F. Trinter

Resonant Auger decay driving intermolecular Coulombic decay in molecular dimers

In 1997, it was predicted that an electronically excited atom or molecule placed in a loosely bound chemical system (such as a hydrogen-bonded or van-der-Waals-bonded cluster) could efficiently decay by transferring its excess energy to a neighbouring species that would then emit a low-energy electron. This intermolecular Coulombic decay (ICD) process has since been shown to be a common phenomenon, raising questions about its role in DNA damage induced by ionizing radiation, in which low-energy electrons are known to play an important part. It was recently suggested that ICD can be triggered efficiently and site-selectively by resonantly core-exciting a target atom, which then transforms through Auger decay into an ionic species with sufficiently high excitation energy to permit ICD to occur. Here we show experimentally that resonant Auger decay can indeed trigger ICD in dimers of both molecular nitrogen and carbon monoxide. By using ion and electron momentum spectroscopy to measure simultaneously the charged species created in the resonant-Auger-driven ICD cascade, we find that ICD occurs in less time than the 20 femtoseconds it would take for individual molecules to undergo dissociation. Our experimental confirmation of this process and its efficiency may trigger renewed efforts to develop resonant X-ray excitation schemes for more localized and targeted cancer radiation therapy.

Vibrationally resolved decay width of interatomic Coulombic decay in HeNe.

We investigate the ionization of HeNe from below the He 1s3p excitation to the He ionization threshold. We observe HeNe+ ions with an enhancement by more than a factor of 60 when the He side couples resonantly to the radiation field. These ions are an experimental proof of a two-center resonant photoionization mechanism predicted by Najjari et al. [Phys. Rev. Lett. 105, 153002 (2010)]. Furthermore, our data provide electronic and vibrational state resolved decay widths of interatomic Coulombic decay in HeNe dimers. We find that the interatomic Coulombic decay lifetime strongly increases with increasing vibrational state.

Evolution of interatomic Coulombic decay in the time domain.

During the past 15 years a novel decay mechanism of excited atoms has been discovered and investigated. This so-called interatomic Coulombic decay (ICD) involves the chemical environment of the electronically excited atom: the excitation energy is transferred (in many cases over long distances) to a neighbor of the initially excited particle usually ionizing that neighbor. It turned out that ICD is a very common decay route in nature as it occurs across van der Waals and hydrogen bonds. The time evolution of ICD is predicted to be highly complex, as its efficiency strongly depends on the distance of the atoms involved and this distance typically changes during the decay. Here we present the first direct measurement of the temporal evolution of ICD using a novel experimental approach.

Imaging the structure of the trimer systems 4He3 and 3He4He2

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.

Enhanced production of low energy electrons by alpha particle impact

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 (Ne2). 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.

Imaging the He2 quantum halo state using a free electron laser

Significance In bound matter on all length scales, from nuclei to molecules to macroscopic solid objects, most of the density of the bound particles is within the range of the interaction potential which holds the system together. Quantum halos on the contrary are a type of matter where the particle density is mostly outside the range of the interaction potential in the tunneling region of the potential. Few examples of these fascinating systems are known in nuclear and molecular physics. The conceptually simplest halo system is made of only two particles. Here we experimentally image the wavefunction of the He2 quantum halo. It shows the predicted exponential shape of a tunneling wavefunction. 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 151.9±13.3 neV, which is in agreement with most recent calculations.

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

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.

Ab initio calculation of ICD widths in photoexcited HeNe

Excitation of HeNe by synchrotron light just below the frequency of the 1s → 3p transition of isolated He has been recently shown to be followed by resonant interatomic Coulombic decay (ICD). The vibrationally resolved widths of the ICD states were extracted with high precision from the photoion spectra. In this paper, we report the results of ab initio calculations of these widths. We show that interaction between electronic states at about the equilibrium distance of HeNe makes dark states of He accessible for the photoexcitation and subsequent electronic decay. Moreover, the values of the calculated widths are shown to be strongly sensitive to the presence of the non-adiabatic coupling between the electronic states participating in the decay. Therefore, only by considering the complete manifold of interacting decaying electronic states a good agreement between the measured and computed ICD widths can be achieved.

Agreement of Experiment and Theory on the Single Ionization of Helium by Fast Proton Impact

Even though the study of ion-atom collisions is a mature field of atomic physics, large discrepancies between experiment and theoretical calculations are still common. Here we present experimental results with high momentum resolution on the single ionization of helium induced by 1-MeV protons, and we compare these to theoretical calculations. The overall agreement is strikingly good, and even the first Born approximation yields good agreement between theory and experiment. This has been expected for several decades, but so far has not been accomplished. The influence of projectile coherence effects on the measured data is briefly discussed in terms of an ongoing dispute on the existence of nodal structures in the electron angular emission distributions.

Ion-impact-induced interatomic Coulombic decay in neon and argon dimers

We investigate the contribution of Interatomic Coulombic Decay induced by ion impact in neon and argon dimers (Ne