Electron Transfer Mediated Decay Research Articles

X-ray radiation damage cycle of solvated inorganic ions

X-ray-induced damage is one of the key topics in radiation chemistry. Substantial damage is attributed to low-energy electrons and radicals emerging from direct inner-shell photoionization or produced by subsequent processes. We apply multi-electron coincidence spectroscopy to X-ray-irradiated aqueous solutions of inorganic ions to investigate the production of low-energy electrons (LEEs) in a predicted cascade of intermolecular charge- and energy-transfer processes, namely electron-transfer-mediated decay (ETMD) and interatomic/intermolecular Coulombic decay (ICD). An advanced coincidence technique allows us to identify several LEE-producing steps during the decay of 1s vacancies in solvated Mg2+ ions, which escaped observation in previous non-coincident experiments. We provide strong evidence for the predicted recovering of the ion’s initial state. In natural environments the recovering of the ion’s initial state is expected to cause inorganic ions to be radiation-damage hot spots, repeatedly producing destructive particles under continuous irradiation.

Full Dynamical and Ab Initio Investigation of the Electron Transfer-Mediated Decay Mechanism of He+ in the Presence of Heavier Alkali Dimers.

We have studied the electron transfer-mediated decay (ETMD) process for the 1s ionized state of the He atom in the presence of a heavier alkali homonuclear dimer (Na2, K2, and Rb2) as well as heteronuclear dimer (LiNa, NaK, and KRb). In our computation, we have considered all the alkali dimers being in the singlet electronic ground state. The electron transfer from the alkali dimer to He (1s-1) leads to the emission of another electron from the alkali dimer into the continuum. We have investigated the impact of the distance of the He atom from the center of mass of the alkali dimer on the ETMD decay width. We also performed the Born-Oppenheimer molecular dynamics simulation to understand the impact of nuclear dynamics on the ETMD process.

Radiation damage by extensive local water ionization from two-step electron-transfer-mediated decay of solvated ions

Biomolecular radiation damage is largely mediated by radicals and low-energy electrons formed by water ionization rather than by direct ionization of biomolecules. It was speculated that such an extensive, localized water ionization can be caused by ultrafast processes following excitation by core-level ionization of hydrated metal ions. In this model, ions relax via a cascade of local Auger–Meitner and, importantly, non-local charge- and energy-transfer processes involving the water environment. Here, we experimentally and theoretically show that, for solvated paradigmatic intermediate-mass Al3+ ions, electronic relaxation involves two sequential solute–solvent electron transfer-mediated decay processes. The electron transfer-mediated decay steps correspond to sequential relaxation from Al5+ to Al3+ accompanied by formation of four ionized water molecules and two low-energy electrons. Such charge multiplication and the generated highly reactive species are expected to initiate cascades of radical reactions.

Effect of charge and solvation shell on non-radiative decay processes in s-block cationic metal ion water clusters.

Intermolecular Coulombic decay or electron transfer-mediated decay are the autoionization processes through which a molecule can relax. This relaxation is only possible if the inner valence's ionization potential (IP) exceeds the system's double ionization potential (DIP). To study the effects of charge and solvation shell, we have calculated the IP, DIP values, and lifetime of Na-2s and Mg-2s temporary bound states in various optimized structures of Na+-(H2O)n and Mg2+-(H2O)n (n = 1-5) micro-solvated clusters, where n water molecules are distributed in a way that some are directly bound to the metal ion and the rest to the water molecules. The first and second solvation shells are the names for the former and the latter water-binding positions, respectively. For a given n, the lifetime of decaying states is longer when water molecules are in the second solvation shell. We found that the Mg-2p state can decay for all n values in Mg2+-(H2O)n clusters, whereas the Na-2p state's decay is possible for n ≥ 2 in Na+-(H2O)n clusters. Our findings highlight the influence of metal ions' charge, different solvation shell structures, and the number of water molecules on the decay rate. These systems are relevant to the human body, which makes this study significant.

Solvated dielectrons from optical excitation: An effective source of low-energy electrons.

