TY - JOUR

T1 - Electron transfer in extended systems

T2 - Characterization by periodic density functional theory including the electronic coupling

AU - Behara, Pavan Kumar

AU - Dupuis, Michel

N1 - Funding Information:
PB gratefully acknowledges the guidance of Dr Nina Tyminska in designing our early polaron calculations and in assisting with the pictorial representation of localized polarons. MD acknowledges many stimulating discussions with Prof. Jochen Blumberger. We dedicate this paper to Prof. Michiel Sprik for his seminal and stimulating contributions to theories, methods, developments, and studies of electron transfer in the condensed phase and of redox reactivity at solid–liquid interfaces. We gratefully acknowledge start-up funds from University at Buffalo, and support from the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Award Number(s) DE-SC0019086. We thank Prof. Juerg Hutter and other participants on the CP2K user forum for assistance and guidance about the methods and their implementations in CP2K. We also acknowledge support from the Center for Computational Research at the University at Buffalo.

PY - 2020/5/21

Y1 - 2020/5/21

N2 - 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 VAB. 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

AB - 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 VAB. 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

UR - http://www.scopus.com/inward/record.url?scp=85084506471&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=85084506471&partnerID=8YFLogxK

U2 - 10.1039/c9cp05133c

DO - 10.1039/c9cp05133c

M3 - Article

C2 - 31670326

AN - SCOPUS:85084506471

VL - 22

SP - 10609

EP - 10623

JO - Physical Chemistry Chemical Physics

JF - Physical Chemistry Chemical Physics

SN - 1463-9076

IS - 19

ER -