DFT and Proton Transfer Reactions: A Benchmark Study on Structure and Kinetics

Area of Science:

• Computational Chemistry
• Quantum Chemistry
• Theoretical Chemistry

Background:

• Proton transfer reactions are fundamental in chemistry and biology.
• Accurate theoretical prediction of reaction energetics and structures is crucial.
• Performance of various exchange-correlation functionals needs rigorous testing.

Purpose of the Study:

• To comprehensively assess the performance of diverse exchange-correlation functionals.
• To evaluate functionals for both energetics and structural features in proton transfer reactions.
• To compare functional rankings with established kinetic datasets.

Main Methods:

• Testing a wide range of exchange-correlation functionals, including generalized gradient approximations and double hybrids.
• Comparing calculated energetics and structural parameters against reference data.
• Analyzing the performance across multiple proton transfer reaction benchmarks.

Main Results:

• ωB97X, BMK, B1LYP, and PBE0-DH functionals demonstrated a good error balance across all tested proton transfer reactions.
• The study identified specific functionals that perform well for both energetic and structural aspects.
• Rankings of functionals were compared to the standard test for kinetics (DBH24/08 set).

Conclusions:

• Certain functionals like ωB97X, BMK, B1LYP, and PBE0-DH are recommended for studying proton transfer reactions.
• General insights were gained into the influence of Hartree-Fock exchange on reaction barriers.
• The relationship between molecular structure and reaction energetics was further elucidated.