Electron transfer in extended systems: characterization by periodic density functional theory including the electronic coupling. Issue 19 (31st October 2019)

• Record Type: Journal Article
• Authors: Behara, Pavan Kumar; Dupuis, Michel
• Is Part Of: Physical chemistry chemical physics. Volume 22:Issue 19(2020)
• Page Start: 10609
• Page End: 10623
• Publication Date: 2019-10-31
• Subjects: Chemistry, Physical and theoretical -- Periodicals; 541.3
• DOI: 10.1039/c9cp05133c
• Languages: English
• ISSNs: 1463-9076

Abstract

Abstract : CP2K implementation describing electron transfer in extended systems treated by periodic-DFT, including the calculation of electronic coupling transition element V AB . 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 Fe2 O3, rutile TiO2, and finally bismuth vanadate BiVO4 .