Chemical reactions of conformationally selected molecules in a beam with Coulomb-crystallized ions

Abstract

Many molecules exhibit multiple conformers that often easily interconvert under thermal conditions. Therefore, single conformations are difficult to isolate which renders the study of their distinct chemical reactivities challenging. We have recently reported a new experimental method for the characterization of conformer-specific effects in chemical reactions [Y. P. Chang et al., Science 342, 98 (2013)]. Different conformers are spatially separated using inhomogeneous electric fields and reacted with a Coulomb crystal of cold, spatially localized ions in a trap. As a first application, we studied reactions between the two conformers of 3-aminophenol and Ca${}^{+}$. We observed a twofold larger rate constant for the $cis$ compared to the $trans$ conformer which was rationalized in terms of the differences in the long-range ion-molecule interactions. The present article provides a detailed description of the new method and a full account of the experimental results as well as the accompanying theoretical calculations.

12 pages, 11 figures

References in corpus (8)

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• Quantum-state selection, alignment, and orientation of large molecules using static electric and laser fields
• A selector for structural isomers of neutral molecules
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• CMISTARK: Python package for the Stark-effect calculation and symmetry classification of linear, symmetric and asymmetric top wavefunctions in dc electric fields
• Manipulating the motion of large neutral molecules
• Spatially separated polar samples of the cis and trans conformers of 3-fluorophenol

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• Conformational and state-specific effects in reactions of 2,3-dibromobutadiene with Coulomb-crystallized calcium ions
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