Interaction Of Low-energy Electrons Research Articles

Low-energy (0–9 eV) electron interaction with gas phase 1,3-dichlorobenzene: an experimental and theoretical study

Abstract Dichlorobenzene used widely in industry for the synthesis of complex products, such as polymers. The processes using this compound require, as the initial step, the breakage of the C–Cl bond. In this work, we study the interaction of electrons with 1,3 dichlorobenzene molecules not only below 2 eV [M Mahmoodi-Darian et al 2001 J. Phys. Chem. A 113 11923–14929] but also at higher energies, i.e., up to 10 eV. In this investigated energy range, the electron induces the cleavage of the C–Cl bond producing essentially a Cl− anion and the chlorobenzene radical via dissociative electron attachment. The experimental measurements are completed with quantum scattering treatments providing the resonant states and also the integral scattering cross sections. These outcomes may potentially contribute to elaborate synthesis strategies using electrons (i.e., cold plasma, surface plasmon resonance, …).

Comparisons between the Direct and Indirect Effect of 1.5 keV X-rays and 0-30 eV Electrons on DNA: Base Lesions, Stand Breaks, Cross-Links, and Cluster Damages.

The interaction of low energy electrons (LEEs; 1-30 eV) with genomic material can induce multiple types of damage that may cause the loss of genetic information, mutations, genome instability, and cell death. For all damages measurable by electrophoresis, we provide the first complete set of G-values (yield of a specific product per energy deposited) induced in plasmid DNA by the direct and indirect effects of LEEs (GLEE) and 1.5 keV X-rays (GX) under identical conditions. Low energy photoelectrons are produced via X-rays incident on a tantalum (Ta) substrate covered with DNA and placed in a chamber filled with nitrogen at atmospheric pressure, under four different humidity levels, ranging from dry conditions to full hydration (Γ = 2.5 to Γ = 33, where Γ is the number of water molecules/nucleotide). Damage yields are measured as a function of X-ray fluence and humidity. GLEE values are between 2 and 27 times larger than those for X-rays. At Γ = 2.5 and 33, GLEE values for double strand breaks are 27 and 16 times larger than GX, respectively. The indirect effect contributes ∼50% to the total damage. These G-values allow quantification of potentially lethal lesions composed of strand breaks and/or base damages in the presence of varying amounts of water, i.e., closer to cellular conditions.

Electron-driven processes in enantiomeric forms of glutamic acid initiated by low-energy resonance electron attachment.

Low-energy (0-14eV) resonance electron interaction and fragment species produced by dissociative electron attachment (DEA) for enantiomeric forms of glutamic acid (Glu) are studied under gas-phase conditions by means of DEA spectroscopy and density functional theory calculations. Contrary to a series of amino acids studied earlier employing the DEA technique, the most abundant species are not associated with the elimination of a hydrogen atom from the parent molecular negative ion. Besides this less intense closed-shell [Glu - H]- fragment, only two mass-selected negative ions, [Glu - 19]- and [Glu - 76]-, are detected within the same electron energy region, with the yield maximum observed at around 0.9eV. This value matches well the energy of vertical electron attachment into the lowest normally empty π* COOH molecular orbital of Glu located at 0.88eV according to the present B3LYP/6-31G(d) calculations. Although the detection of asymmetric DEA properties a priori is not accessible under the present experimental conditions, "chirality non-conservation" can be associated with some decay channels. Evidently, the measured spectra for the L- and D-forms are found to be identical, the results, nevertheless, being of interest for the forthcoming experiments utilizing spin-polarized electron beam as a chiral factor in the framework of conventional DEA technique.

Low Energy (

Benzonitrile (BZN) and carbon tetrachloride (CCl4) are versatile solvents used as a precursor for the synthesis of many products. As multi-usage molecules, these compounds may be involved in sustainable chemistry processes such as the cold plasma techniques for which the generated electrons are known to be responsible for reactions. Therefore, it is desirable to explore the interaction of low energy electrons with the co-compounds in the gas phase. The production of chlorine and cyanine anions, initiated by the electron collision with CCl4 and BZN, respectively, undergo nucleophilic substitution SN2 reaction with the precursors molecules for the synthesis of chlorobenzene and tricholoacetonitrile. The mechanism of fragmentation of benzonitrile and the synthesis reactions are rationalized by DFT calculations. The yield of the cyanine anion produced from the ion reaction increases with the temperature of the admixture gas, probed in the 25-100 °C temperature range. The present work may contribute to a potential process for the production of chlorobenzene for instance via (cold) plasma techniques.

