Disentangling sequential and concerted fragmentations of molecular polycations with covariant native frame analysis
Joseph McManus, Tiffany Walmsley, Kiyonobu Nagaya, James Harries, Yoshiaki Kumagai, Hiroshi Iwayama, Michael N. R. Ashfold, Mathew Britton, P. H. Bucksbaum, Briony Downes-Ward, Taran Driver, David Heathcote, Paul Hockett, Andrew J. Howard, Edwin Kukk, Jason W. L. Lee, Yusong Liu, Dennis Milešević, Russell S. Minns, Akinobu Niozu, Johannes Niskanen, Andrew J. Orr‐Ewing, Shigeki Owada, Daniel Rolles, Patrick A. Robertson, Artem Rudenko, Kiyoshi Ueda, James Unwin, Claire Vallance, Michael Burt, M. Brouard, Ruaridh Forbes, Felix Allum
Abstract
). By incorporating the recently developed native frames analysis approach into the three-dimensional covariance imaging procedure, contributions from three-body concerted and sequential fragmentation mechanisms can be isolated. The angular distribution of the fragment ions is much more complex than in previously reported studies for triatomic polycations, and differs substantially between the two isomeric species. With support of simple simulations of the dissociation channels of interest, detailed physical insights into the fragmentation dynamics are obtained, including how the initial dissociation step in a sequential mechanism influences rovibrational dynamics in the metastable intermediate ion and how signatures of this nuclear motion manifest in the measured signals.