Assessing the performances of some recently proposed density functionals for the description of organometallic structures
| Autor: | Pierre Mignon, Diane Bousquet, Éric Brémond, Ilaria Ciofini, Pietro Cortona, Henry Chermette, Mahboubeh Poor Kalhor, Carlo Adamo |
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| Přispěvatelé: | Laboratoire d'Electrochimie, Chimie des Interfaces et Modélisation pour l'Energie (LECIME - UMR 7575) (LECIME), Ecole Nationale Supérieure de Chimie de Paris - Chimie ParisTech-PSL (ENSCP), Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Institut de Chimie du CNRS (INC), CHEMOD - CHEmometry et MODélisation moléculaire (2011-2014), Institut des Sciences Analytiques (ISA), Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS)-Institut de Chimie du CNRS (INC)-Université Claude Bernard Lyon 1 (UCBL), Université de Lyon-Université de Lyon-Centre National de la Recherche Scientifique (CNRS), Laboratoire Structures, Propriétés et Modélisation des solides (SPMS), Institut de Chimie du CNRS (INC)-CentraleSupélec-Centre National de la Recherche Scientifique (CNRS), the ANR agency (project DinfDFT ANR 2010 BLANC No. 0425 02), Sanofi-Aventis, the GENCI/CINES (HPC resources/computer time Project cpt2130). |
| Jazyk: | angličtina |
| Rok vydání: | 2013 |
| Předmět: |
EXCHANGE FUNCTIONALS
GENERALIZED-GRADIENT-APPROXIMATION ELECTRON-GAS 010402 general chemistry 01 natural sciences CONNECTION Set (abstract data type) Generalized gradient Computational chemistry Spin crossover [CHIM.ANAL]Chemical Sciences/Analytical chemistry 0103 physical sciences Statistical physics THERMOCHEMICAL KINETICS Physical and Theoretical Chemistry ADJUSTABLE-PARAMETERS 010304 chemical physics Series (mathematics) Chemistry Zr GRAC TRANSITION-METAL ATOMS State (functional analysis) CORRELATION-ENERGY MOLECULAR CALCULATIONS TCA 0104 chemical sciences Hybrid functional Organometallic MODEL Benchmark (computing) Density functional theory |
| Zdroj: | Theoretical Chemistry Accounts: Theory, Computation, and Modeling Theoretical Chemistry Accounts: Theory, Computation, and Modeling, Springer Verlag, 2013, 132 (12), pp.UNSP 1401. ⟨10.1007/s00214-013-1401-5⟩ |
| ISSN: | 1432-881X 1432-2234 |
| DOI: | 10.1007/s00214-013-1401-5⟩ |
| Popis: | International audience; The performances of a family of recently developed generalized gradient approximation (GGA) functionals based on the Tognetti-Cortona-Adamo (TCA) family and making use of the gradient-regulated connection (GRAC) approach are here tested on an uncommon benchmark set for the prediction of transition state (TS) structures and energies of a series of four reactions involving an early transition metal (Zr, d (0)). This benchmark test thus represents the first step in the organometallic world in which d (n) ions allowing complex phenomena such as spin crossover represent the higher level of complexity. The results obtained show that the performances of the GRAC-xxx functionals are comparable to those of global hybrid functionals both in the prediction of reaction barriers and of structural features of TSs. More complex functional forms (such as range-separated hybrids) in average enhance the energetic features, but not necessarily the overall accuracy on calculated structures. On the other hand, and as expected, purposely developed functionals for the prediction of chemical reactivity provide both structural and energetic features in good agreement with post-HF results. The present study, besides proving the good performances of GGA functionals of the GRAC-TCA family for the prediction of TS structural parameters and energetics of metal containing systems, also underlines the importance of the use of diversified benchmark sets to allow a fair evaluation of functionals performances. |
| Databáze: | OpenAIRE |
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