ArticlePDF Available

Absolute Configuration from Different Multifragmentation Pathways in Light-Induced Coulomb Explosion Imaging

Authors:
Martin Pitzer at Weizmann Institute of Science
Martin Pitzer
Gregor Kastirke
Gregor Kastirke
Gregor Kastirke
  • This person is not on ResearchGate, or hasn't claimed this research yet.
Maksim Kunitski at Goethe University Frankfurt
Maksim Kunitski
Till Jahnke at European XFEL
Till Jahnke
Show all 29 authorsHide
Download full-text PDFDownload full-text PDF
Read full-text
Download citation

Abstract and Figures

Portrait credits: C. Freudenberger (G.K., C. G., T.B., F.T., H.G., M.W., H.S., M.S.), S. Marquardt (Sa.M., Se.M., R.B.), U. Dettmar (M.P., R.D.) private (M.K., T.J., C.S., K.H., J.B., S.Z., A.K., F.S., R.W., L.S., A..J., M.M., B.S., H.S.-B., J.S.); not shown: H.G. The front cover artwork is provided by the groups of Reinhard Dörner (University of Frankfurt), Robert Berger (University of Marburg) and Jürgen Stohner (Zurich University for Applied Sciences, Wädenswil). The image shows how a single X-ray photon from a synchrotron source induces the Coulomb Explosion of a prototypical chiral molecule (CHBrClF), allowing to distinguish the enantiomers and determine the absolute configuration. Read the full text of the article at 10.1002/cphc.201501118.
Figures - uploaded by Florian Trinter
Author content
All figure content in this area was uploaded by Florian Trinter
Content may be subject to copyright.
cphc.2016008
06.pdf
Content uploaded by Florian Trinter
Author content
All content in this area was uploaded by Florian Trinter on Apr 15, 2021
Content may be subject to copyright.
Pitzer_CPC_20
16.pdf
Content uploaded by Florian Trinter
Author content
All content in this area was uploaded by Florian Trinter on Oct 12, 2017
Content may be subject to copyright.
Absolute Configuration from Different Multifragmentation
Pathways in Light-Induced Coulomb Explosion Imaging
What was the biggest surprise on the way to the results
presented in this paper?
Shortly after we had startedthe measurement, we saw that
the Coulombexplosion process was significantly more efficient
than we had anticipated. This enabled us to collect alarge
data set during the availablebeam-time at the synchrotron.
To which future investigationsdothese results inspire?
One of the next steps will be to apply the method to more
complex chiral molecules.But even for achiral species, multiple
ionization and the coincident detection of diverse charged
fragments of polyatomicmolecules can provide insightinto
awealth of intriguing processes on the molecular scale.
Why did this work involve so many people?
The results presented in our paper are the outcome of an ex-
tensivecollaborationwork:The group in Wdenswil took pri-
marily careofthe synthesis, analytics and handlingofthe
sample;the team in Frankfurt, including Allan from Ottawa,
built the apparatus, performedthe experimentsand accom-
plished the main part of the data analysis. The activities in Mar-
burg focusedonplanning, simulations and data analysis to
enable interpretation of the data. The diverse background of
the collaboratorsinspired fruitful discussions and surprising in-
sights for everybody.
The front cover artwork is provided by the groups of Reinhard Dçrner(University of Frankfurt), Robert Berger (University of
Marburg) and Jìrgen Stohner (Zurich University for Applied Sciences, Wdenswil). The image shows how asingle X-ray
photon from asynchrotronsource inducesthe Coulomb Explosion of aprototypical chiral molecule (CHBrClF),allowingto
distinguishthe enantiomers and determine the absoluteconfiguration. Read the full text of the article at 10.1002/
cphc.201501118.
ChemPhysChem 2016,17,2450 Ó2016 Wiley-VCH Ve rlag GmbH &Co. KGaA, Weinheim2450
Cover Profile
DOI:10.1002/cphc.201600806
... Inner-shell absorption of an X-ray photon can-depending on the photon energy and atomic species-also create multiple charges on a molecule due to Auger cascades. However, among the many studies on Articles Nature Physics 3D momentum imaging using X-ray ionization, only a few of them have studied somewhat larger molecules up to now 12,13 . ...
