Dissociative Electron Attachment Cross Sections Research Articles

Low energy electron induced chemistry for e-bromine molecule scattering

The present study focuses on electron collision with bromine molecule, employing ab-initio scattering calculations. Using the R-matrix method, we calculated elastic and inelastic cross-sections using two different scattering models: static exchange with polarization and close-coupling. Our findings reveal total three low energy resonances for e-Br2 scattering which are primarily formed through transient negative ions. This observation is supported by dissociative electron attachment cross-section analysis, potential energy curves, and molecular orbital diagrams. Out of these three, first is at zero-energy, the electron attachment is recognized as shape-resonance and further two π* resonances as core-excited resonances. Present computation becomes more important as many cross-sections are reported as bench mark results in absence of any reported data. For instance: elastic, differential, momentum transfer, excitation and total cross-section. Comparing our results with sparse existing literature, we find good agreement.

Theoretical Investigation of Electron Impact Scattering on Imidazole.

This study presents the results of electron scattering calculations on a biologically important molecule, imidazole, using the UK molecular R-matrix method. The R-matrix calculations are performed using SE, SEP, and CC models, and the resonance detected in the present SEP model is found to be in better agreement with available experimental data than previous theoretical data. The study also reports an inelastic scattering cross section, which comprises dissociative electron attachment (DEA), excitation, and ionization cross section, for the first time. The total scattering cross sections are also reported for the first time. We confirm the presence of the two well-known π* shape resonances predicted earlier experimentally. Due to the scarcity of total scattering cross section (TCS) data for imidazole, we have compared the TCS of imidazole with its isoelectronic target isoxazole and drawn important conclusions. A comparison among the resonances of imidazole with those of isoxazole helps us to conclude that electron attachment to π* molecular orbitals is a general feature displayed by these five-membered heterocyclic compounds. The comprehensive electron scattering studies presented in this work are expected to provide a deeper understanding of electron-induced biochemical processes and fill gaps in the available data. Furthermore, this study is anticipated to inspire further investigations on imidazole and other five-membered heterocyclic ring molecules, which have significant applications in medicine.

Theoretical Investigation of Dissociative Electron Attachment of Acrylonitrile

Dissociative electron attachment (DEA) of acrylonitrile (C2H3CN) is investigated theoretically for two dominant anions CN- and C3N- for the electron impact energy range of 0-20 eV. The present low-energy DEA calculations are performed using the UK molecular R-matrix code using Quantemol-N. We have performed static exchange polarization (SEP) calculations by employing a cc-pVTZ basis set. Furthermore, present DEA cross-sections along with the appearance potential find good agreement with the three measurements reported many decades ago by Sugiura et al. [J. Mass Spectrom. Soc. Jpn. 1966, 14(4), 187-200], Tsuda et al. [Bull. Chem. Soc. Jpn. 1973, 46 (8), 2273-2277] and Heni and Illenberger [Int. J. Mass Spectrom. Ion Process. 1986, 73 (1-2), 127-144]. The molecule acrylonitrile and the anions are important for understanding interstellar chemistry, and it is the maiden theoretical attempt to compute a DEA cross-section for this molecule.

Fragmentation dynamics and absolute dissociative electron attachment cross sections in the low energy electron collision with ethanol.

Dissociative electron attachment (DEA) to ethanol has been probed to study fragmentation dynamics using Time-of-Flight (ToF) mass spectrometric technique. Several fragment ions, namely, H-, O-, OH-, C2H3O- and C2H5O- have been observed. Extra effort has been made to detect low mass ions (here, H-). Absolute DEA cross sections for the formation of O- and OH- have been measured for the first time using relative flow technique (RFT). The threshold energy of different dissociation channels has been calculated using density functional theory (DFT) method. By combining the experimental and theoretical data, we found evidence of hydrogen migration in the production of O and C2H3O- ions.

Dissociative Electron Attachment Cross Sections for Ni(CO)4, Co(CO)3NO, Cr(CO)6

Ni(CO)4, Cr(CO)6, Co(CO)3NO are some of the most common precursors used for focused electron beam induced deposition. Some of the compounds, even though extensively used have high requirements when it comes to handling being, explosives, highly flammable and with high toxicity levels, as is the case of Ni(CO)4. We are employing simulations to determine values hard to determine experimentally, and compare them with DFT calculations and experimental data where available. The use of Quantemol-N cross section simulations for dissociative electron attachment (DEA) at low electron energy in the range of 0–20 eV, gives valuable information on the fragmentation of the molecules, based on their bond dissociation energies, electron affinities and incident electron energies. The values obtained for the cross sections are 0.12 × 10−18 cm2 for Ni(CO)4, 4.5 × 10−16 cm2 for Co(CO)3NO DEA cross-sections and 4.3 × 10−15 cm2 for Cr(CO)6.

