Capturing the generation and structural transformations of molecular ions

Jun Heo, Doyeong Kim, Alekos Segalina, Hosung Ki, Doo-Sik Ahn, Seonggon Lee, Jungmin Kim, Yongjun Cha, Kyung Won Lee, Jie Yang, J. Pedro F. Nunes, Xijie Wang and Hyotcherl Ihee ()
Additional contact information
Jun Heo: Institute for Basic Science (IBS)
Doyeong Kim: Institute for Basic Science (IBS)
Alekos Segalina: Institute for Basic Science (IBS)
Hosung Ki: Institute for Basic Science (IBS)
Doo-Sik Ahn: Institute for Basic Science (IBS)
Seonggon Lee: Institute for Basic Science (IBS)
Jungmin Kim: Institute for Basic Science (IBS)
Yongjun Cha: Institute for Basic Science (IBS)
Kyung Won Lee: Institute for Basic Science (IBS)
Jie Yang: SLAC National Accelerator Laboratory
J. Pedro F. Nunes: University of Nebraska–Lincoln
Xijie Wang: SLAC National Accelerator Laboratory
Hyotcherl Ihee: Institute for Basic Science (IBS)

Nature, 2024, vol. 625, issue 7996, 710-714

Abstract: Abstract Molecular ions are ubiquitous and play pivotal roles1–3 in many reactions, particularly in the context of atmospheric and interstellar chemistry4–6. However, their structures and conformational transitions7,8, particularly in the gas phase, are less explored than those of neutral molecules owing to experimental difficulties. A case in point is the halonium ions9–11, whose highly reactive nature and ring strain make them short-lived intermediates that are readily attacked even by weak nucleophiles and thus challenging to isolate or capture before they undergo further reaction. Here we show that mega-electronvolt ultrafast electron diffraction (MeV-UED)12–14, used in conjunction with resonance-enhanced multiphoton ionization, can monitor the formation of 1,3-dibromopropane (DBP) cations and their subsequent structural dynamics forming a halonium ion. We find that the DBP+ cation remains for a substantial duration of 3.6 ps in aptly named ‘dark states’ that are structurally indistinguishable from the DBP electronic ground state. The structural data, supported by surface-hopping simulations15 and ab initio calculations16, reveal that the cation subsequently decays to iso-DBP+, an unusual intermediate with a four-membered ring containing a loosely bound17,18 bromine atom, and eventually loses the bromine atom and forms a bromonium ion with a three-membered-ring structure19. We anticipate that the approach used here can also be applied to examine the structural dynamics of other molecular ions and thereby deepen our understanding of ion chemistry.

Date: 2024
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/s41586-023-06909-5 Abstract (text/html)
Access to the full text of the articles in this series is restricted.

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:nature:v:625:y:2024:i:7996:d:10.1038_s41586-023-06909-5

Ordering information: This journal article can be ordered from
https://www.nature.com/

DOI: 10.1038/s41586-023-06909-5

Access Statistics for this article

Nature is currently edited by Magdalena Skipper

More articles in Nature from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().