conformers; cold ions; molecular beams; reaction dynamics; controlled chemistry; cold molecules
Wang Jia, Kilaj Ardita, He Lanhai, Długołęcki Karol, Willitsch Stefan, Küpper Jochen (2020), Spatial Separation of the Conformers of Methyl Vinyl Ketone, in The Journal of Physical Chemistry A
, 124(40), 8341-8345.
Rivero Uxía, Turan Haydar Taylan, Meuwly Markus, Willitsch Stefan (2020), Reactive atomistic simulations of Diels-Alder-type reactions: conformational and dynamic effects in the polar cycloaddition of 2,3-dibromobutadiene radical ions with maleic anhydride, in Molecular Physics
Kilaj Ardita, Gao Hong, Tahchieva Diana, Ramakrishnan Raghunathan, Bachmann Daniel, Gillingham Dennis, von Lilienfeld O. Anatole, Küpper Jochen, Willitsch Stefan (2020), Quantum-chemistry-aided identification, synthesis and experimental validation of model systems for conformationally controlled reaction studies: separation of the conformers of 2,3-dibromobuta-1,3-diene in the gas phase, in Physical Chemistry Chemical Physics
, 22(24), 13431-13439.
Kilaj Ardita, Gao Hong, Rösch Daniel, Rivero Uxia, Küpper Jochen, Willitsch Stefan (2018), Observation of different reactivities of para and ortho-water towards trapped diazenylium ions, in Nature Communications
, 9(1), 2096-2096.
Rivero Uxía, Meuwly Markus, Willitsch Stefan (2017), A computational study of the Diels-Alder reactions between 2,3-dibromo-1,3-butadiene and maleic anhydride, in Chemical Physics Letters
, 683, 598-605.
Rösch Daniel, Willitsch Stefan (2017), Physikalische Chemie 2016: Spektroskopie und Chemie mit kalten Ionen, in Nachrichten aus der Chemie
, 65(3), 326-329.
Willitsch S. (2017), Chemistry with Controlled Ions, in Stuart Rice Aaron Dinner (ed.), Wiley Interscience, Hoboken, 162, 307-307.
Dulieu O., Willitsch S. (2017), Ion Coulomb crystals: From quantum technology to chemistry close to the absolute zero point, in Europhys. News
, 48, 17-17.
Rösch D., Gao H., Kilaj A., Willitsch S. (2016), Design and characterization of a linear quadrupole ion trap for high-resolution Coulomb-crystal time-of-flight mass spectrometry, in Eur. Phys. J. Tech. Instr.
, 3, 044314-044314.
Dulieu O., Willitsch S. (2015), Cristaux coulombiens: De la technologie quantique à la chimie proche du zéro absolu, in Reflets Phys.
, 91, 44-44.
The relationship between structure and reactivity is one of the central tenets of chemistry. In particular, many molecules exhibit structural isomers that interconvert over low barriers through rotations about covalent bonds (conformers). Conformers are the dominant isomers of complex molecules, and the conformation of a molecule can have pronounced effects on its chemical reactivity. Despite the eminent importance of conformational isomers in chemistry, very few studies have been reported thus far characterising conformational effects in chemical reactions under single-collision conditions. Consequently, the role of molecular conformations in fundamental reactions is only poorly understood. This striking lack of data reflects the experimental challenges to isolate und control specific conformers.In a recent proof-of-principle study [Science 342 (2013), 98], we have spatially separated specific conformers in a molecular beam through electrostatic deflection and directed them at a spatially localized reaction target of cold ions in a trap. This approach allowed us to study conformation-specific effects in ion-molecule reactions under precisely controlled experimental conditions in the gas phase. Here, we pro- pose a wide-ranging research programme aiming at extending our method to neutral reactions and applying it to a range of chemically relevant problems in order to explore the relationship between structure and reactivity in unprecedented detail. These methodological advances will enable for the first time detailed and systematic studies of the reaction mechanisms and dynamics of isolated conformers. The fundamental mechanistic insights gained will benefit a wide range of fields as diverse as fundamental reaction dynamics, organic synthesis, catalysis, atmospheric chemistry and rational molecule design.