On the role of interfacial hydrogen bonds in 'on-water' catalysis
- Resource Type
- Working Paper
- Authors
- Karhan, Kristof; Khaliullin, Rustam Z.; Kühne, Thomas D.
- Source
- J. Chem. Phys. 141, 22D528 (2014)
- Subject
- Physics - Chemical Physics
Condensed Matter - Soft Condensed Matter
Physics - Biological Physics
- Language
Numerous experiments have demonstrated that many classes of organic reactions exhibit increased reaction rates when performed in heterogeneous water emulsions. Despite enormous practical importance of the observed "on-water" catalytic effect and several mechanistic studies, its microscopic origins remains unclear. In this work, the second generation Car-Parrinello molecular dynamics method is extended to self-consistent charge density-functional based tight-binding in order to study "on-water" catalysis of the Diels-Alder reaction between dimethyl azodicarboxylate and quadricyclane. We find that the stabilization of the transition state by dangling hydrogen bonds exposed at the aqueous interfaces plays a significantly smaller role in "on-water" catalysis than has been suggested previously.
Comment: 6 pages, 3 figures