Sensitivity of the Properties of Ruthenium “Blue Dimer” to Method, Basis Set, and Continuum Model
Abstract
The ruthenium “blue dimer” [(bpy)2RuIIIOH2]2O4+ is best known as the first well-defined molecular catalyst for water oxidation. It has been subject to numerous computational studies primarily employing density functional theory. However, those studies have been limited in the functionals, basis sets, and continuum models employed. The controversy in the calculated electronic structure and the reaction energetics of this catalyst highlights the necessity of benchmark calculations that explore the role of density functionals, basis sets, and continuum models upon the essential features of blue-dimer reactivity. In this paper, we report Kohn-Sham complete basis set (KS-CBS) limit extrapolations of the electronic structure of “blue dimer” using GGA (BPW91 and BP86), hybrid-GGA (B3LYP), and meta-GGA (M06-L) density functionals. The dependence of solvation free energy corrections on the different cavity types (UFF, UA0, UAHF, UAKS, Bondi, and Pauling) within polarizable and conductor-like polarizable continuum model has also been investigated. The most common basis sets of double-zeta quality are shown to yield results close to the KS-CBS limit; however, large variations are observed in the reaction energetics as a function of density functional and continuum cavity model employed.
- Authors:
- Publication Date:
- Research Org.:
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)
- Sponsoring Org.:
- USDOE
- OSTI Identifier:
- 1053360
- DOE Contract Number:
- AC05-76RL01830
- Resource Type:
- Journal Article
- Journal Name:
- Journal of Chemical Physics, 136(20):204104
- Additional Journal Information:
- Journal Name: Journal of Chemical Physics, 136(20):204104
- Country of Publication:
- United States
- Language:
- English
- Subject:
- Environmental Molecular Sciences Laboratory
Citation Formats
Ozkanlar, Abdullah, and Clark, Aurora E. Sensitivity of the Properties of Ruthenium “Blue Dimer” to Method, Basis Set, and Continuum Model. United States: N. p., 2012.
Web. doi:10.1063/1.4719937.
Ozkanlar, Abdullah, & Clark, Aurora E. Sensitivity of the Properties of Ruthenium “Blue Dimer” to Method, Basis Set, and Continuum Model. United States. https://doi.org/10.1063/1.4719937
Ozkanlar, Abdullah, and Clark, Aurora E. 2012.
"Sensitivity of the Properties of Ruthenium “Blue Dimer” to Method, Basis Set, and Continuum Model". United States. https://doi.org/10.1063/1.4719937.
@article{osti_1053360,
title = {Sensitivity of the Properties of Ruthenium “Blue Dimer” to Method, Basis Set, and Continuum Model},
author = {Ozkanlar, Abdullah and Clark, Aurora E},
abstractNote = {The ruthenium “blue dimer” [(bpy)2RuIIIOH2]2O4+ is best known as the first well-defined molecular catalyst for water oxidation. It has been subject to numerous computational studies primarily employing density functional theory. However, those studies have been limited in the functionals, basis sets, and continuum models employed. The controversy in the calculated electronic structure and the reaction energetics of this catalyst highlights the necessity of benchmark calculations that explore the role of density functionals, basis sets, and continuum models upon the essential features of blue-dimer reactivity. In this paper, we report Kohn-Sham complete basis set (KS-CBS) limit extrapolations of the electronic structure of “blue dimer” using GGA (BPW91 and BP86), hybrid-GGA (B3LYP), and meta-GGA (M06-L) density functionals. The dependence of solvation free energy corrections on the different cavity types (UFF, UA0, UAHF, UAKS, Bondi, and Pauling) within polarizable and conductor-like polarizable continuum model has also been investigated. The most common basis sets of double-zeta quality are shown to yield results close to the KS-CBS limit; however, large variations are observed in the reaction energetics as a function of density functional and continuum cavity model employed.},
doi = {10.1063/1.4719937},
url = {https://www.osti.gov/biblio/1053360},
journal = {Journal of Chemical Physics, 136(20):204104},
number = ,
volume = ,
place = {United States},
year = {Wed May 23 00:00:00 EDT 2012},
month = {Wed May 23 00:00:00 EDT 2012}
}