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

Area of Science:

• Computational Chemistry
• Solid-State Physics
• Materials Science

Background:

• Electron transfer (ET) is crucial in many chemical and physical processes.
• Accurate theoretical descriptions of ET in extended systems are computationally challenging.
• Existing methods often struggle to capture the complexities of ET in solid materials.

Purpose of the Study:

• To introduce a novel computational implementation for electron transfer theory in extended systems.
• To enable the full characterization of electron transfer phenomena within solid-state materials.
• To provide a versatile method applicable across various electronic structure theories.

Main Methods:

• Development of a new computer implementation for ET theory within periodic density functional theory (DFT).
• Calculation of the electronic coupling transition element (VAB) for localized single-determinant wavefunctions.
• Leveraging high-performance functions within the CP2K code for efficient computation.
• The method's computational cost is comparable to a single Hartree-Fock (HF) iteration.

Main Results:

• Successful implementation of ET theory for extended systems using periodic DFT.
• Demonstrated applicability to diverse materials including ferric oxide (Fe2O3), rutile TiO2, and bismuth vanadate (BiVO4).
• Validation of the approach across various theoretical frameworks like HF, DFT, hybrid DFT, DFT+U, and cDFT.

Conclusions:

• The new computational approach significantly advances the study of electron transfer in solid-state systems.
• This method offers a computationally efficient and versatile tool for characterizing electronic coupling.
• It opens new avenues for understanding and designing materials with specific electron transfer properties.