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MECHANOCHEMISTRY

The application of a mechanical force can distort the potential energy surface of a reactive landscape, leading to new, unexpected, and exciting chemistries. Despite numerous mechanophores being developed in the laboratory, computational tools have lagged behind in their ability to accurately and efficiently simulate these processes. To provide atomistic insight into this emerging area, I developed a force functionality for the Growing String Method (GSM) and have demonstrated it to be a powerful means to identify reaction paths and transition states on force-modified potential energy  surfaces.  The use of internal coordinates

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in GSM has proven to be an effective coordinate system for complicated mechanochemical transformations, leading to efficient and reliable reaction path optimization. Additionally, because GSM is able to operate in a single-ended fashion, it is useful in discovering nonintuitive mechanochemical products even when the mechanical perturbations to the potential energy surface eliminate intermediates or transition states along a reaction path. I apply the method to challenging mechanochemical transformations with various functions in force-responsive materials. These smart materials include polymers incorporating ring-opening mechanochromes with potential applications as force sensors as well as mechanophores that exploit flex-activation – angular deformation that occurs during the elongation of polymer segments. For each of the reactions, mechanistic details that were unavailable using other theoretical methods were readily uncovered using GSM, showing it to be a widely useful tool for studying mechanochemistry.

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Loss of a Transition State

Loss of an Intermediate

Transition State Shift

Examples of energy surface deformations that may occur in mechanochemical reactions

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