Barrier Heights for Diels-Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules - Archive ouverte HAL
Article Dans Une Revue Journal of Physical Chemistry Letters Année : 2023

Barrier Heights for Diels-Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules

Maryam Mansoori Kermani
  • Fonction : Auteur
Hanwei Li
  • Fonction : Auteur
Alistar Ottochian
Orlando Crescenzi
Benjamin Janesko
Giovanni Scalmani
Michael Frisch
  • Fonction : Auteur
Carlo Adamo
Donald Truhlar

Résumé

Theoretical characterization of reactions of complex molecules depends on providing consistent accuracy for the relative energies of intermediates and transition states. Here we employ the DLPNO-CCSD(T) method with core-valence correlation, large basis sets, and extrapolation to the CBS limit, to provide benchmark values for Diels-Alder transition states leading to competitive strained pentacyclic adducts. We then use those benchmarks to test a diverse set of wave function and density functional methods for the absolute and relative barrier heights of these transition states. Our results show that only a few of the tested density functionals can predict the absolute barrier heights satisfactorily, although relative barrier heights are more accurate. The most accurate functionals tested are B97M-V, M11plus, B97X-V, PBE-D3(0), M11, and MN15 with MUDs from best estimates less than 3.0 kcal. These findings can guide selection of density functionals for future studies of crowded, strained, transition states of large molecules. TOC graphic

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Dates et versions

hal-04288508 , version 1 (16-11-2023)

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Maryam Mansoori Kermani, Hanwei Li, Alistar Ottochian, Orlando Crescenzi, Benjamin Janesko, et al.. Barrier Heights for Diels-Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules. Journal of Physical Chemistry Letters, 2023, 14 (29), pp.6522-6531. ⟨10.1021/acs.jpclett.3c01309⟩. ⟨hal-04288508⟩
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