Prediction of kinetic product ratios: investigation of a dynamically controlled case

Carpenter, Barry K. ORCID: https://orcid.org/0000-0002-5470-0278 2023. Prediction of kinetic product ratios: investigation of a dynamically controlled case. The Journal of Physical Chemistry A 127 , pp. 224-239. 10.1021/acs.jpca.2c08301

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Abstract

Of the various factors influencing kinetically controlled product ratios, the role of nonstatistical dynamics is arguably the least well understood. In this paper, reactions were chosen in which dynamics played a dominant role in product selection, by design. Specifically, the reactions studied were the ring openings of cyclopropylidene to allene and tetramethylcyclopropylidene to tetramethylallene (2,4-dimethylpenta-2,3-diene). Both reactions have intrinsic reaction coordinates that bifurcate symmetrically, leading to products that are enantiomeric once the atoms are uniquely labeled. The question addressed in the study was whether the outcomes─that is, which product well on the potential energy surface was selected─could be predicted from their initial conditions for individual trajectories in quasiclassical dynamics simulations. Hybrid potentials were developed based on cooperative interaction between molecular mechanics and artificial neural networks, trained against data from electronic structure calculations. These potentials allowed simulations of both gas-phase and condensed-phase reactions. The outcome was that, for both reactions, prediction of initial selection of product wells could be made with >95% success from initial conditions of the trajectories in the gas phase. However, when trajectories were run for longer, looking for “final” products for each trajectory, the predictability dropped off dramatically. In the gas-phase simulations, this drop off was caused by trajectories hopping between product wells on the potential energy surface. That behavior could be suppressed in condensed phases, but then new uncertainty was introduced because the intermolecular interactions between solute and bath, necessary to permit intermolecular energy transfer and cooling of the hot initial products, often led to perturbations of the initial directions of trajectories on the potential energy surface. It would consequently appear that a general ability to predict outcomes for reactions in which nonstatistical dynamics dominate remains a challenge even in the age of sophisticated machine-learning capabilities.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Publisher:	American Chemical Society
ISSN:	1089-5639
Date of First Compliant Deposit:	4 January 2023
Date of Acceptance:	19 December 2022
Last Modified:	03 May 2023 02:50
URI:	https://orca.cardiff.ac.uk/id/eprint/155377

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