Low-Energy Electron Interactions with Methyl-p-benzoquinone: A Study of Negative Ion Formation.

Methyl-p-benzoquinone (MpBQ, CH3C6H3(=O)2) is a prototypical molecule in the study of quinones, which are compounds of relevance in biology and several redox reactions. Understanding the electron attachment properties of MpBQ and its ability to form anions is crucial in elucidating its role in these reactions. In this study, we investigate electron attachment to MpBQ employing a crossed electron-molecular beam experiment in the electron energy range of approximately 0 to 12 eV, as well as theoretical approaches using quantum chemical and electron scattering calculations. Six anionic species were identified: C7H6O2 -, C7H5O2 -, C6H5O-, C4HO-, C2H2 -, and O-. The parent anion is formed most efficiently, with large cross sections, through two resonances at electron energies between 1 and 2 eV. Potential reaction pathways for all negative ions observed are explored, and the experimental appearance energies are compared with calculated thermochemical thresholds. Although exhibiting similar electron attachment properties to pBQ, MpBQ's additional methyl group introduces entirely new dissociative reactions, while quenching others, underscoring its distinctive chemical behavior.

Numerical tools for simulating low-energy electron interactions in experimental nanodosimetry applications

Radiation damages to genes and cells occur at the DNA level, and therefore they are directly related to the spatial distribution of events caused by radiation at nanometer scale. Nanodosimetry introduces new quantities to correlate the initial features of radiation interactions and the likelihood of late radiobiological effects by means of Monte Carlo codes and, experimentally, with gas-detectors operating at low pressure.Within this context, the aim of this work is to develop a numerical approach based on the implementation of different simulation tools to accurately describe the low energy electron transport processes within nanodosimetric devices. This approach was directly applied to perform a proof-of-concept study of the response of the electron collector of the STARTRACK nanodosimeter. Garfield++ was used to simulate the primary track structure of 5.8 MeV He-4 particles, while COMSOL Multiphysics was used to model the geometry and the electrostatic field of the electron collector. Available experimental data, measured with the STARTRACK nanodosimeter, were used to validate Garfield++ nanodosimetric spectrum before proceeding with the simulation of the electron transport stage in the drift volume, again performed with Garfield++. In order to verify the performance and reliability of the implemented codes, the nanodosimetric distributions were studied with the threefold objective of characterizing the time, space, and energy distributions of particles collected at the end of the drift volume. These results can offer a valuable insight into the overall working principle of nanodosimeters: this understanding can be pivotal in optimizing and refining the design of such devices, ultimately extending their effectiveness in particle track characterization during radiation therapy.

Quantum effects in the interaction of low-energy electrons with light.

The interaction between free electrons and optical fields constitutes a unique platform to investigate ultrafast processes in matter and explore fundamental quantum phenomena. Specifically, optically modulated electrons in ultrafast electron microscopy act as noninvasive probes that push space-time-energy resolution to the picometer-attosecond-microelectronvolt range. Electron energies well above the involved photon energies are commonly used, rendering a low electron-light coupling and, thus, only providing limited access to the wealth of quantum nonlinear phenomena underlying the dynamical response of nanostructures. Here, we theoretically investigate electron-light interactions between photons and electrons of comparable energies, revealing quantum and recoil effects that include a nonvanishing coupling of surface-scattered electrons to light plane waves, inelastic electron backscattering from confined optical fields, and strong electron-light coupling under grazing electron diffraction by an illuminated crystal surface. Our exploration of electron-light-matter interactions holds potential for applications in ultrafast electron microscopy.

Interaction of low-energy electrons with radiosensitizers.

We provide an experimentalist's perspective on the present state-of-the-art in the studies of low-energy electron interactions with common radiosensitizers, including compounds used in combined chemo-radiation therapy and their model systems. Low-energy electrons are important secondary species formed during the interaction of ionizing radiation with matter. Their role in the radiation chemistry of living organisms has become an important topic for more than 20 years. With the increasing number of works and reviews in the field, we would like to focus here on a very narrow area of compounds that have been shown to have radio-sensitizing properties on the one hand, and high reactivity towards low-energy electrons on the other hand. Gas phase experiments studying electron attachment to isolated molecules and environmental effects on reaction dynamics are reviewed for modified DNA components, nitroimidazoles, and organometallics. In the end, we provide a perspective on the future directions that may be important for transferring the fundamental knowledge about the processes induced by low-energy electrons into practice in the field of rational design of agents for concomitant chemo-radiation therapy.

