In chemistry and biology, chirality, or handedness, refers to molecules that exist in two spatial configurations that are incongruent mirror images of one another. Almost all biologically active molecules are chiral, and the correct determination of their absolute configuration is essential for the understanding and the development of processes involving chiral molecules. Anomalous x-ray diffraction and vibrational optical activity measurements are broadly used to determine absolute configurations of solid or liquid samples. Determining absolute configurations of chiral molecules in the gas phase is still a formidable challenge. Here we demonstrate the determination of the absolute configuration of isotopically labeled (R,R)-2,3-dideuterooxirane by foil-induced Coulomb explosion imaging of individual molecules. Our technique provides unambiguous and direct access to the absolute configuration of small gas-phase species, including ions and molecular fragments.
Molecular photofragmentation has been studied by event imaging on HeH+ ions at 32 nm (38.7 eV) in a fast ion beam crossed with the free-electron laser in Hamburg (FLASH), analyzing neutral He product directions and energies. Fragmentation into He(1snl,n > or = 2)+H+ was observed to yield significant photodissociation at 32 nm with an absolute cross section of (1.4+/-0.7) x 10(-18) cm2, releasing energies of 10-20 eV. A clear dominance of photodissociation perpendicular to the laser polarization was found in contrast to the excitation paths so far emphasized in theoretical studies.
High-resolution dissociative recombination rate coefficients of rotationally cool and hot H 3 + in the vibrational ground state have been measured with a 22-pole trap setup and a Penning ion source, respectively, at the ion storage-ring TSR. The experimental results are compared with theoretical calculations to explore the dependence of the rate coefficient on ion temperature and to study the contributions of different symmetries to probe the rich predicted resonance spectrum. The kinetic energy release was investigated by fragment imaging to derive internal temperatures of the stored parent ions under differing experimental conditions. A systematic experimental assessment of heating effects is performed which, together with a survey of other recent storage-ring data, suggests that the present rotationally cool rate-coefficient measurement was performed at 380 +50 −130 K and that this is the lowest rotational temperature so far realized in storage-ring rate-coefficient measurements on H 3 + . This partially supports the theoretical suggestion that temperatures higher than assumed in earlier experiments are the main cause for the large gap between the experimental and the theoretical rate coefficients. For the rotationally hot rate-coefficient measurement a temperature of below 3250 K is derived. From these higher-temperature results it is found that increasing the rotational ion temperature in the calculations cannot fully close the gap between the theoretical and the experimental rate coefficients.
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