Velocity map imaging and cross sections of Fe(CO)5 for FEBIP applications

The present paper intends to be a new study of a widely used precursor in nanostructure deposition and FEBID processes with focus on its fragmentation at collisions with low energy electrons. Newer developments in nanotechnology with applications to focused electron beam-induced deposition (FEBID) and extreme ultraviolet lithography (EUVL) based on irradiation-induced chemistry come with advances in the size of the nanostructures at the surface and their flexibility in creating highly complex 3D structures. The deformation in the main structures of the FEBID process characterized by elongation, reduction in diameter of the main structure and the deposition of additional thin layers around the structure, on the substrate, are results of the secondary electrons effect, colliding with energies lower than 20 eV. Fe(CO)5 is one of the most used compounds in FEBID processes as it has a high vaporization pressure and has been shown to provide high-purity deposits (over 90%). This paper combines experiment and simulations to study electron scattering from Fe(CO)5, using Quantemol-N simulations with mass spectroscopy techniques to present the fragmentation pathways and channel distributions for each of the resulting negative ions at low electron energies, while experimental data on dissociative electron attachment make use of the velocity-sliced map imaging (VMI) technique to determine the anions at the incident electron energies. The Quantemol-N simulation package as a standalone is used to study collision processes of low-energy electrons with Fe(CO)5 molecules including elastic, electronic excitation, and dissociative electron attachment (DEA) cross sections for a wide range of process in nuclear industry, medical research and quantum chemistry.Graphical abstract

Resonant electron capture by 5-Br-2'-deoxyuridine.

The results of the study of resonant electron capture by molecules of 5-Br-2'-deoxyuridine (BrdUrd) over the range of electron energies from near zero to 14eV are described. In the thermal energy range, long-lived molecular negative ions, unstable with respect to autoneutralization and dehalogenation, have been registered. Examination of the kinetics of these decay processes led us to the conclusion that the most probable structure for molecular negative ions is that with an extended C-Br bond, which was predicted earlier using quantum-chemical calculations. Estimates have shown that the BrdUrd molecule owns a significant electronic affinity of 0.93-1.38eV. The most intense fragmentation channel leads to the abundant formation of Br- ions. The dissociative electron attachment cross section for Br- ions formation was estimated to amount to no less than 1.65 × 10-15cm2, indirectly implying a fairly intense formation of complementary highly reactive deoxyuridine-5-yl particles. These particles are known to be responsible for the radiosensitizing properties of BrdUrd.

Dissociative electron attachment to 5-bromo-uracil: non-adiabatic dynamics on complex-valued potential energy surfaces.

Electron induced dissociation reactions are relevant to many fields, ranging from prebiotic chemistry to cancer treatments. However, the simulation of dissociation electron attachment (DEA) dynamics is very challenging because the auto-ionization widths of the transient negative ions must be accounted for. We propose an adaptation of the ab initio multiple spawning (AIMS) method for complex-valued potential energy surfaces, along the lines of recent developments based on surface hopping dynamics. Our approach combines models for the energy dependence of the auto-ionization widths, obtained from scattering calculations, with survival probabilities computed for the trajectory basis functions employed in the AIMS dynamics. The method is applied to simulate the DEA dynamics of 5-bromo-uracil in full dimensionality, i.e., taking all the vibrational modes into consideration. The propagation starts on the resonance state and describes the formation of Br- anions mediated by non-adiabatic couplings. The potential energies, gradients and non-adiabatic couplings were computed with the fractional-occupancy molecular orbital complete-active-space configuration-interaction method, and the calculated DEA cross section are consistent with the observed DEA intensities.

Electron Scattering Cross-Section Calculations for Atomic and Molecular Iodine

Cross sections for electron scattering from atomic and molecular iodine are calculated based on the R-matrix (close-coupling) method. Elastic and electronic excitation cross sections are presented for both I and I2. The dissociative electron attachment and vibrational excitation cross sections of the iodine molecule are obtained using the local complex potential approximation. Ionization cross sections are also computed for I2 using the BEB model.