Low-energy electrons dissolved in liquid ammonia or aqueous media are powerful reducing agents that promote challenging reduction reactions but can also cause radiation damage to biological tissue. Knowledge of the underlying mechanistic processes remains incomplete, particularly with respect to the details and energetics of the electron transfer steps. In this work, we show how ultraviolet (UV) photoexcitation of metal-ammonia clusters could be used to generate tunable low-energy electrons in situ. Specifically, we identified UV light-induced generation of spin-paired solvated dielectrons and their subsequent relaxation by an unconventional electron transfer-mediated decay as an efficient, low-energy electron source. The process is robust and straightforward to induce with the prospect of improving our understanding of radiation damage and fostering mechanistic studies of solvated electron reduction reactions.

Electron scattering with ethane adsorbed on rare gas multilayers: Hole transfer, coulomb decay, and ion dissociation.

Positive ion desorption following electron impact dissociative ionization of ethane adsorbed on Ar, Kr, and Xe multilayers has been studied as a function of incident electron energy from threshold to 100eV. Based on the dependence of ion yields on the identity of the rare gas, it is likely that the majority of ethane molecules undergo indirect ionization following hole transfer from the ionized underlying rare gas. This has also been corroborated by density of states calculations showing the energetic alignment of the outer valence states of ethane and the condensed rare gas ionization energies. Due to the near-resonant nature of charge transfer for single-hole states, the ethane molecular ion is excited to different final ionic states on different rare gases, which leads to differences in ion desorption yields and branching ratios. The quantitative yields increase with increasing ionization energy gap between the rare gas and ethane, in the order Ar > Kr > Xe. The large increase in yields from 25eV onwards for all rare gases is likely due to the formation and decay of two-hole states on neighboring rare gas and ethane molecules due to interatomic and intermolecular Coulomb decay (ICD) and not electron transfer mediated decay (ETMD). The ICD and ETMD pathways become accessible when the incoming electron has sufficient energy to excite the inner valence ns level of the rare gas to a Rydberg state or ionize it. The experimental findings are supported by calculations of thresholds, density of states for the final configurations of these processes, and coupling strengths for hole transfer between ethane and rare gases. The fragment ion branching ratios vary with energy from threshold to about 35eV, showing the fragmentation pattern changes with the mode of hole transfer and availability of excess energy. Sigma C-C bonds are more likely to break than C-H bonds in the mid-20eV range, and this effect is most pronounced for Xe, followed by Kr, and then Ar.

Two-Sided Impact of Water on the Relaxation of Inner-Valence Vacancies of Biologically Relevant Molecules.

After ionization of an inner-valence electron of molecules, the resulting cation-radicals store substantial internal energy which, if sufficient, can trigger ejection of an additional electron in an Auger decay usually followed by molecule fragmentation. In the environment, intermolecular Coulombic decay (ICD) and electron-transfer mediated decay (ETMD) are also operative, resulting in one or two electrons being ejected from a neighbor, thus preventing the fragmentation of the initially ionized molecule. These relaxation processes are investigated theoretically for prototypical heterocycle-water complexes of imidazole, pyrrole, and pyridine. It is found that the hydrogen-bonding site of the water molecule critically influences the nature and energetics of the electronic states involved, opening or closing certain relaxation processes of the inner-valence ionized system. Our results indicate that the relaxation mechanisms of biologically relevant systems with inner-valence vacancies on their carbon atoms can strongly depend on the presence of the electron-density donating or accepting neighbor, either water or another biomolecule.

Effect of Protonation and Deprotonation on Electron Transfer Mediated Decay and Interatomic Coulombic Decay.

