Benchmark database of barrier heights for heavy atom transfer, nucleophilic substitution, association, and unimolecular reactions and its use to test theoretical methods.
By Yan Zhao, N. González-García, Donald G. Truhlar. Journal of Physical Chemistry A, 2005
701 citations recorded by the source corpus.
A benchmark database of forward and reverse barrier heights for 19 non-hydrogen-transfer reactions has been developed by using Weizmann 1 calculations, and 29 DFT methods and 6 ab initio wave-function theory (WFT) methods have been tested against the new database as well as against an older database for hydrogen atom transfer reactions. Among the tested hybrid DFT methods without kinetic energy density, MPW1K is the most accurate model for calculations of barrier heights. Among the tested hybrid meta DFT methods, BB1K and MPWB1K are the two most accurate models for the calculations of barrier heights. Overall, the results show that BB1K and MPWB1K are the two best DFT methods for calculating barrier heights, followed in order by MPW1K, MPWKCIS1K, B1B95, MPW1B95, BH and HLYP, B97-2, mPW1PW91, and B98. The popular B3LYP method has a mean unsigned error four times larger than that of BB1K. Of the methods tested, QCISD(T) is the best ab initio WFT method for barrier height calculations, and QCISD is second best, but QCISD is outperformed by the BB1K, MPWB1K, MPWKCIS1K, and MPW1K methods.
Subfields: Atomic and Molecular Physics, and Optics, Organic Chemistry
View Paper: https://www.semanticscholar.org/paper/f7f5013cde870ed5008526715a075eeaf0335122
How researchers see this paper
The researchers whose trusted networks rank it highest, strongest advocate first. Every researcher gets a different order.
In Atomic and Molecular Physics, and Optics
- Roberto Peverati
- Donald G. Truhlar
- J. Perdew
- Stefan Grimme
- Yan Zhao
- M. Head‐Gordon
- Lars Goerigk
- Narbe Mardirossian
In Organic Chemistry
Citations in the corpus
- Accurate and numerically efficient r$^2$SCAN meta-generalized gradient approximation (2020, methodology): “Further Testing The transferablility of the new functionals was further tested for 76 reaction barrier heights [54], 22 weak interaction energies [55], and 20 lattice constants [56], with error statistics summarized in Table II.”