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Barrier Heights for Diels-Alder Transition States Leading to Pentacyclic Adducts: A Benchmark Study of Crowded, Strained Transition States of Large Molecules.
Kermani, Maryam Mansoori; Li, Hanwei; Ottochian, Alistar; Crescenzi, Orlando; Janesko, Benjamin G; Scalmani, Giovanni; Frisch, Michael J; Ciofini, Ilaria; Adamo, Carlo; Truhlar, Donald G.
Afiliación
  • Kermani MM; Department of Chemistry, Chemical Theory Center, and Minnesota Supercomputing Institute, University of Minnesota, Minneapolis, Minnesota 55455-0431, United States.
  • Li H; Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, F-75005 Paris, France.
  • Ottochian A; Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, F-75005 Paris, France.
  • Crescenzi O; Dipartimento di Scienze Chimiche, Università di Napoli Federico II, Complesso Universitario di Monte Sant'Angelo, Via Cinthia, 80126 Napoli, Italy.
  • Janesko BG; Department of Chemistry & Biochemistry, Texas Christian University, Fort Worth, Texas 76129, United States.
  • Scalmani G; Gaussian, Inc., Wallingford, Connecticut 06492, United States.
  • Frisch MJ; Gaussian, Inc., Wallingford, Connecticut 06492, United States.
  • Ciofini I; Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, F-75005 Paris, France.
  • Adamo C; Chimie ParisTech, PSL Research University, CNRS, Institute of Chemistry for Life and Health Sciences, F-75005 Paris, France.
  • Truhlar DG; Institut Universitaire de France, 103 Boulevard Saint Michel, F-75005 Paris, France.
J Phys Chem Lett ; 14(29): 6522-6531, 2023 Jul 27.
Article en En | MEDLINE | ID: mdl-37449565
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 used 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 ωB97M-V, M11plus, ωB97X-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.
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Prognostic_studies Idioma: En Revista: J Phys Chem Lett Año: 2023 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos
Texto completo
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Texto completo: 1 Colección: 01-internacional Base de datos: MEDLINE Tipo de estudio: Prognostic_studies Idioma: En Revista: J Phys Chem Lett Año: 2023 Tipo del documento: Article País de afiliación: Estados Unidos Pais de publicación: Estados Unidos