A high-level ab initio study of the photodissociation of acetaldehyde.

ABSTRACT

Acetaldehyde is a very relevant atmospheric species whose photodissociation has been extensively studied in the first absorption band both experimentally and theoretically. Very few works have been reported on acetaldehyde photodissociation at higher excitation energies. In this work, the photodissociation dynamics of acetaldehyde is investigated by means of high-level multireference configuration interaction ab initio calculations. Five different fragmentation pathways of acetaldehyde are explored by calculating the potential-energy curves of the ground and several excited electronic states along the corresponding dissociating bond distances. The excitation energy range covered in the study is up to 10 eV, nearly the ionization energy of acetaldehyde. We intend to rationalize the available experimental results and, in particular, to elucidate why some of the studied fragmentation pathways are experimentally observed in the different excitation energy regions and some others are not. Based on the shape of the calculated potential curves, we are able to explain the main findings of the available experiments, also suggesting possible dynamical dissociation mechanisms in the different energy regions. Thus, the reported potential curves are envisioned as a useful tool to interpret the currently available experiments as well as future ones on acetaldehyde photodissociation at excitation wavelengths in the range studied here.