development opens up the full characterization of electron transfer in the solid state. The approach is valid for any single-determinant wavefunction with localized character representing the electronic structure of the system, from Hartree–Fock (HF) theory, to density functional theory (DFT), hybrid DFT theory, DFT+U theory, and constrained DFT (cDFT) theory. The implementation in CP2K reuses the high-performance functions of the code. The computational cost is equivalent to only one iteration of an HF calculation. We present test calculations for electron transfer in a number of systems, including a 1D-model of ferric oxide, hematite Fe₂O₃, rutile TiO₂, and finally bismuth vanadate BiVO₄.