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Title: Projector-Based Embedding Eliminates Density Functional Dependence for QM/MM Calculations of Reactions in Enzymes and Solution
Authors: Kara E. Ranaghan
Darya Shchepanovska
Simon J. Bennie
Narin Lawan
Stephen J. Macrae
Jolanta Zurek
Frederick R. Manby
Adrian J. Mulholland
Keywords: Chemical Engineering
Computer Science
Social Sciences
Issue Date: 28-May-2019
Abstract: © 2019 American Chemical Society. Combined quantum mechanics/molecular mechanics (QM/MM) methods are increasingly widely utilized in studies of reactions in enzymes and other large systems. Here, we apply a range of QM/MM methods to investigate the Claisen rearrangement of chorismate to prephenate, in solution, and in the enzyme chorismate mutase. Using projector-based embedding in a QM/MM framework, we apply treatments up to the CCSD(T) level. We test a range of density functional QM/MM methods and QM region sizes. The results show that the calculated reaction energetics are significantly more sensitive to the choice of density functional than they are to the size of the QM region in these systems. Projector-based embedding of a wave function method in DFT reduced the 13 kcal/mol spread in barrier heights calculated at the DFT/MM level to a spread of just 0.3 kcal/mol, essentially eliminating dependence on the functional. Projector-based embedding of correlated ab initio methods provides a practical method for achieving high accuracy for energy profiles derived from DFT and DFT/MM calculations for reactions in condensed phases.
ISSN: 15205142
Appears in Collections:CMUL: Journal Articles

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