Quantum state-specific unimolecular dynamics by SEP
Vibration-rotation quantum state resolved investigations of the unimolecular dissociative dynamics of highly vibrationally excited molecules at and above the dissociation limit performed in our group have led to a new level of understanding of unimolecular elementary chemical reactions.
Highly detailed spectra are recorded using Stimulated Emission Pumping (SEP). For the prototypical radicals CH3O and HCO/DCO as almost ideal model systems, the relation between intramolecular vibrational redistribution (IVR) and "state-specific" or "statistical" molecular dynamics has rarely been elucidated in more detail. In the case of DCO, the unimolecular dissociation rates are predicted directly from the vibrational spectrum.
- J. Wei, A. Tröllsch, C. M. Tesch, F. Temps, "Rotational State Dependent Mixings between Resonance States of Vibrationally Highly Excited DCO (X 2A')," J. Chem. Phys. 120, 10530 - 10542 (2004).
- F. Renth, A. Tröllsch, F. Temps, "Intramolecular Vibrational Energy Redistribution, Mode Specificity, and Non-Exponential Unimolecular Decay of Vibrationally Highly Excited States of DCO (X 2A')", J. Chem. Phys. 118, 659 - 668 (2003).
- F. Temps, A. Troellsch, "Analysis of Highly Excited Vibrational Bound and Resonance States of DCO (X 2A) using an Effective Polyad Model Hamiltonian", Z. Phys. Chem. 215, 207 - 232 (2001).
- C. Stöck, X. Li, H.-M. Keller, R. Schinke, F. Temps, "Unimolecular Dissociation Dynamics of Highly Vibrationally Excited DCO (X 2A'): I. Investigation of Dissociative Resonance States by Stimulated Emission Pumping Spectroscopy", J. Chem. Phys. 106, 5333 - 5358 (1997).
- S. Dertinger, A. Geers, J. Kappert, F. Temps, J. W. Wiebrecht, "Rotation-Vibration State Resolved Unimolecular Dynamics of Highly Vibrationally Excited CH3O (X 2E): III. State Specific Dissociation Rates from Spectroscopic Line Profiles and Time Resolved Measurements", Faraday Discuss. Roy. Soc. 102, 31 - 52 (1995).