Work Group Prof. Dr. F. Temps

Vibration-Rotation Quantum State-Resolved Unimolecular Reaction Dynamics and Photofragment Imaging

Velocity Mapped Photofragment Ion Imaging

Ion image from HBr photodissociation

 

 

 

 

 

 

 

 

Vibration-Rotation Quantum State-Resolved Unimolecular Dynamics by Stimulated Emission Pumping

Stimulated emission pumping

 

 

 

 

 

 

New Theoretical Approaches to Unimolecular Dynamics

Wavepacket propagation with an effective Hamiltonian

While statistical unimolecular theory has been immensely successful, it cannot describe the true dynamics of molecules in specific quantum state. On the other hand, exact quantum dynamics calculations on ab initio potential energy hypersurfaces can only be carried out for small (3- or 4-atom) molecules. We employed an effective Hamiltonian, obtained by fitting to SEP spectra and complemented with an imaginary decay term, to model intramolecular vibrational energy redistribution (IVR) and the unimolecular decay kinetics of DCO (X 2A') by simple wavepacket propagation methods. The model can be extended to larger molecules.