Journal article
Benchmark study of DFT functionals for late-transition-metal reactions
Journal of Physical Chemistry A, Vol.110(2), pp.709-716
Jan/2006
Abstract
The performance of a wide variety of DFT exchange-correlation functionals for a number of late-transition-metal reaction profiles has been considered. Benchmark ab-initio reference data for the prototype reactions Pd + H-2, Pd + CH4, Pd + C2H6 (both C-C and C-H activation), and Pd + CH3Cl are presented, while ab-initio data of lesser quality were obtained for the catalytic hydrogenation of acetone and for the low-oxidation-state and high-oxidation-state mechanisms of the Heck reaction. "Kinetics" functionals such as mPWIK, PWB6K, BB1K, and BMK clearly perform more poorly for late-transition-metal reactions than for main-group reactions, as well as compared to general-purpose functionals. There is no single "best functional" for late-transition-metal reactions, but rather a cluster of several functionals (PBE0, B1B95, PW6B95, and TPSS25B95) that perform about equally well; if main-group thermochemical performance is additionally considered, then B1B95 and PW6B95 emerge as the best performers. TPSS25B95 and TPSS33B95 offer attractive performance compromises if weak interactions and main-group barrier heights, respectively, are also important. In the ab-initio calculations, basis set superposition errors (BSSE) can be greatly reduced by ensuring that the metal spd shell has sufficient radial flexibility in the high-exponent range. Optimal HF percentages in hybrid functionals depend on the class of systems considered. increasing from anions to neutrals to cations to main-group barrier heights; transition-metal barrier heights represent an intermediate situation. The use of meta-GGA correlation functionals appears to be quite beneficial.
Details
- Title
- Benchmark study of DFT functionals for late-transition-metal reactions
- Creators
- Miriam M. Quintal (null) - Harvard UniversityAmir Karton (null) - The Weizmann Institute of ScienceMA Iron (null) - 972WIS_INST___100AD Boese (null) - Karlsruhe Institute of TechnologyJML Martin (null) - The Weizmann Institute of Science
- Resource Type
- Journal article
- Publication Details
- Journal of Physical Chemistry A, Vol.110(2), pp.709-716; Jan/2006
- Number of pages
- 8
- Language
- English
- DOI
- https://doi.org/10.1021/jp054449w
- Grant note
- Acknowledgment. This work was supported by the Israel Science Foundation (Grant 704/05), by the Lise MeitnerMinerva Center for Computational Quantum Chemistry, and by the Helen and Martin Kimmel Center for Molecular Design. M.M.Q. acknowledges a Fulbright fellowship from the United States-Israel Educational Foundation. J.M.L.M. is the Baroness Thatcher Professor of Chemistry.
- Record Identifier
- 993264861303596
Metrics
5 Record Views