A paramedic treatment for modeling explicitly solvated chemical reaction mechanisms

Chemical Science
Yasemin Basdogan, John A Keith

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.

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Citations

Feb 7, 2020·Journal of Computational Chemistry·Gregor N SimmMarkus Reiher
Sep 23, 2019·The Journal of Chemical Physics·Varsha JainNeeraj Rai
Apr 10, 2020·The Journal of Chemical Physics·Alex M MaldonadoJohn A Keith
Apr 25, 2019·The Protein Journal·Kenneth A Rubinson
Jan 10, 2021·Journal of Computer-aided Molecular Design·Rebecca SurePeter Deglmann
May 5, 2020·Journal of Chemical Theory and Computation·Jun ZhangManh-Thuong Nguyen
May 22, 2021·Chemical Society Reviews·Chang-Xin ZhaoQiang Zhang
Dec 7, 2019·Journal of Chemical Theory and Computation·Yasemin BasdoganJohn A Keith
Nov 2, 2018·Journal of the American Chemical Society·Arkajyoti SenguptaKenneth M Merz
Jan 5, 2021·The Journal of Physical Chemistry. a·Alex M MaldonadoJohn A Keith
Sep 18, 2020·ACS Applied Materials & Interfaces·Yan WangLeanne M Gilbertson

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Software Mentioned

ReMatch
IGRRHO
ABCluster
Plata
TINKER
ORCA
- SOAP
COSMO

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