<i>Ab initio</i> molecular dynamics study on dissociation process of 2-thiouracil and its tautomers under low-energy electron interactions

When biomolecules interact with high-energy particles and rays, they are directly ionized or dissociated, then a large number of low-energy electrons are formed as secondary particles. These low-energy electrons will attach to biomolecules, and trigger off the secondary dissociation, forming free radicals and ions with high reactivity, which can damage the structure and function of the biomolecule and cause irreversible radiation damage to the biomolecule. It is important to study the low-energy dissociative electron attachment (DEA) process of biomolecules for understanding radiation damage to biological organisms. Currently, the theoretical studies of DEA have mainly focused on the bound states of negative ions and the types of resonances in the dissociation process. The dissociation process is well described by quantum computational method, but the diversity and complexity of dissociation channels present in the dissociation process of 2-thiouracil molecule also pose a great computational challenge to these methods. In addition, the quantum computational methods are not ideal for dealing with the discrete states of chemical bonds and the problem of continuity coupling of electrons. The dissociation dynamics of biomolecules mainly results from ionization and electron attachment. <i>Ab initio</i> molecular dynamics simulation can reasonably describe these processes. In light of these considerations, <i>ab initio</i> molecular dynamics simulation is used in this work to study dynamic variation process in DEA. The low-energy electron dissociative attachment to 2-thiouracil in the gas phase is studied by using the Born-Oppenheimer molecular dynamics model combined with density functional theory. It is found that an important dehydrogenation phenomenon of 2-thiouracil and its tautomers occurs in the DEA process, and that the N—H and C—H bond are broken at specific locations. Due to the loss of hydrogen atoms at the N and C sites, the closed-shell dehydrogenated negative ion (TU-H)<sup>–</sup> forms, which is the most important negative ion fragments in the dissociation process. The potential energy curves, the bond dissociation energy and the electron affinity energy of the broken bond show that the N—H bond is the most likely to break, indicating the formation of the negative ion (TU-H)<sup>–</sup> mainly comes from the breaking of N—H bond. The theoretical calculations in this work are in good agreement with the available experimental results, indicating that the chosen calculation method is fully reliable. ​The BOMD simulations can not only dynamically recover the process of dissociative attachment of low-energy electrons to 2-thiouracil, but also more importantly provide an insight into the mechanisms of dehydrogenation and dissociation channels of 2-thiouracil molecules in DEA process.

Experimental and Theoretical Investigations of the Fragmentation of Ethylenediamine Induced by Low-Energy (

Ethylenediamine is industrially used as an intermediate for the fabrication of many products. The development of new methodologies for synthesis compatible with the environment and sustainability, such as cold plasma processes, implicates reactions induced by nonthermal electrons. In this contribution, we study the interaction of low-energy (<10 eV) electrons with ethylenediamine. We show that electrons induce the fragmentation of the molecule into various anion fragments and associated neutral counterparts via dissociative electron attachment. The fragmentation mechanisms and energetics are discussed in the frame of DFT calculations. The fragmentation processes are quantified by the estimation of the cross sections and the branching ratios for competitive accessible dissociation routes.

Mechanistic study of low-energy electron interactions in the fragmentation of cisplatin

Theoretical calculations were performed to investigate the consequence of excess electron attachment to cisplatin, a widely used chemotherapeutic drug. The complex absorbing potential (CAP) methodology was utilized to identify resonance states. The analysis of the resonance states, together with the computation and characterization of the target molecular normal modes, provided insights into potential break-up pathways for cisplatin fragmentation, particularly in the Pt-Cl bond. The most probable fragmentation channel was found to involve the release of the [(NH3)2PtCl]• radical species, which can cause DNA damage.

Fragmentation of the DNA Lesion 8-oxo-Guanine by Low-Energy Electrons.

