Issue 24, 2018

A paramedic treatment for modeling explicitly solvated chemical reaction mechanisms

Abstract

We report a static quantum chemistry modeling treatment to study how solvent molecules affect chemical reaction mechanisms without dynamics simulations. This modeling scheme uses a global optimization procedure to identify low energy intermediate states with different numbers of explicit solvent molecules and then the growing string method to locate sequential transition states along a reaction pathway. Testing this approach on the acid-catalyzed Morita–Baylis–Hillman (MBH) reaction in methanol, we found a reaction mechanism that is consistent with both recent experiments and computationally intensive dynamics simulations with explicit solvation. In doing so, we explain unphysical pitfalls that obfuscate computational modeling that uses microsolvated reaction intermediates. This new paramedic approach can promisingly capture essential physical chemistry of the complicated and multistep MBH reaction mechanism, and the energy profiles found with this model appear reasonably insensitive to the level of theory used for energy calculations. Thus, it should be a useful and computationally cost-effective approach for modeling solvent mediated reaction mechanisms when dynamics simulations are not possible.

Graphical abstract: A paramedic treatment for modeling explicitly solvated chemical reaction mechanisms

Supplementary files

Article information

Article type
Edge Article
Submitted
28 mar 2018
Accepted
28 mai 2018
First published
30 mai 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 5341-5346

A paramedic treatment for modeling explicitly solvated chemical reaction mechanisms

Y. Basdogan and J. A. Keith, Chem. Sci., 2018, 9, 5341 DOI: 10.1039/C8SC01424H

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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