American Chemical Society
ct600281g_si_001.pdf (84.98 kB)
Download file

Representative Benchmark Suites for Barrier Heights of Diverse Reaction Types and Assessment of Electronic Structure Methods for Thermochemical Kinetics

Download (84.98 kB)
journal contribution
posted on 2007-03-13, 00:00 authored by Jingjing Zheng, Yan Zhao, Donald G. Truhlar
We propose three small sets of barrier heights for heavy-atom transfer, nucleophilic substitution, and unimolecular and association reactions as benchmarks for comparing and developing theoretical methods. We chose the data sets to be statistically representative subsets of the NHTBH38/04 database. Each data set consists of 6 barrier heights; we call these small benchmark suites HATBH6, NSBH6, and UABH6. Benchmark values are tabulated for 205 combinations of theory level and basis set. The theory levels studied include single-level wave function theory like Hartree−Fock, Møller−Plesset perturbation theory, quadratic configuration interaction, and coupled cluster theory; they also include multicoefficient correlation methods, local and hybrid density functional theory, and semiempirical molecular orbital methods. The three new representative data sets are combined with a previous representative data set for hydrogen-transfer reactions to form a new compact but diverse and representative data set called DBH24. Comparison of a large number of methods for their performance on DBH24 leads us to recommend the following methods for barrier height calculations, in order of decreasing cost:  G3SX, BMC-CCSD, PWB6K, BB1K, M06-L, MPW1K, HF/MIDI!, and PM3.