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Development of a True Transition State Force Field from Quantum Mechanical Calculations

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Research Center for Natural Sciences, Hungarian Academy of Sciences, Magyar Tudosok Korutja 2, H-1117 Budapest, Hungary
Chemistry Research Laboratory, University of Oxford, Mansfield Road, Oxford OX1 3TA, U.K.
§ Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, U.K.
Cite this: J. Chem. Theory Comput. 2016, 12, 4, 1833–1844
Publication Date (Web):February 29, 2016
https://doi.org/10.1021/acs.jctc.5b01237
Copyright © 2016 American Chemical Society

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    Abstract

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    Transition state force fields (TSFF) treated the TS structure as an artificial minimum on the potential energy surface in the past decades. The necessary parameters were developed either manually or by the Quantum-to-molecular mechanics method (Q2MM). In contrast with these approaches, here we propose to model the TS structures as genuine saddle points at the molecular mechanics level. Different methods were tested on small model systems of general chemical reactions such as protonation, nucleophilic attack, and substitution, and the new procedure led to more accurate models than the Q2MM-type parametrization. To demonstrate the practicality of our approach, transferrable parameters have been developed for Mo-catalyzed olefin metathesis using quantum mechanical properties as reference data. Based on the proposed strategy, any force field can be extended with true transition state force field (TTSFF) parameters, and they can be readily applied in several molecular mechanics programs as well.

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    The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.jctc.5b01237.

    • QM geometries, force field parameters, and data related to the fitting procedure (PDF)

    • Gaussian, MacroModel, and Tinker input files for TS optimization (ZIP)

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