Automated prediction of the pyrolysis of chemical bonds

• Applicant: Dr.-Ing. Malte Döntgen
• Subject Area: Energy Process Engineering
• Term: since 2021
• Project identifier: Deutsche Forschungsgemeinschaft (DFG) - Project number 467725635

Elevated temperatures lead to pyrolytic reactivity. The resulting dissociation of chemical bonds is relevant for gaseous, liquid, and solid compounds and can be observed in nature and technical processes. Quantification of dissociation kinetics is therefore key for avoiding or utilizing pyrolysis in natural and technical processes. In the proposed research, an automated scheme for predicting bond dissociation kinetics will be developed. With this scheme, the chemical stability of substances under various conditions can be tested. Temperature- and pressure-dependent rate coefficients will be obtained from microscopic balancing of all bond dissociation reactions via Master Equation simulations. The bond dissociation reactions will be described by their bond dissociation energy profiles, which will be obtained via multi-reference ab initio methods. A key challenge will be the determination of chemically relevant molecular orbitals for multi-reference calculation. The proposed automation scheme will be validated against experimentally determined rate coefficients. These rate coefficients will be obtained from modeling of the concentration decay of relevant reactant and product molecules measured during high-temperature shock tube experiments. A cutting-edge infrared laser absorption setup will be used to achieve a high temporal resolution for the concentration profiles of multiple species. With the present work, a milestone in the automated prediction of complete chemical kinetic models of complex chemical processes will be accomplished.

• DFG Programme: Research Grants