X-ray multiphoton-induced Coulomb explosion images complex single molecules
Article
Full-text available
  • Apr 2022
  • NAT PHYS
Following structural dynamics in real time is a fundamental goal towards a better understanding of chemical reactions. Recording snapshots of individual molecules with ultrashort exposure times is a key ingredient towards this goal, as atoms move on femtosecond (10−15 s) timescales. For condensed-phase samples, ultrafast, atomically resolved structure determination has been demonstrated using X-ray and electron diffraction. Pioneering experiments have also started addressing gaseous samples. However, they face the problem of low target densities, low scattering cross sections and random spatial orientation of the molecules. Therefore, obtaining images of entire, isolated molecules capturing all constituents, including hydrogen atoms, remains challenging. Here we demonstrate that intense femtosecond pulses from an X-ray free-electron laser trigger rapid and complete Coulomb explosions of 2-iodopyridine and 2-iodopyrazine molecules. We obtain intriguingly clear momentum images depicting ten or eleven atoms, including all the hydrogens, and thus overcome a so-far impregnable barrier for complete Coulomb explosion imaging—its limitation on molecules consisting of three to five atoms. In combination with state-of-the-art multi-coincidence techniques and elaborate theoretical modelling, this allows tracing ultrafast hydrogen emission and obtaining information on the result of intramolecular electron rearrangement. Our work represents an important step towards imaging femtosecond chemistry via Coulomb explosion. Visualizing the structural dynamics of isolated molecules would help to understand chemical reactions, but this is difficult for complex structures. Intense femtosecond X-ray pulses allow the full imaging of exploding photoionized molecules, in this case, with eleven atoms.
View
... Jusqu'à Pitzer et al. 36 (2015), seul Bijovet 37 a réussi à extraire la configuration absolue des molécules chirales. Les autres méthodes sont relatives, et demandent une calibration annexe ou la comparaison avec des calculs. ...
Dichroïsme circulaire de photoélectrons (PECD) en couche de valence : systèmes à base d’acides aminés et dérivés de binaphtyles
Thesis
Full-text available
  • Jul 2020
Nous avons étudié en détail la photodynamique VUV et le PECD (un effet chiroptique intense) de l'acide aminé Proline (Pro) en phase gaz, seul acide aminé naturel contenant un cycle pyrrolidine. Plusieurs températures ont été utilisées pour faire varier la population de conformères de Pro native, afin d'effectuer une analyse complète des conformères à l'aide des calculs PECD CMS Xα, et ce faisant de raffiner le paysage conformationnel. Le signe des asymétries, similaire au cas de l’alanine, renforce le scenario astrophysique en lien avec l’homochiralité, sans contraintes de température. De plus, nous avons étudié, le PECD sur des acides aminés aromatiques (tryptophane & tyrosine), des chromophores importants des protéines. Nous avons également étendu la portée de nos études de PECD vers de grands édifices moléculaires tels que des dipeptides à base d’acides aminés (c-Pro-Pro, Gly-Pro et Pro-Gly), jusqu’à des systèmes beaucoup plus complexes comme des nanoparticules homochirales (Pro, Trp et Tyr), pour tester, phénoménologiquement, les limites de sensibilité du PECD par rapport à la complexité moléculaire. Enfin, nous présentons pour la première fois l'étude d'une famille de 3 molécules à chiralité axiale (dérivées de binaphtyles), dont nous avons notamment étudié l'influence de l'angle diédral sur le PECD.
View
... To serve the explosion-proof and explosion venting designs of industrial buildings, we need to conduct targeted studies on the destructive effects of flammable gas implosion. Since combustible gas implosion involves many theories, such as thermodynamics, fluid mechanics, chemical kinetics, heat transfer medium, and turbulent medium, the mechanism is very complicated and difficult to describe accurately [2][3][4]. A common and effective method is to study the combustion and explosion processes of combustible gases through model tests. ...
Strain Monitoring of Combustible Gas Implosion Test Based on Fiber Bragg Grating
Article
Full-text available
  • May 2019
Strain measurement is an important component in model tests of combustible internal explosions. Strain gauges are used to measure strain in traditional electrical measurement methods and have some limitations, such as susceptibility to electromagnetic interference, short life, and inability to distribute. Fiber Bragg gratings (FBGs) are developing into useful sensing tools that can respond to changes in stress, strain, and temperature by changing wavelengths. FBGs have excellent sensing performance, such as long life, antielectromagnetic interference, easy networking, and good reusability. In this paper, FBG sensors are applied to strain monitoring in ethylene flammable implosion experiments. In the ethylene flammable implosion tests, an FBG was placed on the inner surface of the bottom plate of the rectangular steel test device near the detonation vent by the sticking method. The reliability and repeatability of the strain change of the FBG affected by detonation overpressure and combustion were tested at this point. Four explosion tests were carried out. The test results showed that FBG sensors could obtain stable and reliable strain data in all four tests. The strain variation reflects the development of overpressure and combustion in the whole process from ignition. For the strain amplitude formed by overpressure, the minimum was 1.449 με (the third test), and the maximum was 48.181 με (the fourth test).For the strain amplitude step change formed by the deflagration flame front passing the measurement points, the minimum was 1.673 με (the second test), and the maximum was 19.724 με (the fourth test).The strain amplitude produced by the deflagration temperature effect in the four tests ranged from 72.803 με (the first test) to 143.381 με (the fourth test).The results show that FBG sensors can provide reliable and effective strain monitoring data for the experimental study of flammable implosions.
