Journal Article

PUBDB-2021-03818

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Conformational and state-specific effects in reactions of 2,3-dibromobutadiene with Coulomb-crystallized calcium ions

Kilaj, A. (First author) ; Käser, S. ; Wang, J.CFEL*Extern*DESY* ; Stranak, P. ; Schwilk, M. ; Xu, L. ; von Lilienfeld, O. A. ; Küpper, J. (Corresponding author)CFEL*XFEL.EU*DESY* ; Meuwly, M. (Corresponding author) ; Willitsch, S. (Corresponding author)

2023
RSC Publ. Cambridge

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Please use a persistent id in citations: doi:10.1039/D3CP01416A  doi:10.3204/PUBDB-2021-03818

Report No.: arXiv:2303.11813

Abstract: Recent advances in experimental methodology enabled studies of the quantum-state- and conforma- tional dependence of chemical reactions under precisely controlled conditions in the gas phase. Here, we generated samples of selected gauche and s-trans 2,3-dibromobutadiene (DBB) by electrostatic deflection in a molecular beam and studied their reaction with Coulomb crystals of laser-cooled Ca$^+$ ions in an ion trap. The rate coefficients for the total reaction were found to strongly depend on both the conformation of DBB and the electronic state of Ca$^+$. In the (4p) $^2P_{1/2}$ and (3d) $^2D_{3/2}$ excited states of Ca$^+$, the reaction is capture-limited and faster for the gauche conformer due to long-range ion-dipole interactions. In the (4s) $^2S_{1/2}$ ground state of Ca$^+$, the reaction rate for s-trans DBB still conforms with the capture limit, while that for gauche DBB is strongly suppressed. The exper- imental observations were analysed with the help of adiabatic capture theory, ab-initio calculations, and reactive molecular dynamics simulations on a machine-learned full-dimensional potential en- ergy surface of the system. The theory yields near-quantitative agreement for s-trans-DBB, but overestimates the reactivity of the gauche- conformer compared to the experiment. The present study points to the important role of molecular geometry even in strongly reactive exothermic systems and illustrates striking differences in the reactivity of individual conformers in gas-phase ion-molecule reactions.

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Contributing Institute(s):

1. CFEL-Controlled Molecule Imaging (FS-CFELCMI)
2. Uni Hamburg / Experimentalphysik (UNI/EXP)
3. beauftragt von UNI (UNI/CUI)

Research Program(s):

1. 631 - Matter – Dynamics, Mechanisms and Control (POF4-631) (POF4-631)
2. DFG project 390715994 - EXC 2056: CUI: Advanced Imaging of Matter (390715994) (390715994)
3. Ex-Net-0002-Phase2-3 - Advanced Imaging of Matter: Structure, Dynamics and Control on the Atomic Scale - AIM (2018_Ex-Net-0002-Phase2-3) (2018_Ex-Net-0002-Phase2-3)

Experiment(s):

1. Experiments at CFEL

Appears in the scientific report 2023

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Database coverage:
; ; ; Clarivate Analytics Master Journal List ; Current Contents - Physical, Chemical and Earth Sciences ; IF < 5 ; JCR ; National-Konsortium ; SCOPUS ; Web of Science Core Collection

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Linked articles:

http://join2-wiki.gsi.de/foswiki/pub/Main/Artwork/join2_logo100x88.png Preprint Kilaj, A. ; Käser, S. ; Wang, J.CFEL*Extern*DESY* ; Straňák, P. ; Schwilk, M. ; Xu, L. ; von Lilienfeld, O. A. ; Küpper, J. (Corresponding author)CFEL*XFEL.EU*DESY* ; Meuwly, M. (Corresponding author) ; Willitsch, S. (Corresponding author)
Conformational and state-specific effects in reactions of 2,3-dibromobutadiene with Coulomb-crystallized calcium ions
[10.3204/PUBDB-2024-01157]     Files  Fulltext by arXiv.org BibTeX | EndNote: XML, Text | RIS

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