coulomb-explosion-imaging-as-tool-to-distinguish-between

Coulomb Explosion Imaging as a Tool to Distinguish Between Stereoisomers

This article shows how the COLTRIMS (Cold Target Recoil Ion Momentum Spectroscopy) or the "reaction microscope" technique can be used to distinguish ...

Goethe-Universität Frankfurt am Main

We describe a momentum imaging setup for direct time-resolved studies of ionization-induced molecular dynamics. This system uses a tabletop ultrafast extreme-ultraviolet (EUV) light source based on high harmonic upconversion of a femtosecond laser. The high photon energy (around 42 eV) allows access to inner-valence states of a variety of small molecules via single photon excitation, while the sub--10-fs pulse duration makes it possible to follow the resulting dynamics in real time. To obtain a complete picture of molecular dynamics following EUV induced photofragmentation, we apply the versatile cold target recoil ion momentum spectroscopy reaction microscope technique, which makes use of coincident three-dimensional momentum imaging of fragments resulting from photoexcitation. This system is capable of pump-probe spectroscopy by using a combination of EUV and IR laser pulses with either beam as a pump or probe pulse. We report several experiments performed using this system.

Time-resolved momentum imaging system for molecular dynamics studies using a tabletop ultrafast extreme-ultraviolet light source.

The interatomic electronic decay after inner-valence ionization of a neon atom by a single photon in a neon-helium dimer is investigated. The excited neon atom relaxes via interatomic Coulombic decay and the excess energy is transferred to the helium atom and ionizes it. We show that the decay process is only possible if the dimer's bond stretches up to 6.2 Å, i.e., to more than twice the equilibrium interatomic distance of the neutral dimer. Thus, it is demonstrated that the electronic decay, taking place at such long distances, is driven by the nuclear motion.

Interatomic electronic decay driven by nuclear motion.

Radiation damage to living tissue stems not only from primary ionizing particles but to a substantial fraction from the dissociative attachment of secondary electrons with energies below the ionization threshold. We show that the emission yield of those low energy electrons increases dramatically in ion-atom collisions depending on whether or not the target atoms are isolated or embedded in an environment. Only when the atom that has been ionized and excited by the primary particle impact is in immediate proximity of another atom is a fragmentation route known as interatomic Coulombic decay (ICD) enabled. This leads to the emission of a low energy electron. Over the past decade ICD was explored in several experiments following photoionization. Most recent results show its observation even in water clusters. Here we show the quantitative role of ICD for the production of low energy electrons by ion impact, thus approaching a scenario closer to that of radiation damage by alpha particles: We choose ion energies on the maximum of the Bragg peak where energy is most efficiently deposited in tissue. We compare the electron production after colliding He(+) ions on isolated Ne atoms and on Ne dimers (Ne(2)). In the latter case the Ne atom impacted is surrounded by a most simple environment already opening ICD as a deexcitation channel. As a consequence, we find a dramatically enhanced low energy electron yield. The results suggest that ICD may have a significant influence on cell survival after exposure to ionizing radiation.

Enhanced production of low energy electrons by alpha particle impact.

We present a new experimental setup to study electron-electron coincidences from superconducting surfaces. In our approach, electrons emitted from a surface are projected onto a time- and position-sensitive microchannel plate detector with delayline position readout. Electrons that are emitted within 2 π solid angle with respect to the surface are detected in coincidence. The detector used is a hexagonal delayline detector with enhanced multiple hit capabilities. It is read out with a Flash analog-to-digital converter. The three-dimensional momentum vector is obtained for each electron. The intrinsic dead time of the detector has been greatly reduced by implementing a new algorithm for pulse analysis. The sample holder has been matched to fit the spectrometer while being capable of cooling down the sample to 4.5 K during the measurement and heating it up to 420 K for the cleaning procedure.

Momentum spectrometer for electron-electron coincidence studies on superconductors.

We compare different tilted-pulse-front pumping schemes for single-cycle THz generation in LiNbO(3) crystals both theoretically and experimentally in terms of conversion efficiency. The conventional setup with a single lens as an imaging element has been found to be highly inefficient in the case of sub-50 fs pump pulses, mainly due to the resulting chromatic aberrations. These aberrations are avoided in the proposed new setup, which employs two concave mirrors in a Keplerian telescope arrangement as the imaging sequence. This partially compensates spherical aberrations and results in a ca. six times higher conversion efficiency in the case of 35-fs optical pump pulse duration compared to the single-lens setup. A THz field strength of 60 kV/cm was obtained using 0.5 mJ pump pulses. The divergence of the THz beam has been found experimentally to depend on the pump imaging scheme employed.

Optimization of single-cycle terahertz generation in LiNbO3 for sub-50 femtosecond pump pulses.

Bijvoet's method, which makes use of anomalous x-ray diffraction or dispersion, is the standard means of directly determining the absolute (stereochemical) configuration of molecules, but it requires crystalline samples and often proves challenging in structures exclusively comprising light atoms. Herein, we demonstrate a mass spectrometry approach that directly images the absolute configuration of individual molecules in the gas phase by cold target recoil ion momentum spectroscopy after laser ionization-induced Coulomb explosion. This technique is applied to the prototypical chiral molecule bromochlorofluoromethane and the isotopically chiral methane derivative bromodichloromethane.