Toward a complete and comprehensive cross section database for electron scattering from NO using machine learning

We review experimental and theoretical cross sections for electron scattering in nitric oxide (NO) and form a comprehensive set of plausible cross sections. To assess the accuracy and self-consistency of our set, we also review electron swarm transport coefficients in pure NO and admixtures of NO in Ar, for which we perform a multi-term Boltzmann equation analysis. We address observed discrepancies with these experimental measurements by training an artificial neural network to solve the inverse problem of unfolding the underlying electron-NO cross sections while using our initial cross section set as a base for this refinement. In this way, we refine a suitable quasielastic momentum transfer cross section, a dissociative electron attachment cross section, and a neutral dissociation cross section. We confirm that the resulting refined cross section set has an improved agreement with the experimental swarm data over that achieved with our initial set. We also use our refined database to calculate electron transport coefficients in NO, across a large range of density-reduced electric fields from 0.003 to 10000 Td.

Thymidine and stavudine molecules in reactions with low-energy electrons

The negative ion formation and fragmentation processes in thymidine and stavudine were studied by means of resonant electron capture mass spectrometry in the electron energy range 0–14 eV. Stavudine is a nucleoside analog of thymidine, that differs from the latter by the presence of double bond in the deoxyribose moiety. In the energy range below 5 eV transient negative ions have been found to arise via shape resonances resulting in electron attachment into the empty π*-orbitals. The main fragmentation channels for molecular ions are the H-atom loss and N-glycosidic bond cleavage between sugar and a nucleobase moieties. The dissociative electron attachment cross sections for the fragment negative ions were measured. The structures for some observed anions and neutral counterparts were suggested basing on the thermochemical approach for dissociative reactions energy balance under the support of quantum chemical calculations. The processes of ion formation in thymidine were found to be similar to those revealed previously for deoxyuridine nucleoside. In contrast, very strong dissociative channel was found for stavudine yielding [M–R]– ions (where R is a sugar moiety) in the energy range <3 eV. The efficient fragmentation found for stavudine in the low energy electron attachment reactions may have implications for the design of nucleoside radiosensitizers for cancer therapy.

Resonant collisions of electrons with O2 via the lowest-lying 2Πg state of O2−

We report the results of an ab initio study of resonant vibrational excitation of molecular oxygen by electron impact at low energies where the lowest-lying ${}^{2}{\mathrm{\ensuremath{\Pi}}}_{g}$ resonant state of ${\mathrm{O}}_{2}^{\ensuremath{-}}$ dominantly contributes to the cross sections. The contribution of this resonance to the dissociative electron attachment cross section is also determined and the origin of its unusual oscillations is discussed. Calculations were performed within the nonlocal resonance model describing the nuclear dynamics of ${\mathrm{O}}_{2}^{\ensuremath{-}}$ after electron capture into the resonant state. The model was constructed using potential-energy curves obtained with standard quantum-chemical methods and eigenphase sums from the fixed-nuclei $R$-matrix calculations of electron scattering off ${\mathrm{O}}_{2}$. The effect of the spin-orbit interaction is taken into account when determining the potential-energy curves of the molecular negative ion. The vibrational excitation cross sections are compared with other available theoretical and experimental results.

Взаимодействие низкоэнергетических электронов с молекулами D-рибозы

Abstract– The interactions of low-energy electrons (&lt;20 eV) with D-ribose molecules, namely, electron scattering and dissociative attachment, are studied. The results of these studies showed that the fragmentation of D-ribose molecules occurs effectively even at an electron energy close to zero. as well as in the energy range 5.50–9.50 eV. In the total cross section of electron scattering by molecules, resonance features at energies of 5.00–9.00 eV in the region of formation of ionic fragments C3H4O2–, C2H3O2–, OH–, associated with the destruction of molecular heterocycles, were experimentally discovered for the first time. The correlation of the features observed in the scattering and dissociative electron attachment cross sections is analyzed.

Absolute dissociative electron attachment cross-section measurement of difluoromethane

Dissociative electron attachment (DEA) and ion-pair dissociation (IPD) processes of Difluoromethane (CH$_2$F$_2$) have been studied in the incident electron energy range 0 to 45 eV. Three different fragment anions (F$^-$, CHF$^-$ and F$_2^-$) are detected in the DEA range and two anions (F$^-$ and CHF$^-$) are detected in IPD range. Absolute cross-section of the F$^-$ fragment ion is measured for the first time. Three different resonances for both F$^-$ and CHF$^-$ ions and one single resonance peak for the F$_2^-$ ions are observed. Constant increase in ion counts above 8 eV incident electron energy indicates the involvement of IPD process. From the experimental observation, it is speculated that near 11 eV incident electron energy both DEA and IPD processes occur simultaneously.

