A simple topology-based model for predicting the activation barriers of reactive processes at 0 K.

Phys Chem Chem Phys

Facultad de Ciencias Exactas, Centro de Química Teórica & Computacional (CQT&C), Departamento de Ciencias Químicas, Universidad Andrés Bello, Avenida República 275, 8370146, Santiago de Chile, Chile.

Published: May 2023

This work reveals an underlying correlation between the topology and energetic features of matter configurations/rearrangements by exploiting two topological concepts, namely, structural stability and persistency, leading thus to a model capable of predicting activation energies at 0 K. This finding provides some answers to the difficulties of applying Thom's functions for extracting energetic information of rate processes, which has been a limitation for exact, biological, and technological sciences. A linear relationship between the experimental barriers of 17 chemical reactions and both concepts was found by studying these systems' topography along the intrinsic reaction coordinate. Such a procedure led to the model , which accurately predicts the activation energy in reacting systems involving organic and organometallic compounds under different conditions, , the gas-phase, solvent media, and temperature. This function was further recalibrated to enhance its predicting capabilities, generating the equation for this procedure, characterized by a squared Pearson correlation coefficient ( = 0.9774) 1.1 times higher. Surprisingly, no improvement was observed.

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http://dx.doi.org/10.1039/d3cp01008bDOI Listing

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