Design of Density Functionals That Are Broadly Accurate for Thermochemistry, Thermochemical Kinetics, and Nonbonded Interactions

作者：Yan Zhao, Donald G. Truhlar · 发表于：The Journal of Physical Chemistry A · 年份：2005 · DOI：10.1021/jp050536c · 被引用次数：1730 · 研究领域：Advanced Chemical Physics Studies、Free Radicals and Antioxidants、Chemical Thermodynamics and Molecular Structure

This paper develops two new hybrid meta exchange-correlation functionals for thermochemistry, thermochemical kinetics, and nonbonded interactions. The new functionals are called PW6B95 (6-parameter functional based on Perdew-Wang-91 exchange and Becke-95 correlation) and PWB6K (6-parameter functional for kinetics based on Perdew-Wang-91 exchange and Becke-95 correlation). The resulting methods were comparatively assessed against the MGAE109/3 main group atomization energy database, against the IP13/3 ionization potential database, against the EA13/3 electron affinity database, against the HTBH38/4 and NHTBH38/04 hydrogen-transfer and non-hydrogen-transfer barrier height databases, against the HB6/04 hydrogen bonding database, against the CT7/04 charge-transfer complex database, against the DI6/04 dipole interaction database, against the WI7/05 weak interaction database, and against the new PPS5/05 pi-pi stacking interaction database. From the assessment and comparison of methods, we draw the following conclusions, based on an analysis of mean unsigned errors: (i) The PW6B95, MPW1B95, B98, B97-1, and TPSS1KCIS methods give the best results for a combination of thermochemistry and nonbonded interactions. (ii) PWB6K, MPWB1K, BB1K, MPW1K, and MPW1B95 give the best results for a combination of thermochemical kinetics and nonbonded interactions. (iii) PWB6K outperforms the MP2 method for nonbonded interactions. (iv) PW6B95 gives errors for main group covalent bond energies that are...