Electronically excited atoms or molecules in an environment are often subject to interatomic/intermolecular Coulombic decay (ICD) and/or electron transfer mediated decay (ETMD) mechanisms. A few of the numerous variables that can impact these non-radiative decay mechanisms include bond distance, the number of nearby atoms or molecules, and the polarisation effect. In this paper, we have studied the effect of protonation and deprotonation on the ionization potential (IP), double ionization potential (DIP), and lifetime (or decay width) of the temporary bound state in these non-radiative decay processes. We have chosen LiH-NH3 and LiH-H2 O as test systems. The equation of motion coupled cluster singles and doubles method augmented by complex absorbing potential (CAP-EOM-CCSD) has been used in calculating the energetic position of the decaying state and the system's decay rate. Deprotonation of LiH-NH3 /LiH-H2 O either from the metal center (LiH) or from ammonia/water lowers the IP and DIP compared to the neutral systems. In contrast, protonation increases these quantities compared to neutral systems. The protonation closes the inner valence state relaxation channels for ICD/ETMD. For example, the decay of the O-2s/N-2s state stops in protonated systems (LiH2 + -H2 O, LiH2 + -NH3 , and LiH-NH4 + ). Our study also shows that the efficiency, i. e., the rate of ICD/ETMD, can be altered by protonation and deprotonation. It is expected to have implications for chemical and biological systems.

Decay Processes in Cationic Alkali Metals in Microsolvated Clusters: A Complex Absorbing Potential Based Equation-of-Motion Coupled Cluster Investigation.

We have employed the highly accurate complex absorbing potential based ionization potential equation-of-motion coupled cluster singles and doubles (CAP-IP-EOM-CCSD) method to study the various intermolecular decay processes in ionized metals (Li+, Na+, K+) microsolvated by water molecules. For the Li atom, the electron is ionized from the 1s subshell. However, for Na and K atoms, the electron is ionized from 2s and both 2s and 2p subshells, respectively. We have investigated decay processes for the Li+-(H2O)n (n = 1-3) systems, as well as Na+-(H2O)n (n = 1, 2), and K+-H2O. The lithium cation in water can decay only via electron transfer mediated decay (ETMD) as there are no valence electrons in lithium. We have investigated how the various decay processes change in the presence of different alkali metal atoms and how the increasing number of water molecules play a significant role in the decay of microsolvated systems. To see the effect of the environment, we have studied Li+-NH3 in comparison to Li+-H2O. In the case of Na+-H2O, we have studied the impact of bond distance on the decay width. The effect of polarization on decay width was checked for the X+-H2O (X = Li, Na) systems. We used the PCM model to study the polarization effect. We have compared our results with existing theoretical and experimental results wherever available in the literature.

Signature of the neighbor's quantum nuclear dynamics in the electron transfer mediated decay spectra.

We computed fully quantum nuclear dynamics, which accompanies electron transfer mediated decay (ETMD) in weakly bound polyatomic clusters. We considered two HeLi2 clusters – with Li2 being either in the singlet electronic ground state or in the triplet first excited state – in which ETMD takes place after ionization of He. The electron transfer from Li2 to He+ leads to the emission of another electron from Li2 into the continuum. Due to the weak binding of He to Li2 in the initial states of both clusters, the involved nuclear wavepackets are very extended. This makes both the calculation of their evolution and the interpretation of the results difficult. We showed that despite the highly delocalized nature of the wavepackets the nuclear dynamics in the decaying state is imprinted on the ETMD electron spectra. The analysis of the latter helps understanding the effect which electronic structure and binding strength in the cluster produce on the quantum motion of the nuclei in the decaying state. The results produce a detailed picture of this important charge transfer process in polyatomic systems.

Efficient Intermolecular Energy Exchange and Soft Ionization of Water at Nanoplatelet Interfaces.

X-ray, energetic photon, and electron irradiation can ionize and electronically excite target atoms and molecules. These excitations undergo complicated relaxation and energy-transfer processes that ultimately determine the manifold system responses to the deposited excess energy. In weakly bound gas- and solution-phase samples, intermolecular Coulomb decay (ICD) and electron-transfer-mediated decay (ETMD) can occur with neighboring atoms or molecules, leading to efficient transfer of the excess energy to the surroundings. In ionic solids such as metal oxides, intra- and interatomic Auger decay produces localized final states that lead to lattice damage and typically the removal of cations from the substrate. The relative importance of Auger-stimulated damage (ASD) versus ICD and ETMD in microsolvated nanoparticle interfaces is not known. Though ASD is generally expected, essentially no lattice damage resulting from the ionization and electronic excitation of microsolvated boehmite (AlOOH) nanoplatelets has been detected. Rather efficient energy transfer and soft ionization of interfacial water molecules has been observed. This is likely a general phenomenon at gas-oxyhydroxide nanoparticle interfaces where the density of states of the ionized chemisorbed species significantly overlaps with the core hole states of the solid.

