Dissociative Attachment Of Low-energy Electrons Research Articles

<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.

Dissociative attachment of low-energy electrons to acetonitrile

Dissociative attachment of low-energy electrons to acetonitrile

Probing the Potential Energy Surfaces of BrCN- by Dissociative Electron Attachment.

State coupling certainly determines the topologic features of the molecular potential energy surface (PES) and potentially diversifies chemical reaction pathways. Here we report the new PESs of BrCN- in the low-lying electronic states that are distinctly different from the previous predictions in the short Br-CN bond region but validated by the high-resolution ion velocity imaging measurements of low-energy dissociative electron attachment (DEA) to BrCN. Besides the vibrating CN- ions produced in the fast Br-CN bond stretching motions, we confirm that the ro-vibrating CN- ions with a nearly isotropic angular distribution are produced by receiving a torque in the combinational motion of Br-CN bond bending and stretching. The latter process is closely related to the potential well of BrCN- at the first excited state A2Π3/2 that arises from the Π-Σ state couplings. Our findings not only suggest that the PESs of other anionic cyanogen halides are in dire need of reexamination but also show that ion velocity imaging of the DEA process is a powerful experimental method for evaluating the theoretical PESs of molecular anions.

Dissociative Electron Attachment to Molecular Acetonitrile.

Low-energy dissociative electron attachment to molecular acetonitrile (CH3CN) is investigated by recording the efficiency curves of CH2CN-, CHCN-, and CN- products, but the present curves are distinctly different from those in the previous reports. Now it is recommended that the reaction thresholds of e- + CH3CN → H2 + CHCN- and CH3 + CN- are respectively about 1.51 and 1.52 eV, and four shape-resonant states, one 2Π and three 2∑, of CH3CN- are involved in the fragmentations at the low and high electron-attachment energies. By using a high-resolution anion velocity-map imaging spectrometer, we obtain the CN- momentum images at the electron attachment energies of 7.10, 7.60, and 8.10 eV and interpret them with four pathways concerning two- and three-body dissociations.

Electron-Induced Dissociation of the Potential Radiosensitizer 5-Selenocyanato-2'-deoxyuridine.

5-Selenocyanato-2'-deoxyuridine (SeCNdU) is a recently proposed radiosensitizer based on 2'-deoxyuridine (dU) with the electron-affinic selenocyanato (-SeCN) side group attached at the C5 position of uracil. Since electron interaction processes may be an important source of DNA damage by ionizing radiation, we have studied low-energy dissociative electron attachment to SeCNdU in the gas phase. Negative ion formation has been obtained by means of mass spectrometry, where a rich fragmentation pattern is observed even at ∼0 eV. The reaction pathways exhibiting the highest ion yields are C4N2O2H2Se•- and CN-, both involving a cleavage of the Se-CN bond. The heaviest fragment anion observed is C9N2O5H10Se•-, where besides the charged species, the hydrogen and cyano radicals are also formed. Further decomposition channels also yield the highly reactive hydroxyl radical, which possesses a high DNA damage potential. All observed channels have experimentally determined onsets at 0 eV, which are supported by calculations performed at the M06-2X/aug-cc-pVTZ level. The calculations comprise the thermochemical thresholds at standard and experimental (428.15 K, 3 × 10-11 atm) conditions together with the adiabatic electron affinities. The present study shows that low-energy electrons very effectively decompose SeCNdU upon attachment of thermal electrons, producing a large variety of charged fragments and radicals.

Effects of the plasma-facing materials on the negative ion H− density in an ECR (2.45 GHz) plasma

Within the framework of fundamental research, the present work focuses on the role of surface material in the production of H− negative ion, with a potential application of designing cesium-free H− negative ion sources oriented to fusion application. It is widely accepted that the main reaction leading to H− production, in the plasma volume, is the dissociative attachment of low-energy electrons (Te ≤ 1 eV) on highly ro-vibrationally excited hydrogen molecules. In parallel with other mechanisms, the density of these excited molecules may be enhanced by means of the recombinative desorption, i.e. the interaction between surface absorbed atoms with other atoms (surface adsorbed or not) through the path . Accordingly, a systematic study on the role played by the surface in this reaction, with respect to the production of H− ion in the plasma volume, is here performed. Thus, tantalum and tungsten (already known as H− enhancers) and quartz (inert surface) materials are employed as inner surfaces of a test bench chamber. The plasma inside the chamber is produced by electron cyclotron resonance (ECR) driving and it is characterized with conventional electrostatic probes, laser photodetachment, and emission and absorption spectroscopy. Two different positions (close to and away from the ECR driving zone) are investigated under various conditions of pressure and power. The experimental results are supported by numerical data generated by a 1D model. The latter couples continuity and electron energy balance equations in the presence of magnetic field, and incorporates vibrational kinetics, H2 molecular reactions, H electronically excited states and ground-state species kinetics. In the light of this study, recombinative desorption has been evidenced as the most probable mechanism, among others, responsible for an enhancement by a factor of about 3.4, at 1.6 Pa and 175 W of microwave power, in the case of tantalum.

