Solvated Reaction Mechanisms

Our work in this field aims to unravel complicated reaction mechanisms where processes are not only determined by chemical transformations of intermediates in solution, but also interactions between the intermediates, the solvent, and other species in the solvent (e.g. counter ions from the electrolyte).

In collaboration with Karl Johnson’s (Pitt-ChemE) group and Graeme Henkelman (UT Austin), we showed how atomic scale reaction pathways can be generated for complex solvent phase reactions without pre-defining collective variables for reaction pathways. A large number of reaction pathways for borohydride hydrolysis in water were discussed.

Mitch then showed how reaction energies from explicit solvation modeling are reasonably well reproduced using subsets of coordinates from the nudged-elastic band calculations embedded in continuum solvation models. This provides a simple way to incorporate higher levels of QM theory into computational simulations with explicit solvation. We then tested how reaction energetics differ when using different levels of quantum chemistry theory and found that level of theory plays a far lesser role in energetics than explicit solvent interactions and nearby counterions.


Tae Hoon Choi, Alex Maldonado, Yasemin Basdogan, Mitch Groenenboom, Ethan Henderson

Basdogan and Keith, Chem. Sci., 2018, 9, 5341-5346, DOI: 10.1039/c8sc01424h.
Groenenboom and Keith, J. Phys. Chem. B, 2016, 120, 10797-10807, DOI: 10.1021/acs.jpcb.6b07606.

We are further investigating the performance of other reaction pathway searching technqiues (e.g. GSM, NEB, QM/MM PMF).