Modeling of Reactions in Confined Spaces

Abstract: 
In this talk, I will describe our recent effort in using quantum chemistry to model binding and reactions inside self-assembled capsules.[1-4] Description of these systems requires: 1) structural and energetic characterization of the capsules, 2) accurate determination of the binding free energies of all possible guests, including reactants, solvent and solvent impurities, and 3) calculation of the reaction pathways inside and outside the capsule.
We show that the modern density functional theory (DFT) methodology provides a reasonable approach for this purpose. Detailed energy decomposition analysis is applied to identify the factors causing the rate enhancement and the selectivity introduced by the capsule. However, host-guest binding free energies in aqueous solution require special treatment. A new approach is presented which gives very promising results.

References:
[1] Henrik Daver, Jeremy N. Harvey, Julius Rebek Jr., Fahmi Himo, 
Quantum Chemical Modeling of Cycloaddition Reaction in a Self-Assembled Capsule, 
J. Am. Chem. Soc. 2017, 139, 15494-15503.
[2] Henrik Daver, Andrés G. Algarra, Jeremy N. Harvey, Julius Rebek Jr., Fahmi Himo, 
A Mixed Explicit-Implicit Solvation Approach for Modeling of Alkane Complexation in Water-Soluble Self-Assembled Capsules, 
J. Am. Chem. Soc. 2018, 140, 12527-12537.
[3] Oriana Brea, Henrik Daver, Julius Rebek Jr., Fahmi Himo,
Modeling Decomposition of N-Nitrosoamides in a Self-Assembled Capsule
J. Org. Chem. 2019, 84, 7354-7361.
[4] Henrik Daver, Julius Rebek Jr., Fahmi Himo, 
Modeling Reaction of Carboxylic Acids and Isonitriles in a Self-Assembled Capsule, 
Chem. Eur. J. 2020, 26, 10861-10870.