Photodissociation Dynamics of Cyclopropenylidene,c‐C3H2 |
| |
| Authors: | Dr Michael S Schuurman Jens Giegerich Kai Pachner Dr Daniel Lang Benjamin Kiendl Ryan J MacDonell Prof?Dr Anke Krueger Prof?Dr Ingo Fischer |
| |
| Affiliation: | 1. National Research Council of Canada, 100 Sussex Drive, Ottawa, ON, K1A 0R6 (Canada);2. Department of Chemistry, University of Ottawa, D'Iorio Hall, 10 Marie Curie, Ottawa, ON, K1N 6N5 (Canada);3. Institute of Physical and Theoretical Chemistry, University of Würzburg, Am Hubland, 97074 Würzburg (Germany);4. Institute of Organic Chemistry, Am Hubland, 97074 Würzburg (Germany) |
| |
| Abstract: | In this joint experimental and theoretical study we characterize the complete dynamical “life cycle” associated with the photoexcitation of the singlet carbene cyclopropenylidene to the lowest lying optically bright excited electronic state: from the initial creation of an excited‐state wavepacket to the ultimate fragmentation of the molecule on the vibrationally hot ground electronic state. Cyclopropenylidene is prepared in this work using an improved synthetic pathway for the preparation of the precursor quadricyclane, thereby greatly simplifying the assignment of the molecular origin of the measured photofragments. The excitation process and subsequent non‐adiabatic dynamics have been previously investigated employing time‐resolved photoelectron spectroscopy and are now complemented with high‐level ab initio trajectory simulations that elucidate the specific vibronic relaxation pathways. Lastly, the fragmentation channels accessed by the molecule following internal conversion are probed using velocity map imaging (VMI) so that the identity of the fragmentation products and their corresponding energy distributions can be definitively assigned. |
| |
| Keywords: | ab initio molecular dynamics flash pyrolysis gas‐phase reactions non‐adiabatic processes reactive intermediate |
|
|