8-oxo-Guanine is a mutagenic lesion produced by reactions involving reactive oxygen species and guanine in DNA. Its production induces mispairing between the canonical nucleobases during DNA replication such that various types of cancers are associated with the DNA lesion. Since radiation therapy is used in some cases, the interaction of low-energy electrons with 8-oxo-guanine can in turn produce other reactive species, which in principle could have either a detrimental or protective effect on the organism. Motivated by these facts, we report a comparative experimental study of electron-induced fragmentation of guanine and 8-oxo-guanine, along with a theoretical study of the π* shape resonances and bound anion states, which may trigger those dissociation reactions. The electron-induced fragmentation of 8-oxo-guanine is remarkably distinct from the native form. More complex reactions were observed for the oxidized species, which may produce several anion fragments at very low energies (∼0 eV). The dehydrogenated parent anion, which is already a minor fragment in guanine, was completely suppressed in 8-oxo-guanine. The calculated thermodynamical thresholds also suggest that NH2 elimination in guanine, at sub-excitation energies, proceeds via a complex reaction involving rearrangement steps.

Low energy electron interaction with citric acid: a local complex potential based time-dependent wavepacket study

Low energy electron interaction with citric acid: a local complex potential based time-dependent wavepacket study

Angular distribution of photons emitted in collision of low-energy electrons with noble gases

The angular distribution of photons emitted at interaction of low-energy electrons with atoms of noble gases is investigated. The angular asymmetry of the bremsstrahlung cross section is significant and strongly depends on the electron and photon energies. The effect of polarization radiation is considered. It is shown that this effect is noticeable even below the electroluminescence threshold, in contrast to the generally accepted point of view. In the case of argon, the account for the polarization radiation improves the agreement between the predictions and the available experimental data for the yield of bremsstrahlung photons.

Low-energy electron interaction with 2-(trifluoromethyl)acrylic acid, a potential component for EUVL resist material.

Motivated by the current introduction of extreme ultraviolet lithography (EUVL) into chip manufacturing processes, and thus the transition to electron-induced chemistry within the respective resist materials, we have studied low energy electron-induced fragmentation of 2-(trifluoromethyl)acrylic acid (TFMAA). This compound is chosen as a potential resist component, whereby fluorination enhances the EUV adsorption and may at the same time promote electron-induced dissociation. Dissociative ionization and dissociative electron attachment are studied, and to aid the interpretation of the observed fragmentation channels, the respective threshold values are calculated at the DFT and coupled cluster level of theory. Not surprisingly, we find significantly more extensive fragmentation in DI than in DEA and in fact, the only significant DEA fragmentation channel is the cleavage of HF from the parent molecule upon electron attachment. Rearrangement and new bond formation are substantial in DI and are, in fact, similar to DEA, mainly associated with HF formation. The observed fragmentation reactions are discussed in relation to the underlying reactions and potential implications for the suitability of TFMAA as a component of EUVL resist materials.

Low-Energy Electron Interactions with Resveratrol and Resorcinol: Anion States and Likely Dissociation Pathways.

We report a computational study of the anion states of the resveratrol (RV) and resorcinol (RS) molecules, also investigating dissociative electron attachment (DEA) pathways. RV has well-known beneficial effects in human health, and its antioxidant activity was previously associated with DEA reactions producing H2. Our calculations indicate a valence bound state and four resonances ( to ) for that system. While the computed thermodynamic thresholds are compatible with DEA reactions producing H2 at 0 eV, the well-known mechanism involving vibrational Feshbach resonances built on a dipole bound state should not be present in RV. Our results suggest that the shallow valence bound state is expected to account for H2 elimination, probably involving / couplings along the vibration dynamics. The RS molecule is also an oxidant and a subunit of RV. Because two close-lying hydroxyl groups are found in the RS moiety, the H2-elimination reaction in RV should take place at the RS site. Our calculations point out a correspondence between the anion states of RV and RS and even between the thresholds. Nevertheless, the absence of bound anion states in RS, indicated by our calculations, is expected to suppress the H2-formation channel at 0 eV. One is led to conclude that the ethene and phenol subunits in RV stabilize the state, thus switching on the DEA mechanism producing H2.

Localized direct material removal and deposition by nanoscale field emission scanning probes

