000604541 001__ 604541
000604541 005__ 20240426151320.0
000604541 0247_ $$2arXiv$$aarXiv:2303.11813
000604541 0247_ $$2datacite_doi$$a10.3204/PUBDB-2024-01157
000604541 037__ $$aPUBDB-2024-01157
000604541 041__ $$aEnglish
000604541 082__ $$a540
000604541 088__ $$2arXiv$$aarXiv:2303.11813
000604541 1001_ $$aKilaj, Ardita$$b0
000604541 245__ $$aConformational and state-specific effects in reactions of 2,3-dibromobutadiene with Coulomb-crystallized calcium ions
000604541 260__ $$c2023
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000604541 520__ $$aRecent 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.
000604541 536__ $$0G:(DE-HGF)POF4-631$$a631 - Matter – Dynamics, Mechanisms and Control (POF4-631)$$cPOF4-631$$fPOF IV$$x0
000604541 536__ $$0G:(GEPRIS)390715994$$aDFG project 390715994 - EXC 2056: CUI: Advanced Imaging of Matter (390715994)$$c390715994$$x1
000604541 536__ $$0G:(EU-Grant)772834$$aQML - Quantum Machine Learning: Chemical Reactions with Unprecedented Speed and Accuracy (772834)$$c772834$$fERC-2017-COG$$x2
000604541 588__ $$aDataset connected to arXivarXiv, CrossRef, Journals: bib-pubdb1.desy.de
000604541 693__ $$0EXP:(DE-H253)CFEL-Exp-20150101$$5EXP:(DE-H253)CFEL-Exp-20150101$$eExperiments at CFEL$$x0
000604541 7001_ $$00000-0002-3641-8519$$aKäser, Silvan$$b1
000604541 7001_ $$0P:(DE-H253)PIP1084960$$aWang, Jia$$b2
000604541 7001_ $$00000-0001-7012-6192$$aStraňák, Patrik$$b3
000604541 7001_ $$0P:(DE-HGF)0$$aSchwilk, Max$$b4
000604541 7001_ $$0P:(DE-HGF)0$$aXu, Lei$$b5
000604541 7001_ $$00000-0001-7419-0466$$avon Lilienfeld, O. Anatole$$b6
000604541 7001_ $$0P:(DE-H253)PIP1012175$$aKüpper, Jochen$$b7$$eCorresponding author
000604541 7001_ $$00000-0001-7930-8806$$aMeuwly, Markus$$b8$$eCorresponding author
000604541 7001_ $$0P:(DE-HGF)0$$aWillitsch, Stefan$$b9$$eCorresponding author
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000604541 9141_ $$y2023
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