Basis set effects in the description of the Cl-O bond in ClO and XClO/ClOX isomers (X = H, O, and Cl) using DFT and CCSD(T) methods

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Título

Basis set effects in the description of the Cl-O bond in ClO and XClO/ClOX isomers (X = H, O, and Cl) using DFT and CCSD(T) methods

Tema

OXIDOS DE CLORO
METODOS FUNCIONALES DE DENSIDAD
BIBLIOGRAFIA NACIONAL QUIMICA
2019

Abstract

The performance of a group of density functional methods of progressive complexity for the description of the ClO bond in a series of chlorine oxides was investigated. The simplest ClO radical species as well as the two isomeric structures XClO/ClOX for each X=H, Cl and O were studied using the PW91, TPSS, B3LYP, PBE0, M06, M06-2X, BMK and B2PLYP functionals. Geometry optimizations as well as reaction enthalpies and enthalpies of formation for each species were calculated using Pople basis sets and the (aug)-cc-pVnZ Dunning sets, with n=2-6. For the calculation of enthalpies of formation, atomization as well as isodesmic reactions were employed. Both the precision of the methods with respect to the increase of the basis sets, as well as their accuracy, were gauged by comparing the results with the more accurate CCSD(T) calculations, performed using the same basis sets as for the DFT methods. The results obtained employing composite chemical methods (G4, CBS-QB3 and W1BD) were also used for the comparisons, as well as the experimental results when they are available. The results obtained show that error compensation is the key for successful description of molecular properties (geometries and energies) by carefully selecting method and basis sets. In general, expansion of the one-electron basis set to the limit of completeness does not improve results at the DFT level, but just the opposite. The enthalpies of formation calculated at the CCSD(T)/aug-cc-pV6Z for the species considered are generally in agreement with experimental determinations, and the most accurate derived theoretically up to present. Different sources of error in the calculations are discussed in detail.

Autor

Irving, Kenneth
Kieninger, Martina

Fuente

Journal of Chemistry  v. 2019, 2019. -- 23p.--e4057848

Editor

Hindawi

Fecha

2019

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PDF

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Inglés

Tipo

Artículo

Identificador

DOI: 10.1155/2019/4057848

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PDF
Fecha de agregación
August 20, 2019
Colección
Bibliografía Nacional Química
Tipo de Elemento
Document
Citación
Irving, Kenneth, “Basis set effects in the description of the Cl-O bond in ClO and XClO/ClOX isomers (X = H, O, and Cl) using DFT and CCSD(T) methods,” RIQUIM - Repositorio Institucional de la Facultad de Química - UdelaR, accessed September 24, 2019, http://riquim.fq.edu.uy/items/show/5845.
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