Direct determination of absolute molecular stereochemistry in gas phase by Coulomb explosion imaging.

We investigate electron momentum distributions from single ionization of Ar by two orthogonally polarized laser pulses of different color. The two-color scheme is used to experimentally control the interference between electron wave packets released at different times within one laser cycle. This intracycle interference pattern is typically hard to resolve in an experiment. With the two-color control scheme, these features become the dominant contribution to the electron momentum distribution. Furthermore, the second color can be used for streaking of the otherwise interfering wave packets establishing a which-way marker. Our investigation shows that the visibility of the interference fringes depends on the degree of the which-way information determined by the controllable phase between the two pulses.

Streaking temporal double-slit interference by an orthogonal two-color laser field.

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 (4)He3 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.

Three-body physics. Observation of the Efimov state of the helium trimer.

The absolute configuration of individual small molecules in the gas phase can be determined directly by light-induced Coulomb explosion imaging (CEI). Herein, this approach is demonstrated for ionization with a single X-ray photon from a synchrotron light source, leading to enhanced efficiency and faster fragmentation as compared to previous experiments with a femtosecond laser. In addition, it is shown that even incomplete fragmentation pathways of individual molecules from a racemic CHBrClF sample can give access to the absolute configuration in CEI. This leads to a significant increase of the applicability of the method as compared to the previously reported complete break-up into atomic ions and can pave the way for routine stereochemical analysis of larger chiral molecules by light-induced CEI.

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

Quantum tunneling is a ubiquitous phenomenon in nature and crucial for many technological applications. It allows quantum particles to reach regions in space which are energetically not accessible according to classical mechanics. In this "tunneling region," the particle density is known to decay exponentially. This behavior is universal across all energy scales from nuclear physics to chemistry and solid state systems. Although typically only a small fraction of a particle wavefunction extends into the tunneling region, we present here an extreme quantum system: a gigantic molecule consisting of two helium atoms, with an 80% probability that its two nuclei will be found in this classical forbidden region. This circumstance allows us to directly image the exponentially decaying density of a tunneling particle, which we achieved for over two orders of magnitude. Imaging a tunneling particle shows one of the few features of our world that is truly universal: the probability to find one of the constituents of bound matter far away is never zero but decreases exponentially. The results were obtained by Coulomb explosion imaging using a free electron laser and furthermore yielded He2's binding energy of [Formula: see text] neV, which is in agreement with most recent calculations.

Imaging the He2 quantum halo state using a free electron laser.

Most large molecules are chiral in their structure: they exist as two enantiomers, which are mirror images of each other. Whereas the rovibronic sublevels of two enantiomers are almost identical (neglecting a minuscular effect of the weak interaction), it turns out that the photoelectric effect is sensitive to the absolute configuration of the ionized enantiomer. Indeed, photoionization of randomly oriented enantiomers by left or right circularly polarized light results in a slightly different electron flux parallel or antiparallel with respect to the photon propagation direction-an effect termed photoelectron circular dichroism (PECD). Our comprehensive study demonstrates that the origin of PECD can be found in the molecular frame electron emission pattern connecting PECD to other fundamental photophysical effects such as the circular dichroism in angular distributions (CDAD). Accordingly, distinct spatial orientations of a chiral molecule enhance the PECD by a factor of about 10.

Article	Year
Time-resolved momentum imaging system for molecular dynamics studies using a tabletop ultrafast extreme-ultraviolet light source. The Review of scientific instruments\| PubMed ID: 18601392	2008
Interatomic electronic decay driven by nuclear motion. Physical review letters\| PubMed ID: 21231042	2010
Enhanced production of low energy electrons by alpha particle impact. Proceedings of the National Academy of Sciences of the United States of America\| PubMed ID: 21730184	2011
Momentum spectrometer for electron-electron coincidence studies on superconductors. The Review of scientific instruments\| PubMed ID: 23126780	2012
Optimization of single-cycle terahertz generation in LiNbO3 for sub-50 femtosecond pump pulses. Optics express\| PubMed ID: 23546064	2013
Direct determination of absolute molecular stereochemistry in gas phase by Coulomb explosion imaging. Science (New York, N.Y.)\| PubMed ID: 24009390	2013
Streaking temporal double-slit interference by an orthogonal two-color laser field. Physical review letters\| PubMed ID: 25910115	2015
Three-body physics. Observation of the Efimov state of the helium trimer. Science (New York, N.Y.)\| PubMed ID: 25931554	2015
Absolute Configuration from Different Multifragmentation Pathways in Light-Induced Coulomb Explosion Imaging. Chemphyschem : a European journal of chemical physics and physical chemistry\| PubMed ID: 27298209	2016
Imaging the He2 quantum halo state using a free electron laser. Proceedings of the National Academy of Sciences of the United States of America\| PubMed ID: 27930299	2016
Observation of Enhanced Chiral Asymmetries in the Inner-Shell Photoionization of Uniaxially Oriented Methyloxirane Enantiomers. The journal of physical chemistry letters\| PubMed ID: 28582620	2017

Till Jahnke

Biography

JoVE Journal Publications

Other Publications