View
Molecular Beams in Physics and Chemistry From Otto Stern's Pioneering Exploits to Present-Day Feats: From Otto Stern's Pioneering Exploits to Present-Day Feats
Book
Full-text available
  • Jan 2021
This Open Access book gives a comprehensive account of both the history and current achievements of molecular beam research. In 1919, Otto Stern launched the revolutionary molecular beam technique. This technique made it possible to send atoms and molecules with well-defined momentum through vacuum and to measure with high accuracy the deflections they underwent when acted upon by transversal forces. These measurements revealed unforeseen quantum properties of nuclei, atoms, and molecules that became the basis for our current understanding of quantum matter. This volume shows that many key areas of modern physics and chemistry owe their beginnings to the seminal molecular beam work of Otto Stern and his school. Written by internationally recognized experts, the contributions in this volume will help experienced researchers and incoming graduate students alike to keep abreast of current developments in molecular beam research as well as to appreciate the history and evolution of this powerful method and the knowledge it reveals.
View
STIRAP: A Historical Perspective and Some News
Chapter
Full-text available
  • Jun 2021
A very brief outline of what STIRAP is and does is followed by the presentation of the sequence of experiments, which started some 50 years ago, the visions developed and experimental efforts undertaken, that finally led to the development of STIRAP.
View
Otto Stern’s Legacy in Quantum Optics: Matter Waves and Deflectometry
Chapter
Full-text available
  • Jun 2021
Otto Stern became famous for molecular beam physics, matter-wave research and the discovery of the electron spin, with his work guiding several generations of physicists and chemists. Here we discuss how his legacy has inspired the realization of universal interferometers, which prepare matter waves from atomic, molecular, cluster or eventually nanoparticle beams. Such universal interferometers have proven to be sensitive tools for quantum-assisted force measurements, building on Stern’s pioneering work on electric and magnetic deflectometry. The controlled shift and dephasing of interference fringes by external electric, magnetic or optical fields have been used to determine internal properties of a vast class of particles in a unified experimental framework.
View
High-Resolution Momentum Imaging—From Stern’s Molecular Beam Method to the COLTRIMS Reaction Microscope
Chapter
Full-text available
  • Jun 2021
Multi-particle momentum imaging experiments are now capable of providing detailed information on the properties and the dynamics of quantum systems in Atomic, Molecular and Photon (AMO) physics. Historically, Otto Stern can be considered the pioneer of high-resolution momentum measurements of particles moving in a vacuum and he was the first to obtain sub-atomic unit (a.u.) momentum resolution (Schmidt-Böcking et al. in The precision limits in a single-event quantum measurement of electron momentum and position, these proceedings [1]). A major contribution to modern experimental atomic and molecular physics was his so-called molecular beam method [2], which Stern developed and employed in his experiments. With this method he discovered several fundamental properties of atoms, molecules and nuclei [2, 3]. As corresponding particle detection techniques were lacking during his time, he was only able to observe the averaged footprints of large particle ensembles. Today it is routinely possible to measure the momenta of single particles, because of the tremendous progress in single particle detection and data acquisition electronics. A “state-of-the-art” COLTRIMS reaction microscope [4–11] can measure, for example, the momenta of several particles ejected in the same quantum process in coincidence with sub-a.u. momentum resolution. Such setups can be used to visualize the dynamics of quantum reactions and image the entangled motion of electrons inside atoms and molecules. This review will briefly summarize Stern’s work and then present in longer detail the historic steps of the development of the COLTRIMS reaction microscope. Furthermore, some benchmark results are shown which initially paved the way for a broad acceptance of the COLTRIMS approach. Finally, a small selection of milestone work is presented which has been performed during the last two decades.
