Ultrafast isomerization in acetylene dication after carbon K-shell ionization

0508743 - ÚFP 2020 RIV GB eng J - Journal Article
Li, Z. - Inhester, L. - Liekhus-Schmaltz, C. - Curchod, B.F.E. - Snyder Jr., J.W. - Medvedev, Nikita - Cryan, J.P. - Osipov, T. - Pabst, S. - Vendrell, O. - Bucksbaum, P. - Martínez, T. J.
Ultrafast isomerization in acetylene dication after carbon K-shell ionization.
Nature Communications. Roč. 8, September (2017), č. článku 453. E-ISSN 2041-1723
R&D Projects: GA MŠMT(CZ) LM2015083; GA MŠMT LG15013
Institutional support: RVO:61389021
Keywords : molecular-dynamics * conical intersection * electronic states * ab-initio * vinylidene
OECD category: Fluids and plasma physics (including surface physics)
Impact factor: 12.353, year: 2017
Method of publishing: Open access
https://www.nature.com/articles/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 [H2CC](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, while reproducing the salient features of the time-resolved Coulomb imaging experiment. This work resolves the seeming contradiction between experiment and theory and also calls for careful interpretation of structural information from the widely applied Coulomb momentum imaging method.
Permanent Link: http://hdl.handle.net/11104/0299570