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Issue 30, 2011
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Validation of electronic structure methods for isomerization reactions of large organic molecules

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Abstract

In this work the ISOL24 database of isomerization energies of large organic molecules presented by Huenerbein et al. [Phys. Chem. Chem. Phys., 2010, 12, 6940] is updated, resulting in the new benchmark database called ISOL24/11, and this database is used to test 50 electronic model chemistries. To accomplish the update, the very expensive and highly accurate CCSD(T)-F12a/aug-cc-pVDZ method is first exploited to investigate a six-reaction subset of the 24 reactions, and by comparison of various methods with the benchmark, MCQCISD-MPW is confirmed to be of high accuracy. The final ISOL24/11 database is composed of six reaction energies calculated by CCSD(T)-F12a/aug-cc-pVDZ and 18 calculated by MCQCISD-MPW. We then tested 40 single-component density functionals (both local and hybrid), eight doubly hybrid functionals, and two other methods against ISOL24/11. It is found that the SCS-MP3/CBS method, which is used as benchmark for the original ISOL24, has an MUE of 1.68 kcal mol−1, which is close to or larger than some of the best tested DFT methods. Using the new benchmark, we find ωB97X-D and MC3MPWB to be the best single-component and doubly hybrid functionals respectively, with PBE0-D3 and MC3MPW performing almost as well. The best single-component density functionals without molecular mechanics dispersion-like terms are M08-SO, M08-HX, M05-2X, and M06-2X. The best single-component density functionals without Hartree–Fock exchange are M06-L-D3 when MM terms are included and M06-L when they are not.

Graphical abstract: Validation of electronic structure methods for isomerization reactions of large organic molecules

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Publication details

The article was received on 20 Mar 2011, accepted on 25 May 2011 and first published on 04 Jul 2011


Article type: Paper
DOI: 10.1039/C1CP20834A
Citation: Phys. Chem. Chem. Phys., 2011,13, 13683-13689
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    Validation of electronic structure methods for isomerization reactions of large organic molecules

    S. Luo, Y. Zhao and D. G. Truhlar, Phys. Chem. Chem. Phys., 2011, 13, 13683
    DOI: 10.1039/C1CP20834A

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