Dissociative electron attachment cross sections for ro-vibrationally excited NO molecule and N − anion formation

Motivated by the huge need for data for non-equilibrium plasma modeling, a theoretical investigation of dissociative electron attachment to the NO molecule is performed. The calculations presented here are based on the local-complex-potential approach, taking into account five NO− resonances. Three specific channels of the process are studied, including the production of excited nitrogen atoms N(2D) and of its anions N−. Interpretation of the existing experimental data and their comparison with our theoretical result are given. A full set of ro-vibrationally-resolved cross sections and the corresponding rate coefficients are reported. In particular, a relatively large cross sections for N− ion formation at low energy of the incident electron and for vibrationally excited NO target are predicted. Finally, molecular rotation effects are discussed.

Electron Scattering Cross Sections for Anthracene and Pyrene.

UK molecular R-matrix calculations have been carried out for electron scattering from anthracene and pyrene. These molecules belong to the family of polycyclic hydrocarbons (PAHs) and are found in a nebula known as the Red Rectangle. Static exchange (SE), static exchange plus polarization (SEP), and close coupling (CC) approximations are used for scattering calculations. Different elastic and inelastic cross sections are computed in the present work in the energy range of 0.1-15 eV. Dissociative electron attachment cross sections are also calculated for both the molecules. Various shape, Feshbach/core-excited, and mixed resonances are detected for these molecules below 10 eV. All of the resonances detected in the present study are in agreement with the existing experimental and theoretical results. Due to the complexity of the present targets, electron collision cross sections are essentially unknown and hence most of the results are presented for the first time.

Nonlocal complex potential theory of dissociative electron attachment: Inclusion of two vibrational modes

The process of dissociative electron attachment (DEA) to molecules with several vibrational degrees of freedom is usually treated in the approximation of the local potential for the description of the nuclear motion. We develop the nonlocal complex potential theory to treat the dissociation dynamics when there is more than one vibrational mode in the neutral molecule. We demonstrate the application of the multimode nonlocal theory to a generic molecule of the type $\mathrm{C}{Y}_{3}X$, where Y denotes the H or F atom and X denotes the halogen atom, with the inclusion of symmetric C--X stretch and $\mathrm{C}{Y}_{3}$ deform (``umbrella'') vibrational modes. We present results for the dependence of DEA cross sections on the electron energy and vibrational energy for the ${\mathrm{CF}}_{3}\mathrm{Cl}$ molecule in the two-mode approximation. The 1.5 eV peak in the DEA cross section is well described in the one-mode approximation. However, inclusion of additional modes is required to explain the experimentally observed low-energy peak in the DEA cross section at the vibrational temperature ${T}_{v}=800$ K.

Formation of positive and negative ions in the gas phase of D-ribose by low-energy electrons

SynopsisUsing a hypocycloidal electron spectrometer the total dissociative electron attachment cross section and the ionization cross section for D-ribose molecule were studied in the E<30 eV energy range. A clear structure near zero energy and in the 6.0-9.5 eV range is observed in the dissociative electron attachment cross section. These features appear due to the formation of negative ion fragments of the molecule. The ionization potential of the D-ribose molecule was determined at 9.74 ± 0.02 eV. In the total ionization cross section weak features are observed, which most likely due to the formation of positive ion fragments of the initial molecule.

Low-energy electron scattering by cyanamide: anion spectra and dissociation pathways.

The low-energy anion spectra of cyanamide and its rare tautomer carbodiimide were surveyed with elastic electron scattering calculations. Our assignments differ qualitatively and quantitatively from a previous theoretical report. We support that both tautomers present two π* and two shape resonances, while cyanamide should also display a dipole bound state and a shape resonance. Available dissociative electron attachment measurements have shown several structures for dehydrogenation below 4 eV, but no sharp peaks related to vibrational Feshbach resonances. The absence of these resonances is explained by the lack of a potential barrier for tunneling of the hydrogen atom, despite the coupling between dipole bound and states. We found that the π* resonances initiate the dynamics that lead to hydrogen loss at 1.5, 2.5 and 3 eV. The later two structures arise from the anion states of cyanamide, while carbodiimide should account for the lower-lying one. The rarity of the second tautomer would be offset by its larger dissociative electron attachment cross section, enough to leave a distinct signature in the measured ion yield spectra. Low-energy electrons should thus decompose carbodiimide much more efficiently than cyanamide.

Theoretical study of vibrational excitation and dissociative electron attachment of NO2 by an electron impact

SynopsisCross sections for vibrational excitation and dissociative electron attachment (DEA) of the nitrogen dioxide (NO2) molecule in collisions with low-energy electrons are determined theoretically. The thermally-averaged rate coefficients of vibrational excitation are presented for the temperatures from 10 K to 10000 K. The obtained DEA cross section for NO2 agrees well with experimental data.