View
Quantum Effects in Cold and Controlled Molecular Dynamics
Chapter
Full-text available
  • Jun 2021
This chapter discusses three examples of quantum effects that can be observed in state-of-the-art experiments with molecular beams—scattering resonances as a probe of interparticle interactions in cold collisions, the protection of Fano-Feshbach resonances against decay despite resonant coupling to a scattering continuum, and a circular dichroism in photoelectron angular distributions arising in the photoionization of randomly oriented chiral molecules. The molecular beam setup provides molecules in well-defined quantum states. This, together with a theoretical description based on first principles, allows for excellent agreement between theoretical prediction and experimental observation and thus a rigorous understanding of the observed quantum effects.
View
Otto Stern’s Molecular Beam Method and Its Impact on Quantum Physics
Chapter
Full-text available
  • Jun 2021
Motivated by his interest in thermodynamics and the emerging quantum mechanics, Otto Stern (1888–1969) launched in 1919 his molecular beam method to examine the fundamental assumptions of theory that transpire in atomic, molecular, optical, and nuclear physics. Stern’s experimental endeavors at Frankfurt (1919–1922), Hamburg (1923–1933), and Pittsburgh (1933–1945) provided insights into the quantum world that were independent of spectroscopy and that concerned well-defined isolated systems, hitherto accessible only to Gedanken experiments. In this chapter we look at how Stern’s molecular beam research came about and review six of his seminal experiments along with their context and reception by the physics community: the Stern-Gerlach experiment; the three-stage Stern-Gerlach experiment; experimental evidence for de Broglie’s matter waves; measurements of the magnetic dipole moment of the proton and the deuteron; experimental demonstration of momentum transfer upon absorption or emission of a photon; the experimental verification of the Maxwell-Boltzmann velocity distribution via deflection of a molecular beam by gravity. Regarded as paragons of thoroughness and ingenuity, these experiments entail accurate transversal momentum measurements with resolution better than 0.1 atomic units. Some of these experiments would be taken up by others where Stern left off only decades later (matter-wave scattering or photon momentum transfer). We conclude by highlighting aspects of Stern’s legacy as reflected by the honors that have been bestowed upon him to date.
View
Photoelectron circular dichroism of O 1s-photoelectrons of uniaxially oriented trifluoromethyloxirane: Energy dependence and sensitivity to molecular configuration
Preprint
Full-text available
  • Jun 2021
The photoelectron circular dichroism (PECD) of the O 1s-photoelectrons of trifluoromethyloxirane(TFMOx) is studied experimentally and theoretically for different photoelectron kinetic energies. The experiments were performed employing circularly polarized synchrotron radiation and coincidentelectron and fragment ion detection using Cold Target Recoil Ion Momentum Spectroscopy. The corresponding calculations were performed by means of the Single Center method within the relaxed-core Hartree-Fock approximation. We concentrate on the energy dependence of the differential PECD of uniaxially oriented TFMOx molecules, which is accessible through the employed coincident detection. We also compare results for differential PECD of TFMOx to those obtained for the equivalent fragmentation channel and similar photoelectron kinetic energy of methyloxirane (MOx), studied in our previous work. Thereby, we investigate the influence of the substitution of the methyl-group by the trifluoromethyl-group at the chiral center on the molecular chiral response. Finally, the presently obtained angular distribution parameters are compared to those available in literature.
View
Three-body physics. Observation of the Efimov state of the helium trimer
Article
Full-text available
  • May 2015
Quantum theory dictates that upon weakening the two-body interaction in a three-body system, an infinite number of three-body bound states of a huge spatial extent emerge just before these three-body states become unbound. Three helium (He) atoms have been predicted to form a molecular system that manifests this peculiarity under natural conditions without artificial tuning of the attraction between particles by an external field. Here we report experimental observation of this long-predicted but experimentally elusive Efimov state of 4He3 by means of Coulomb explosion imaging. We show spatial images of an Efimov state, confirming the predicted size and a typical structure where two atoms are close to each other while the third is far away.
View
Imaging the structure of the trimer systems 4He3 and 3He4He2
Article
Full-text available
  • Dec 2014
Helium shows fascinating quantum phenomena unseen in any other element. In its liquid phase, it is the only known superfluid. The smallest aggregates of helium, the dimer (He2) and the trimer (He3) are, in their predicted structure, unique natural quantum objects. While one might intuitively expect the structure of (4)He3 to be an equilateral triangle, a manifold of predictions on its shape have yielded an ongoing dispute for more than 20 years. These predictions range from (4)He3 being mainly linear to being mainly an equilateral triangle. Here we show experimental images of the wave functions of (4)He3 and (3)He(4)He2 obtained by Coulomb explosion imaging of mass-selected clusters. We propose that (4)He3 is a structureless random cloud and that (3)He(4)He2 exists as a quantum halo state.