Electron transfer mediated decay of alkali dimers attached to He nanodroplets.

Alkali metal dimers attached to the surface of helium nanodroplets are found to be efficiently doubly ionized by electron transfer mediated decay (ETMD) when photoionizing the helium droplets. This process is evidenced by detecting in coincidence two energetic ions created by Coulomb explosion and one low-kinetic energy electron. The kinetic energy spectra of ions and electrons are reproduced by simple model calculations based on diatomic potential energy curves, and are in agreement with ab initio calculations for the He-Na2 and He-KRb systems. This work demonstrates that ETMD is an important decay channel in heterogeneous nanosystems exposed to ionizing radiation.

Molecular-bond breaking induced by interatomic decay processes

Selective bond breaking in a molecule with the use of photons opens the way to control chemical reactions. We demonstrate here that dissociation of a molecule can be efficiently achieved by first photoexciting a neighboring atom or molecule. On the example of the giant $\mathrm{He}\ensuremath{-}{\mathrm{H}}_{2}$ dimer, we show that simultaneous ionization and excitation of the helium atom induces ${\mathrm{H}}_{2}$ dissociation with a high probability. The excited ${\mathrm{He}}^{+}$ ion transfers its excess energy via interatomic Coulombic decay (ICD) or electron transfer mediated decay (ETMD) to ${\mathrm{H}}_{2}$ which is then singly or doubly ionized, respectively. In both cases, the molecular ion dissociates effectively within a few tens of femtoseconds. Molecular-bond breaking induced by ICD and ETMD are expected to be general phenomena, which provide alternatives to standard photochemistry.

Electron transfer mediated decay in HeLi2 cluster: Potential energy surfaces and decay widths.

Electron transfer mediated decay (ETMD) is a process responsible for double ionization of dopants in He droplets. It is initiated by producing He+ in the droplet, which is neutralized by ETMD, and has been shown to strongly enhance the dopant's double ionization cross section. The efficiency of ETMD, the spectra of emitted secondary electrons, and the character of the ionic products depend on the nuclear dynamics during the decay. To date, there has been no theoretical investigation of multimode dynamics which accompanies ETMD, which could help to understand such dynamics in a He droplet. In this article, we consider the He-Li2 cluster where an ab initio examination of multimode dynamics during the electronic decay is feasible. Moreover, this cluster can serve as a minimal model for Li2 adsorbed on the droplet's surface-a system where ETMD can be observed experimentally. In He droplets, Li2 can be formed in both the ground X1Σg + and the first excited a3Σu + states. In this article, we present ab initio potential energy surfaces of the electronic states of the He-Li2 cluster involved in ETMD, as well as the respective decay widths. We show that the structure of these surfaces and expected nuclear dynamics strongly depend on the electronic state of Li2. Thus, the overall decay rate and the appearance of the observable electron spectra will be dictated by the electronic structure of the dopant.

Sensitivity of Electron Transfer Mediated Decay to Ion Pairing.

Ion pairing in electrolyte solutions remains a topic of discussion despite a long history of research. Very recently, nearest-neighbor mediated electronic de-excitation processes of core hole vacancies (electron transfer mediated decay, ETMD) were proposed to carry a spectral fingerprint of local solvation structure and in particular of contact ion pairs. Here, for the first time, we apply electron-electron coincidence detection to a liquid microjet, and record ETMD spectra of Li 1s vacancies in aqueous solutions of lithium chloride (LiCl) in direct comparison to lithium acetate (LiOAc). A change in the ETMD spectrum dependent on the electrolyte anion identity is observed for 4.5 M salt concentration. We discuss these findings within the framework of the formation and presence of contact ion pairs and the unique sensitivity of ETMD spectroscopy to ion pairing.