Suppression of low-energy dissociative electron attachment in Fe(CO)5 upon clustering.

In this work, we probe anion production upon electron interaction with Fe(CO)5 clusters using two complementary cluster-beam setups. We have identified two mechanisms that lead to synthesis of complex anions with mixed Fe/CO composition. These two mechanisms are operative in distinct electron energy ranges. It is shown that the elementary decomposition mechanism that has received perhaps the most attention in recent years (i.e., dissociative electron attachment at energies close to 0 eV) becomes suppressed upon increasing aggregation of iron pentacarbonyl. We attribute this suppression to the electrostatic shielding of a long-range interaction that strongly enhances the dissociative electron attachment in isolated Fe(CO)5.

Investigation of the Radio-Frequency Discharge in a High Current Negative Hydrogen Ion Source With a Global Enhanced Vibrational Kinetic Model

A numerical investigation of the radio-frequency hydrogen discharge in the high current negative hydrogen ion source (HCNHIS) is presented using a global enhanced vibrational kinetic model (GEVKM). The HCNHIS consists of a high-pressure (2–65 torr) radio-frequency discharge chamber where the main production of high-lying vibrational states of the hydrogen molecules occurs. The hydrogen plasma flow in the discharge chamber is reduced by a series of bypass tubes and enters through a nozzle into a low-pressure (1–15 mtorr) negative hydrogen ion production chamber where H− are generated mainly by the dissociative attachment of low-energy electrons to rovibrationally excited hydrogen molecules. The GEVKM is applied to the HCNHIS discharge and involves volume-averaged equations for 21 hydrogen species (atoms, ions, and molecules in excited states) and electrons. The GEVKM is supplemented with outlet boundary conditions for the nozzle and bypass tubes of the HCNHIS and accounts for compressibility, viscous, and rarefaction effects. GEVKM simulations of the RF discharge are performed with inlet flow rates of 5–1000 sccm and absorbed powers of 200–1000 W using the HCNHIS-2 design which is configured with an extractor grid attached to a short negative ion production region. These simulations investigate the effects of the absorbed power and the inlet flow rate on the chemical composition, electron and heavy particles temperature, wall temperature, the maximum extractable H− current in the discharge chamber, as well as optimum operational parameters of HCNHIS-2. GEVKM simulations of the HCNHIS-2 discharge are used to obtain estimates of the H− current and compared with Faraday cup measurements taken at the extraction grid.

Carbon monoxide dissociative attachment and resonant dissociation by electron-impact

Low-energy dissociative electron attachment and resonant electron impact dissociation of CO molecule are considered. Ro-vibrationally resolved cross sections and rate coefficients for both the processes are calculated using an ab-initio model based on the low-lying resonance of CO−. Final results show that the cross sections increases very rapidly as a function of the ro-vibrational level; these cross sections should be useful for understanding kinetic dissociation of CO in strongly non-equilibrium plasmas.

Low-energy dissociative electron attachment toCF2

We present the results of a theoretical study of dissociative electron attachment (DEA) of low-energy electrons to ${\mathrm{CF}}_{2}$. We carried out electron scattering calculations using the complex Kohn variational method at the static-exchange and relaxed self-consistent field (SCF) level at the equilibrium geometry and compare our differential cross sections to other results. We then repeated these calculations as a function of the three internal degrees of freedom to obtain the resonance energy surfaces and autoionization widths. We use this data as input to form the Hamiltonian relevant to the nuclear dynamics. The multidimensional wave equation is solved using the multiconfiguration time-dependent Hartree (MCTDH) approach within the local approximation.

