Ions in solution: Density corrected density functional theory (DC-DFT)
Abstract
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{sup −} and HO·H{sub 2}O 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.
- Authors:
-
- Department of Chemistry and Institute of Nano-Bio Molecular Assemblies, Yonsei University, 50 Yonsei-ro Seodaemun-gu, Seoul 120-749 (Korea, Republic of)
- Department of Chemistry, University of California, Irvine, California 92697 (United States)
- Publication Date:
- OSTI Identifier:
- 22253393
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics
- Additional Journal Information:
- Journal Volume: 140; Journal Issue: 18; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; DENSITY; DENSITY FUNCTIONAL METHOD; INTERACTIONS; IONS; POTENTIAL ENERGY; SOLVENTS
Citation Formats
Kim, Min-Cheol, Sim, Eunji, and Burke, Kieron. Ions in solution: Density corrected density functional theory (DC-DFT). United States: N. p., 2014.
Web. doi:10.1063/1.4869189.
Kim, Min-Cheol, Sim, Eunji, & Burke, Kieron. Ions in solution: Density corrected density functional theory (DC-DFT). United States. https://doi.org/10.1063/1.4869189
Kim, Min-Cheol, Sim, Eunji, and Burke, Kieron. 2014.
"Ions in solution: Density corrected density functional theory (DC-DFT)". United States. https://doi.org/10.1063/1.4869189.
@article{osti_22253393,
title = {Ions in solution: Density corrected density functional theory (DC-DFT)},
author = {Kim, Min-Cheol and Sim, Eunji and Burke, Kieron},
abstractNote = {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{sup −} and HO·H{sub 2}O 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.},
doi = {10.1063/1.4869189},
url = {https://www.osti.gov/biblio/22253393},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 18,
volume = 140,
place = {United States},
year = {Wed May 14 00:00:00 EDT 2014},
month = {Wed May 14 00:00:00 EDT 2014}
}