Ultrafast isomerization in acetylene dication after carbon K-shell ionization

Nature Communications 8(1), 453(2017). doi:10.1038/s41467-017-00426-6
Ultrafast proton migration and isomerization are key processes for acetylene and its ions. However, the mechanism for ultrafast isomerization of acetylene [HCCH]$^{2+}$to vinylidene [H$_2$CC]$^{2+}$ dication remains nebulous. Theoretical studies show a large potential barrier (> 2 eV) for isomerization on low-lying dicationic states, implying picosecond or longer isomerization timescales. However, a recent experiment at a femtosecond X-ray free-electron laser suggests sub-100 fs isomerization. Here we address this contradiction with a complete theoretical study of the dynamics of acetylene dication produced by Auger decay after X-ray photoionization of the carbon atom K shell. We find no sub-100 fs isomerization, whilereproducing the salient features of the time-resolved Coulomb imaging experiment. This work resolves the seeming contradiction between experiment and theory and also calls forcareful interpretation of structural information from the widely applied Coulomb momentum imaging method.
Published by Nature Publishing Group, London