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@ARTICLE{Kilaj:604541,
      author       = {Kilaj, Ardita and Käser, Silvan and Wang, Jia and
                      Straňák, Patrik and Schwilk, Max and Xu, Lei and von
                      Lilienfeld, O. Anatole and Küpper, Jochen and Meuwly,
                      Markus and Willitsch, Stefan},
      title        = {{C}onformational and state-specific effects in reactions of
                      2,3-dibromobutadiene with {C}oulomb-crystallized calcium
                      ions},
      reportid     = {PUBDB-2024-01157, arXiv:2303.11813},
      year         = {2023},
      abstract     = {Recent advances in experimental methodology enabled studies
                      of the quantum-state and conformational 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 $\mathrm{Ca^{+}}$ 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 $\mathrm{Ca^{+}}$. In the
                      $\mathrm{(4p)~^{2}P_{1/2}}$ and $\mathrm{(3d)~^{2}D_{3/2}}$
                      excited states of $\mathrm{Ca^{+}}$, the reaction is
                      capture-limited and faster for the gauche conformer due to
                      long-range ion-dipole interactions. In the
                      $\mathrm{(4s)~^{2}S_{1/2}}$ ground state of
                      $\mathrm{Ca^{+}}$, the reaction rate for s-trans DBB still
                      conforms with the capture limit, while that for gauche DBB
                      is strongly suppressed. The experimental 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
                      energy 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.},
      cin          = {FS-CFEL-CMI / UNI/EXP / UNI/CUI},
      ddc          = {540},
      cid          = {I:(DE-H253)FS-CFEL-CMI-20220405 /
                      $I:(DE-H253)UNI_EXP-20120731$ /
                      $I:(DE-H253)UNI_CUI-20121230$},
      pnm          = {631 - Matter – Dynamics, Mechanisms and Control
                      (POF4-631) / DFG project 390715994 - EXC 2056: CUI: Advanced
                      Imaging of Matter (390715994) / QML - Quantum Machine
                      Learning: Chemical Reactions with Unprecedented Speed and
                      Accuracy (772834)},
      pid          = {G:(DE-HGF)POF4-631 / G:(GEPRIS)390715994 /
                      G:(EU-Grant)772834},
      experiment   = {EXP:(DE-H253)CFEL-Exp-20150101},
      typ          = {PUB:(DE-HGF)25},
      eprint       = {2303.11813},
      howpublished = {arXiv:2303.11813},
      archivePrefix = {arXiv},
      SLACcitation = {$\%\%CITATION$ = $arXiv:2303.11813;\%\%$},
      doi          = {10.3204/PUBDB-2024-01157},
      url          = {https://bib-pubdb1.desy.de/record/604541},
}