View
Imaging the Absolute Configuration of a Chiral Epoxide in the Gas Phase
Article
Full-text available
  • Nov 2013
  • SCIENCE
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.
View
The SEXTANTS beamline at SOLEIL: a new facility for elastic, inelastic and coherent scattering of soft X-rays
Article
Full-text available
  • Mar 2013
  • J Phys Conf
SEXTANTS is a new SOLEIL beamline dedicated to soft X-ray scattering techniques. The beamline, covering the 50-1700 eV energy range, features two Apple-II undulators for polarization control and a fixed-deviation monochromator. Two branch-lines host three end-stations for elastic, inelastic and coherent scattering experiments.
View
View
Specification of Molecular Chirality
Article
  • Apr 1966
  • Angew Chem
The topological analysis of chiral molecular models has provided the framework of a general system for the specification of their chirality. The application, made in and before 1956, of this system to organic-chemical configurations is generally retained, but is redefined with respect to certain types of structure, largely in the light of experience gained since 1956 in the Beilstein Institute and elsewhere. The system is now extended to deal, on the one hand, with organic-chemical conformations, and, on the other, with inorganic-chemical configurations to ligancy six. Matters arising in connexion with the transference of chiral specifications from model to name are considered, notably that of the symbiosis in nomenclature of expressions of the general system and of systems of confined scope. For corrigendum see DOI:10.1002/anie.196605111
View
Direct Determination of Absolute Molecular Stereochemistry in Gas Phase by Coulomb Explosion Imaging
Article
  • Sep 2013
  • SCIENCE
Absolute Images Molecules are held together by a balance of charge between negative electrons and positive nuclei. When multiple electrons are expelled by laser irradiation, the remaining, mutually repulsive nuclei fly apart in a Coulomb explosion. Instead of traditional x-ray diffraction methods that require crystalline samples, Pitzer et al. (p. 1096 ) show that by tracking the fragment trajectories from laser-induced Coulomb explosions of relatively simple gas phase molecules, they can determine the absolute stereochemical configuration of enantiomers (mirror-image isomers).
View
Relative Abundances of Ions Formed as the Result of Inner-Shell Vacancies in Atoms
Article
  • Nov 1966
Relative abundances of differently charged ions were measured following the x irradiation of Xe, and, in separate experiments, of Hg. These studies were carried out for a variety of x-ray energies in order to obtain data as a function of the initial inner-shell vacancies. From the data we have derived charge spectra that result from producing an initial vacancy in each of the following shells: the K, LI, LII,III, MI, MII,III, MIV,V, and N shells of Xe; and the L, M, N, and O shells of Hg. These data are correlated with earlier measurements on He, Ne, Ar, and Kr; and empirical rules are set up whereby one may estimate the average charge resulting from the atomic readjustment to a vacancy in any shell of any atom.
View
Cold Target Recoil Ion Momentum Spectroscopy: A 'momentum microscope' to view atomic collision dynamics
Article
  • Jun 2000
  • PHYS REP
Cold Target Recoil Ion Momentum Spectroscopy (COLTRIMS) is a novel momentum space imaging technique for the investigation of the dynamics of ionizing ion, electron or photon impact reactions with atoms or molecules. It allows the measurement of the previously undetectable small three dimensional momentum vector of the recoiling target ion created in those reactions with high resolution and 4π solid angle. Combined with novel 4π electron momentum analysers it is a momentum microscope for kinematically complete scattering experiments. We review the technical development, outline the kinematics of atomic reactions from the perspective of the recoil ion, and give an overview of the studies performed with this technique. These studies yield kinematically complete pictures of the correlated motion of the fragments of atomic and molecular breakup processes, unprecedented in resolution, detail and completeness. The multiple-dimensional momentum-space images often directly unveil the physical mechanism underlying the many-particle transitions investigated. The experiments reviewed here include reactions of single and multiple capture and ionization induced by keV proton to GeV/u U92+ impact, electron and antiproton impact ionization as well as single and double ionization by photoabsorbtion and Compton scattering from threshold to 100 keV. We give an outlook on the exciting future prospects of the method for atomic physics and other fields of science.
View
Direct observation of “dynamic” chirality by Coulomb explosion imaging
Article
  • Jul 2001
Instantaneous chirality induced by zero-point vibrations was observed directly by using the Coulomb explosion imaging (CEI) technique. The present results suggest the CEI would be generally applicable to diagnosis of the chirality of the isolated molecules in gas phase. © 2001 American Institute of Physics.
View