A Global Enhanced Vibrational Kinetic Model for High-Pressure Hydrogen RF Discharges

A global enhanced vibrational kinetic model (GEVKM) is developed for multitemperature, chemically reacting hydrogen plasmas in inductively coupled cylindrical discharges for lowto high-pressure regimes. The species in a GEVKM are ground-state hydrogen atoms H and molecules H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> , 14 vibrationally excited hydrogen molecules H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> (v), v = 1 - 14, electronically excited hydrogen atoms H(2) and H(3), groundstate positive ions H <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> , H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">2</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> , and H <sub xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sub> <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">+</sup> , ground-state negative ions H <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">-</sup> , and electrons e. The GEVKM involves volume-averaged steady-state continuity equations for the plasma species, an electron energy equation, a total energy equation, a heat transfer equation to the chamber walls, and a comprehensive set of surface and volumetric chemical processes governing vibrational and ionization kinetics of hydrogen plasmas. The GEVKM is verified and validated by comparisons with previous numerical simulations and experimental measurements of a negative hydrogen ion source in the low-pressure (20-100 mtorr), low-absorbed-power-density (0.053-0.32 W/cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sup> ) regime and of a microwave plasma reactor in the intermediate to high-pressure (1-100 torr), high-absorbed-power-density (8.26-22 W/cm <sup xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink">3</sup> ) regime. The GEVKM is applied to the simulation of a high-current negative hydrogen ion source (HCNHIS). The HCNHIS consists of a high-pressure (20-65 torr) radio-frequency discharge chamber in which the main production of high-lying vibrational states of the hydrogen molecules occurs, a bypass system, and a low-pressure (0.1-0.4 torr) negative hydrogen ion production region where negative ions are generated by the dissociative attachment of low-energy electrons to rovibrationally excited hydrogen molecules. The discharge pressure and negative hydrogen ion current predicted by the GEVKM compare well with the measurements in the HCNHIS.

Negative Ion Generation and Isotopic Effect in Electron Cyclotron Resonance Plasma

The impact of the thermoelectron emission upon the efficiency of negative hydrogen ion production in an electron cyclotron resonance source with driven plasma rings is studied. The obtained data demonstrate that the negative ion production is realized in two stages. At the first stage, the hydrogen and deuterium molecules are excited to vibrational states and high-lying Rydberg levels in collisions with the plasma electrons in the discharge volume. The second stage leads to the negative ion production through the process of dissociative attachment of low-energy electrons by the excited molecules. The low-energy electrons are originated due to a bombardment of the plasma electrode by ions of a driven plasma ring and the thermoemission from heated tungsten filaments. The experiments prove that the negative hydrogen ion generation occurs predominantly in a plasma electrode superficial layer filled with thermoelectrons. The negative ion generation through the vibrational excitation channel requires the isotope effect that appears due to the difference in the velocities of the vibrational movement of the nuclei in light and heavy molecular isotopes. From the experimental data for the negative ion generation rate, it follows that the main channel for $H^{-}$ and $D^{-}$ ion production involves the process of high Rydberg states excitation of $H_{2}$ and $D_{2}$ molecules.

Electron attachment to molecules in a cluster environment

Low-energy dissociative electron attachment (DEA) to the CF(2)Cl(2) and CF(3)Cl molecules in a water cluster environment is investigated theoretically. Calculations are performed for the water trimer and water hexamer. It is shown that the DEA cross section is strongly enhanced when the attaching molecule is embedded in a water cluster, and that this cross section grows as the number of water molecules in the cluster increases. This growth is explained by a trapping effect that is due to multiple scattering by water molecules while the electron is trapped in the cluster environment. The trapping increases the resonance lifetime and the negative ion survival probability. This confirms qualitatively existing experiments on electron attachment to the CF(2)Cl(2) molecule placed on the surface of H(2)O ice. The DEA cross sections are shown to be very sensitive to the position of the attaching molecule within the cluster and the orientation of the electron beam relative to the cluster.

Vibrational Feshbach resonances in dissociative electron attachment to uracil

Low-energy dissociative electron attachment to uracil molecules in the gas phase is partly controlled by interaction between the lowest ${\ensuremath{\sigma}}^{*}$ resonance with a dipole-supported anion state. We calculate this contribution using a combination of the finite element discrete model with the resonance $R$-matrix theory. Deuterated uracil is investigated, also, and a strong isotope effect is found. The results agree qualitatively and semiquantitatively with experimental data, but for a complete description of the process the interaction between a second N---H bond ${\ensuremath{\sigma}}^{*}$ resonance in the molecule and the second ${\ensuremath{\pi}}^{*}$ resonance should be included.