Evidence for Efficient Pathway to Produce Slow Electrons by Ground-state Dication in Clusters

SynopsisWe present an experimental evidence for a so-far unobserved, but potentially very important step relaxation cascades following inner-shell ionization of a composite system: Multiply charged ionic states created after Auger decay may be neutralized by electron transfer from a neighboring species, producing at the same time a low-energy free electron. This electron transfer-mediated decay (ETMD) called process is effective even after Auger decay into the dicationic ground state. Here, we report the ETMD of Ne2+ produced after Ne 1s photoionization in Ne–Kr mixed clusters.

Observation of electron-transfer-mediated decay in aqueous solution

Photoionization is at the heart of X-ray photoelectron spectroscopy (XPS), which gives access to important information on a sample's local chemical environment. Local and non-local electronic decay after photoionization-in which the refilling of core holes results in electron emission from either the initially ionized species or a neighbour, respectively-have been well studied. However, electron-transfer-mediated decay (ETMD), which involves the refilling of a core hole by an electron from a neighbouring species, has not yet been observed in condensed phase. Here we report the experimental observation of ETMD in an aqueous LiCl solution by detecting characteristic secondary low-energy electrons using liquid-microjet soft XPS. Experimental results are interpreted using molecular dynamics and high-level ab initio calculations. We show that both solvent molecules and counterions participate in the ETMD processes, and different ion associations have distinctive spectral fingerprints. Furthermore, ETMD spectra are sensitive to coordination numbers, ion-solvent distances and solvent arrangement.

Charge transfer to ground-state ions produces free electrons

Inner-shell ionization of an isolated atom typically leads to Auger decay. In an environment, for example, a liquid or a van der Waals bonded system, this process will be modified, and becomes part of a complex cascade of relaxation steps. Understanding these steps is important, as they determine the production of slow electrons and singly charged radicals, the most abundant products in radiation chemistry. In this communication, we present experimental evidence for a so-far unobserved, but potentially very important step in such relaxation cascades: Multiply charged ionic states after Auger decay may partially be neutralized by electron transfer, simultaneously evoking the creation of a low-energy free electron (electron transfer-mediated decay). This process is effective even after Auger decay into the dicationic ground state. In our experiment, we observe the decay of Ne2+ produced after Ne 1s photoionization in Ne–Kr mixed clusters.

Theoretical and experimental investigation of Electron Transfer Mediated Decay in ArKr clusters

We investigate the electronic decay of an Ar 3s-1 vacancy in medium sized ArKr clusters. The only energetically accessible, radiationless decay mechanism is Electron Transfer Mediated Decay Three (ETMD3). Here, the argon vacancy is filled by an electron from one krypton atom, and the excess energy is transferred to a second krypton atom which consequently emits an electron. For the theoretical calculation of ETMD3 spectra, in a bottom-up approach, we study the dependence of the decay width on the geometry of elementary sets of three atoms, from which any cluster can be composed. We simulate the ETMD3 spectra of medium sized ArKr clusters and compare the resulting spectra to experimental ETMD electron spectra presented earlier (Förstel et al, 2011) and in this work. We show that ETMD3 is the dominating relaxation mechanism for the cases studied here. Experimental secondary electron spectra from ArKr clusters are compared to pure Ar and pure Kr clusters.

Interatomic Coulombic decay and electron-transfer-mediated decay following triple ionization of Ne2 and NeAr

We report observations of the interatomic Coulombic decay (ICD) and electron-transfer-mediated decay (ETMD) from the triply charged states in Ne2 and NeAr dimers. The ICD processes leading to fragmentation of Ne3+-Ne into Ne3+-Ne+ and Ne3+-Ar into Ne3+-Ar+, and ETMD processes leading to fragmentation of Ne3+-Ne into Ne2+-Ne2+ are unambiguously identified by electron–ion-ion coincidence spectroscopy in which the kinetic energy of the ICD or ETMD electron and the kinetic energy release between the two fragment ions are measured in coincidence.