Theoretical and Computational Chemistry

Determination of Kinetic Properties in Unimolecular Dissociation of Complex Systems from Graph-Theory Based Analysis of an Ensemble of Reactive Trajectories.

Riccardo Spezia Sorbonne Université, Laboratoire de Chimie Théorique, UMR 7616 CNRS

Abstract

We describe and apply a general approach based on graph-theory to obtain kinetic and structural properties from direct dynamics simulations. In particular, we focus on the unimolecular fragmentation of complex systems in which, prior to dissociation, different events can take place, and notably isomerizations and formation of ion-molecule complex.
3-state and 4-state kinetic models are thus obtained and rate constants for global or specific pathways are obtained from direct counting and flux calculation, both being in agreement.
Finally, we show how a theoretical mass spectrum can also be obtained automatically.

Content

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Supplementary material

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SI