Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study

Quantum chemical calculations using density functional theory have been carried out to investigate the basicity of pentaammine(pyrazine)ruthenium(II) and pentacyano(pyrazine)ruthenate(II) ions. Gas phase equilibrium geometries were fully optimized at the local density approximation (LDA) level. Sing...

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Autores principales: Hamra, O.Y., Slep, L.D., Olabe, J.A., Estrin, D.A.
Formato: JOUR
Acceso en línea:http://hdl.handle.net/20.500.12110/paper_00201669_v37_n8_p2033_Hamra
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Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA) de Universidad de Buenos Aires
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spelling todo:paper_00201669_v37_n8_p2033_Hamra2023-10-03T14:16:49Z Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study Hamra, O.Y. Slep, L.D. Olabe, J.A. Estrin, D.A. Quantum chemical calculations using density functional theory have been carried out to investigate the basicity of pentaammine(pyrazine)ruthenium(II) and pentacyano(pyrazine)ruthenate(II) ions. Gas phase equilibrium geometries were fully optimized at the local density approximation (LDA) level. Single-point calculations were performed at the optimized gas phase geometries using a generalized gradient approximation (GGA) functional. The basicity of the uncoordinated nitrogen on pyrazine was investigated in gas phase and in aqueous solution, modeling solvent effects using a self-consistent reaction field (SCRF) Onsager model, a discrete electrostatic representation of the water molecules in the first solvation shell, and also a combined SCRF-discrete model within the DFT-GGA methodology. A reasonable level of agreement between theory and experiment is obtained only when using the SCRF-discrete model, suggesting that both specific interactions in the first solvation shell and long-range dielectric effects affect the reactivity of the complexes. JOUR info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/2.5/ar http://hdl.handle.net/20.500.12110/paper_00201669_v37_n8_p2033_Hamra
institution Universidad de Buenos Aires
institution_str I-28
repository_str R-134
collection Biblioteca Digital - Facultad de Ciencias Exactas y Naturales (UBA)
description Quantum chemical calculations using density functional theory have been carried out to investigate the basicity of pentaammine(pyrazine)ruthenium(II) and pentacyano(pyrazine)ruthenate(II) ions. Gas phase equilibrium geometries were fully optimized at the local density approximation (LDA) level. Single-point calculations were performed at the optimized gas phase geometries using a generalized gradient approximation (GGA) functional. The basicity of the uncoordinated nitrogen on pyrazine was investigated in gas phase and in aqueous solution, modeling solvent effects using a self-consistent reaction field (SCRF) Onsager model, a discrete electrostatic representation of the water molecules in the first solvation shell, and also a combined SCRF-discrete model within the DFT-GGA methodology. A reasonable level of agreement between theory and experiment is obtained only when using the SCRF-discrete model, suggesting that both specific interactions in the first solvation shell and long-range dielectric effects affect the reactivity of the complexes.
format JOUR
author Hamra, O.Y.
Slep, L.D.
Olabe, J.A.
Estrin, D.A.
spellingShingle Hamra, O.Y.
Slep, L.D.
Olabe, J.A.
Estrin, D.A.
Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study
author_facet Hamra, O.Y.
Slep, L.D.
Olabe, J.A.
Estrin, D.A.
author_sort Hamra, O.Y.
title Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study
title_short Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study
title_full Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study
title_fullStr Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study
title_full_unstemmed Influence of Solvent Effects on the Basicity of Pentaammine(pyrazine)ruthenium (H) and Pentacyano(pyrazine)ruthenate(II) Ions: A Density Functional Study
title_sort influence of solvent effects on the basicity of pentaammine(pyrazine)ruthenium (h) and pentacyano(pyrazine)ruthenate(ii) ions: a density functional study
url http://hdl.handle.net/20.500.12110/paper_00201669_v37_n8_p2033_Hamra
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