Site-dependent nuclear dynamics in core-excited butadiene

Symmetry breaking and competition between electronic decay and nuclear dynamics are major factors determining whether the memory of the initial core-hole localisation in a molecule is retained long enough to affect fragmentation. We investigate the fate of core holes localised at different sites in the free 1,3 trans butadiene molecule by using synchrotron radiation to selectively excite core electrons from different C 1s sites to π* orbitals. Fragmentation involving bonds localised at the site of the core hole provides clear evidence for preferential bond breaking for a core hole located at the terminal carbon site, while the signature of localisation is weak for a vacancy on the central carbon site. The origin of this difference is attributed to out-of-plane vibrations, and statistical evaporation of protons for vacancies located at the central carbon sites

Site-dependent nuclear dynamics in core-excited butadiene

Symmetry breaking and competition between electronic decay and nuclear dynamics are major factors determining whether the memory of the initial core-hole localisation in a molecule is retained long enough to affect fragmentation. We investigate the fate of core holes localised at different sites in the free 1,3 trans butadiene molecule by using synchrotron radiation to selectively excite core electrons from different C 1s sites to the π∗ orbital (LUMO). Fragmentation involving bonds localised at the site of the core hole provides clear evidence for preferential bond breaking for a core hole located at the terminal carbon site, while the signature of localisation is weak for a vacancy on the central carbon site. The origin of this difference is attributed to out-of-plane vibrations, and statistical evaporation of protons for central carbon vacancies

Photofragmentation of gas-phase acetic acid and acetamide clusters in the vacuum ultraviolet region

Photofragmentation of gas-phase acetamide and acetic acid clusters produced by a supersonic expansion source has been studied using time-of-flight mass spectrometry and the partial ion yield (PIY) technique combined with tunable vacuum-ultraviolet synchrotron radiation. Appearance energies of the clusters and their fragments were experimentally determined from the PIY measurements. The effect of clusterization conditions on the formation and fragmentation of acetic acid clusters was investigated. Ab initio quantum mechanical calculations were performed on both samples' dimers to find their neutral and ionized geometries as well as proton transfer energy barriers leading to the optimal geometries. In the case of the acetamide dimer, the reaction resulting in the production of ammoniated acetamide was probed, and the geometry of the obtained ion was calculated