Ions in solution: density corrected density functional theory (DC-DFT).
Standard density functional approximations often give questionable results for odd-electron radical complexes, with the error typically attributed to self-interaction. In density corrected density functional theory (DC-DFT), certain classes of density functional theory calculations are significantly improved by using densities more accurate than the self-consistent densities. We discuss how to identify such cases, and how DC-DFT applies more generally. To illustrate, we calculate potential energy surfaces of HO·Cl(-) and HO·H2O complexes using various common approximate functionals, with and without this density correction. Commonly used approximations yield wrongly shaped surfaces and/or incorrect minima when calculated self consistently, while yielding almost identical shapes and minima when density corrected. This improvement is retained even in the presence of implicit solvent.
Department of Chemistry and Institute of Nano-Bio Molecular Assemblies, Yonsei University, 50 Yonsei-ro Seodaemun-gu, Seoul 120-749, South Korea.
Min-Cheol
MC
Kim
Department of Chemistry and Institute of Nano-Bio Molecular Assemblies, Yonsei University, 50 Yonsei-ro Seodaemun-gu, Seoul 120-749, South Korea.
Eunji
E
Sim
Department of Chemistry, University of California, Irvine, California 92697, USA.
Kieron
K
Burke
D000465:Algorithms; D016477:Artifacts; D003198:Computer Simulation; D006878:Hydroxides / Q000737:chemistry*; D008956:Models, Chemical; D008958:Models, Molecular; D014867:Water / Q000737:chemistry*
D006878:Hydroxides; D014867:Water; C031356:hydroxide ion