The impact of molecular configuration on the bond breaking rates of hydrocarbons: a computational study

The dissociation of hydrocarbon bonds plays a pivotal role in their utilization, whether through fuel combustion or the thermo-cracking of large hydrocarbons in petroleum refinement. Previous studies have primarily focused on the effects of temperature, pressure, and chemical environment on hydrocarbon reactions. However, the influence of molecular configuration on bond breaking rates has not been thoroughly explored. In this study, we propose an approach to compute bond dissociation rates, and apply it to the reactive molecular dynamics simulation (ReaxFF) trajectories of three molecules: n-tridecane, n-pentane, and 1,3-propanediol. Our results reveal that the bond dissociation rate depends not only on the bond position in the chain, but also on the molecular configuration. Stretched configurations exhibit higher dissociation rates, particularly favoring the breaking of central bonds. Conversely, when the molecule is coiled, resulting in a reduced size, terminal bonds exhibit higher dissociation rates. This research contributes to a deeper understanding of molecular dissociation properties in the oxidation of hydrocarbons, and provides a way to explore the bond breaking properties of other molecules.