The manufactory of advanced micro- and nanoscale devices relies on capable patterning strategies. Focused electron beams, as for instance implemented since long in electron beam lithography and electron beam induced deposition, are in this regard key enabling tools especially at the early stages of device development and research. We show here that nanoscale field emission scanning probes can be potentially utilized as well for a prospective direct device fabrication by localized material deposition but notably, also by localized material removal. Field emission scanning probe processing was specifically realized on 10 nm chromium and 50 nm gold thin film stacks deposited on a (1 × 1) cm 2 fused silica substrate. Localized material deposition and metal removal was studied in various atmospheres comprising high vacuum, nitrogen, ambient air, naphthalene and carbon-dioxide. Stable and reliable regimes were in particular obtained in a carbonaceous atmosphere. Hence, localized carbon deposits were obtained but also localized metal removal was realized. We demonstrate furthermore that the selected electron emission parameters (20 V - 80 V, 180 pA) and the overall operation environment are crucial aspects that determine the degree of material deposition and removal. Based on our findings, direct tip-based micro- to nanoscale material patterning appears possible. The applied energy regime is also enabling new insights into low energy (< 100 eV) electron interaction. However, the underlying mechanisms must be further elucidated. • implementation of field-emission scanning probes to create localized 3D carbonaceous deposits from the gas phase. • demonstration of gold removal below the tip (line scans) by adjusting the experimental conditions. • first exploration of the impact of various atmospheres on the degree of material deposition and removal. • reproducible generation of line patterns by material removal and deposition.

Low-Energy Electron Damage to Plasmid DNA in Thin Films: Dependence on Substrates, Surface Density, Charging, Environment, and Uniformity.

The interaction of low-energy electrons (LEEs) with DNA plays a significant role in the mechanisms leading to biological damage induced by ionizing radiation, particularly in radiotherapy, and its sensitization by chemotherapeutic drugs and nanoparticles. Plasmids constitute the form of DNA found in mitochondria and appear as a suitable model of genomic DNA. In a search for the best LEE targets, damage was induced to plasmids, in thin films in vacuum, by 6, 10, and 100 eV electrons under single collision conditions. The yields of single- and double-strand breaks, other cluster damage, isolated base lesions, and crosslinks were measured by electrophoresis and enzyme treatment. The films were deposited on oriented graphite or polycrystalline tantalum, with or without DNA autoassembly via diaminopropane (Dap) intercalation. Yields were correlated with the influence of vacuum, film uniformity, surface density, substrates, and the DNA environment. Aided by surface potential measurements and scanning electron microscopy and atomic force microscopy images, the lyophilized Dap-DNA films were found to be the most practical high-quality targets. These studies pave the way to the fabrication of LEE target-films composed of plasmids intercalated with biomolecules that could mimic the cellular environment; for example, as a first step, by replacing Dap with an amino acid.

Low-energy electron interaction and focused electron beam-induced deposition of molybdenum hexacarbonyl (Mo(CO)6).

Motivated by the potential role of molybdenum in semiconductor materials, we present a combined theoretical and experimental gas-phase study on dissociative electron attachment (DEA) and dissociative ionization (DI) of Mo(CO)6 in comparison to focused electron beam-induced deposition (FEBID) of this precursor. The DEA and DI experiments are compared to previous work, differences are addressed, and the nature of the underlying resonances leading to the observed DEA processes are discussed in relation to an earlier electron transmission study. Relative contributions of individual ionic species obtained through DEA and DI of Mo(CO)6 and the average CO loss per incident are calculated and compared to the composition of the FEBID deposits produced. These are also compared to gas phase, surface science and deposition studies on W(CO)6 and we hypothesize that reductive ligand loss through electron attachment may promote metal–metal bond formation in the deposition process, leading to further ligand loss and the high metal content observed in FEBID for both these compounds.

Dissociative ionization and electron beam induced deposition of tetrakis(dimethylamino)silane, a precursor for silicon nitride deposition.

Motivated by the use of tetrakis(dimethylamino)silane (TKDMAS) to produce silicon nitride-based deposits and its potential as a precursor for Focused Electron Beam Induced Deposition (FEBID), we have studied its reactivity towards low energy electrons in the gas phase and the composition of its deposits created by FEBID. While no negative ion formation was observed through dissociative electron attachment (DEA), significant fragmentation was observed in dissociative ionization (DI). Appearance energies (AEs) of fragments formed in DI were measured and are compared to the respective threshold energies calculated at the DFT and coupled cluster (CC) levels of theory. The average carbon and nitrogen loss per DI incident is calculated and compared to its deposit composition in FEBID. We find that hydrogen transfer reactions and new bond formations play a significant role in the DI of TKDMAS. Surprisingly, a significantly lower nitrogen content is observed in the deposits than is to be expected from the DI experiments. Furthermore, a post treatment protocol using water vapour during electron exposure was developed to remove the unwanted carbon content of FEBIDs created from TKDMAS. For comparison, these were also applied to FEBID deposits formed with tetraethyl orthosilicate (TEOS). In contrast, effective carbon removal was achieved in post treatment of TKDMAS, while his approach only marginally affected the composition of deposits made with TEOS.