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Issue 24, 2018
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A paramedic treatment for modeling explicitly solvated chemical reaction mechanisms

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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

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Publication details

The article was received on 28 Mar 2018, accepted on 28 May 2018 and first published on 30 May 2018


Article type: Edge Article
DOI: 10.1039/C8SC01424H
Chem. Sci., 2018,9, 5341-5346
  • Open access: Creative Commons BY license
    All publication charges for this article have been paid for by the Royal Society of Chemistry

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    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

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