Recent progress in the theory of dissociative attachment: From diatomics to biomolecules

We present a summary of recent progress in theoretical studies of low-energy dissociative electron attachment (DEA) to halogen molecules and polyatomic molecules based on the resonance R-matrix theory. It explains many observed features in DEA cross sections including low-energy behavior, threshold resonances and cusps. It also gives correct description of the temperature dependence of the attachment rate coefficients. More recently the theory was applied to two molecules of biological interest, formic acid and glycine. DEA mechanisms in these systems are very similar to those in hydrogen halides.

Comment on “Electron-induced bond breaking at low energies in HCOOH and glycine: The role of very short-livedσ∗anion states”

Recent model calculations by Gallup et al. [Phys. Rev. A79, 042710 (2009)] suggest that low-energy dissociative electron attachment to formic acid can be explained solely in terms of a very short-lived ${\ensuremath{\sigma}}^{\ensuremath{\ast}}$ anion state and that no ${\ensuremath{\sigma}}^{\ensuremath{\ast}}/{\ensuremath{\pi}}^{\ensuremath{\ast}}$ coupling is required. We argue that this interpretation of the experimental data, which is at odds with our earlier study, is flawed.

Dissociative electron attachment: Threshold phenomena and multimode effects

We present a summary of recent progress on studies of threshold phenomena in low-energy dissociative electron attachment to polyatomic molecules: vibrational Feshbach resonances and threshold cusps. The theoretical approach is based on the resonance R-matrix theory. It allows us to analyze threshold effects in other channels, particularly vibrational excitation. If the molecular long-range field is not strong enough, virtual-state cusps are observed at vibrational excitation thresholds. The second part of the paper illustrates the multimode effects in dissociative attachment using attachment to the CF3Cl molecule as an example. Symmetric stretch C-Cl vibrations v3 and symmetric deformation (or so-called "umbrella") vibrations v2 are included. Calculations allow us to study the final-state vibrational distribution in the CF3(v2) fragment.

Theoretical Study on the Mechanism of Low-Energy Dissociative Electron Attachment for Uracil

The lowest electronically adiabatic potential energy surface of the uracil anion has been theoretically investigated with density-functional theory methods in order to understand the mechanism of the N-H bond dissociation induced by low-energy electron attachment. We found that the BH&HLYP level can reasonably describe both the dipole-bound and valence anionic states in a balanced way. With this density-functional theory level, we have constructed two-dimensional potential energy surfaces as a function of appropriate internal coordinates and discuss the importance of electronic coupling between the dipole-bound and valence anion states in dissociative electron attachment of uracil. The transition state geometry for the electronic isomerization between the dipole-bound anion and the pi* valence anion was successfully optimized and the barrier height for this isomerization was found to be relatively low. It was found that the out-of-plane motion of H at the C6 position plays the most important role in this isomerization process. Reduced-dimensionality quantum wave packet calculations taking two active internal coordinates into account have also been performed to interpret the resonance structures observed in cross sections for the N-H dissociation channel at a qualitative level.

Three-body breakup in dissociative electron attachment to the water molecule

We report the results of ab initio calculations on dissociative electron attachment to water that demonstrate the importance of including three-body breakup in the dissociation dynamics. While three-body breakup is ubiquitous in the analogous process of dissociative recombination, its importance in low-energy dissociative electron attachment to a polyatomic target has not previously been quantified. Our calculations indicate that three-body breakup is a major component of the observed ${\mathrm{O}}^{\ensuremath{-}}$ cross section. Our studies suggest that the local complex potential model provides a generally accurate picture of the experimentally observed features in this polyatomic system.

Ion beam cancer therapy: Fundamental aspects of the problem

We discuss different physical processes which may be responsible for biological damage induced by an ion beam propagating through living tissue. The creation of free radicals and an electron plasma, dissociative attachment of low-energy electrons, and local heating mechanisms are considered. Numerical estimates are performed for the case of carbon ion beams. We conclude that all three mechanisms are capable of inflicting single and double strand breaks in DNA molecules and thus can be responsible for the observed enhanced biological effectiveness of ion beams in cancer therapy.