A performance comparison between the CEP effective core potential/triple-split basis set approach and an all-electron computational method with emphasis on small Ti and V alkoxide complexes

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Abstract

The structures of 30 neutral and positively charged small clusters were optimized and a number of hypothetical reaction pathways were investigated to compare the performance of the B3LYP/CEP-121G(d) Effective Core Potential/triple-split basis set method (ECP, method 1) and the B3LYP/6- 311G(d) approach (method 2) for geometry optimizations. In addition, single point calculations at the B3LYP/CEP-121+G(d,p) (on geometries optimized by method 1) and at the B3LYP/6-311+G(d,p) (on optimized structures from methods 1 and 2) levels were also carried out. The augmented CEP-121G scheme is roughly 1.4 to 2.0 times computationally cheaper than full electron calculations, and is able to reproduce structures, infrared frequencies, thermochemical parameters and dipole moments predicted by the all-electron basis set employed in this study. From a practical viewpoint, the results confirm that ECPs can be used in combination with density functional methods, despite the fact that the former are typically generated via a Hartree-Fock approach.

Original languageEnglish (US)
Pages (from-to)206-211
Number of pages6
JournalCanadian Journal of Chemistry
Volume78
Issue number2
DOIs
StatePublished - Jan 1 2000

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Computational methods
Geometry
Electrons
Dipole moment
Infrared radiation
oligomycin sensitivity-conferring protein

Keywords

  • Alkoxides
  • CEP
  • DFT
  • Effective Core Potentials
  • Ti

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Organic Chemistry

Cite this

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title = "A performance comparison between the CEP effective core potential/triple-split basis set approach and an all-electron computational method with emphasis on small Ti and V alkoxide complexes",
abstract = "The structures of 30 neutral and positively charged small clusters were optimized and a number of hypothetical reaction pathways were investigated to compare the performance of the B3LYP/CEP-121G(d) Effective Core Potential/triple-split basis set method (ECP, method 1) and the B3LYP/6- 311G(d) approach (method 2) for geometry optimizations. In addition, single point calculations at the B3LYP/CEP-121+G(d,p) (on geometries optimized by method 1) and at the B3LYP/6-311+G(d,p) (on optimized structures from methods 1 and 2) levels were also carried out. The augmented CEP-121G scheme is roughly 1.4 to 2.0 times computationally cheaper than full electron calculations, and is able to reproduce structures, infrared frequencies, thermochemical parameters and dipole moments predicted by the all-electron basis set employed in this study. From a practical viewpoint, the results confirm that ECPs can be used in combination with density functional methods, despite the fact that the former are typically generated via a Hartree-Fock approach.",
keywords = "Alkoxides, CEP, DFT, Effective Core Potentials, Ti",
author = "Gustavo Larsen",
year = "2000",
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doi = "10.1139/v99-225",
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journal = "Canadian Journal of Chemistry",
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N2 - The structures of 30 neutral and positively charged small clusters were optimized and a number of hypothetical reaction pathways were investigated to compare the performance of the B3LYP/CEP-121G(d) Effective Core Potential/triple-split basis set method (ECP, method 1) and the B3LYP/6- 311G(d) approach (method 2) for geometry optimizations. In addition, single point calculations at the B3LYP/CEP-121+G(d,p) (on geometries optimized by method 1) and at the B3LYP/6-311+G(d,p) (on optimized structures from methods 1 and 2) levels were also carried out. The augmented CEP-121G scheme is roughly 1.4 to 2.0 times computationally cheaper than full electron calculations, and is able to reproduce structures, infrared frequencies, thermochemical parameters and dipole moments predicted by the all-electron basis set employed in this study. From a practical viewpoint, the results confirm that ECPs can be used in combination with density functional methods, despite the fact that the former are typically generated via a Hartree-Fock approach.

AB - The structures of 30 neutral and positively charged small clusters were optimized and a number of hypothetical reaction pathways were investigated to compare the performance of the B3LYP/CEP-121G(d) Effective Core Potential/triple-split basis set method (ECP, method 1) and the B3LYP/6- 311G(d) approach (method 2) for geometry optimizations. In addition, single point calculations at the B3LYP/CEP-121+G(d,p) (on geometries optimized by method 1) and at the B3LYP/6-311+G(d,p) (on optimized structures from methods 1 and 2) levels were also carried out. The augmented CEP-121G scheme is roughly 1.4 to 2.0 times computationally cheaper than full electron calculations, and is able to reproduce structures, infrared frequencies, thermochemical parameters and dipole moments predicted by the all-electron basis set employed in this study. From a practical viewpoint, the results confirm that ECPs can be used in combination with density functional methods, despite the fact that the former are typically generated via a Hartree-Fock approach.

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KW - Effective Core Potentials

KW - Ti

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