1. Quantum Mechanical Modeling of Reaction Rate Acceleration in Microdroplets
- Author
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Namita Narendra, James Charles, R. Graham Cooks, Xingshuo Chen, Tillmann Kubis, and Jinying Wang
- Subjects
010304 chemical physics ,Chemistry ,Orders of magnitude (temperature) ,Solvation ,010402 general chemistry ,01 natural sciences ,0104 chemical sciences ,Reaction rate ,Acceleration ,Organic reaction ,Chemical physics ,0103 physical sciences ,Physical and Theoretical Chemistry ,Quantum - Abstract
Organic reactions in microdroplets can be orders of magnitude faster than their bulk counterparts. We hypothesize that solvation energy differences between bulk and interface play a key role in the intrinsic rate constant increase and test the hypothesis with explicit solvent calculations. We demonstrate for both the protonated phenylhydrazine reagent and the hydrazone transition state (TSB) that molecular orientations which place the charge sites at the surface confer high energy. A pathway in which this high-energy form transforms into a fully solvated TSB has a lower activation energy than bulk by some 59 kJ/mol, a result that is consistent with experimental rate acceleration studies.
- Published
- 2020