Modeling Multi-Step Organic Reactions: Can Density Functional Theory Deliver Misleading Chemistry?

doi:10.1021/jacs.3c12713

Modeling Multi-Step Organic Reactions: Can Density Functional Theory Deliver Misleading Chemistry?

2024-02-27

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AI

H

Hanwei Li

M

Maryam Mansoori Kermani

DOI：10.1021/jacs.3c12713

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Abstract

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Many organic reactions are characterized by a complex mechanism with a variety of transition states and intermediates of different chemical natures. Their correct and accurate theoretical characterization critically depends on the accuracy of the computational method used. In this work, we study a complex ambimodal cycloaddition with five transition states, two intermediates, and three products, and we ask whether density functional theory (DFT) can provide a correct description of this type of complex and multifaceted reaction. Our work fills a gap in that most systematic benchmarks of DFT for chemical reactions have considered much simpler reactions. Our results show that many density functionals not only lead to seriously large errors but also differ from one another in predicting whether the reaction is ambimodal. Only a few of the available functionals provide a balanced description of the complex and multifaceted reactions. The parameters varied in the tested functionals are the ingredients, the treatment of medium-range and nonlocal correlation energy, and the inclusion of Hartree-Fock exchange. These results show a clear need for more benchmarks on the mechanisms of large molecules in complex reactions.

Keywords:

MAIN-GROUP THERMOCHEMISTRY

GENERALIZED GRADIENT APPROXIMATION

RANGE-SEPARATED HYBRID

NONCOVALENT INTERACTIONS

DISPERSION CORRECTIONS

NONLOCAL CORRELATION

IMPROVED ACCURACY

BROAD ACCURACY

HARTREE-FOCK

BASIS-SETS

Modeling Multi-Step Organic Reactions: Can Density Functional Theory Deliver Misleading Chemistry?

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