How does microkinetic modeling bring DFT closer to experiment?

Calculations based on density functional theory (DFT) and density functional theory / molecular mechanics (DFT/MM) are a well-established approach in the treatment of a variety of problems in chemistry, and in particular those in homogeneous catalysis.^[1] Calculations lead to a free energy profile, from where the feasibility of reactions can be ascertained, and the competition between different paths can be evaluated.

The information in the free energy profile is sufficient to explain the reactivity of systems in most cases. But the raw experimental results usually involve reaction times rather than energy barriers. Microkinetic models can make the connection between rate constants calculated from DFT free energy profiles and reaction times. In this communication we will present selected examples from work in our group^[2-4]  showing the utility of this treatment.

 

REFERENCES

[1] Harvey, J. N.; Himo, F.; Maseras, F.; Perrin, L. ACS Catal. 2019, 9, 6803-6813.

[2] Besora, M.; Maseras, F.  WIREs Comput. Mol. Sci. 2018, 8, e1372.

[3] Pérez-Soto, R.; Besora, M.; Maseras, F. Org. Lett. 2020, 22, 2873-2877.

[4] Álvarez, M.; Besora, M.; Molina, F.; Maseras, F.; Belderrain, T.; Pérez, P. J. J. Am. Chem. Soc. 2021, 143, 487-4843.