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Exploring mechanochemical reactions at the nanoscale: theory <i>versus</i> experiment

Nicholas Hopper, François Sidoroff, Resham Rana, Robert Bavisotto, Juliette Cayer-Barrioz, Denis Mazuyer, Wilfred T. Tysoe

2023Physical Chemistry Chemical Physics23 citationsDOIOpen Access PDF

Abstract

slab displacement for both structures. The reaction rate was also measured experimentally under compression using a nanomechanochemical reactor comprising an atomic-force-microscopy (AFM) instrument tip compressing a methyl thiolate overlayer on Cu(100) (the same system for which the calculations were carried out). The rate was measured from the indent created on a defect-free region of the methyl thiolate overlayer, which also enabled the contact area to be measured. Knowing the force applied by the AFM tip yields the reaction rate as a function of the contact stress. The result agrees well with the theoretical prediction without the use of adjustable parameters. This confirms that the postulate is correct and will facilitate the calculation of the rates of more complex mechanochemical reactions. An advantage of this approach, in addition to the results agreeing with the experiment, is that it provides insights into the effects that control mechanochemical reactivity that will assist in the targeted design of new mechanochemical syntheses.

Topics & Concepts

OverlayerReaction rateSlabWork (physics)Transition state theoryChemistryTransition stateMaterials scienceKineticsThermodynamicsReaction rate constantPhysical chemistryPhysicsClassical mechanicsBiochemistryGeophysicsCatalysisForce Microscopy Techniques and ApplicationsMicrostructure and mechanical propertiesAdvanced Electron Microscopy Techniques and Applications
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