Negative Ion States Research Articles

Resonance electron capture by perylene molecules. Relation with negative differential conductance

Five resonant states of long-lived negative molecular ions were defined during the gas-phase resonant electron capture by perylene. Three states are the ground state (0.05 eV) and two shape resonances (0.4 eV and 0.7 eV). Core-excited Feshbach resonance (1.4 eV) transits into a quartet state, which delays the autodetachment of additional electron and causes the negative differential conductance in tunneling transition due to the spin prohibition. Inter-shell resonance (2.5 eV) is mixed with the ground state with the same symmetry and is likely to be stabilized through the light emission with simultaneous transition to a quartet state.

Low-lying Negative Ion States Probed in Potassium - Ethanol Collisions.

Dissociative electron transfer in collisions between neutral potassium atoms and neutral ethanol molecules yields mainly OH-, followed by C2H5O-, O-, CH3 - and CH2 -. The dynamics of negative ions have been investigated by recording time-of-flight mass spectra in a wide range of collision energies from 17.5 to 350 eV in the lab frame, where the branching ratios show a relevant energy dependence for low/intermediate collision energies. The dominant fragmentation channel in the whole energy range investigated has been assigned to the hydroxyl anion in contrast to oxygen anion from dissociative electron attachment (DEA) experiments. This result shows the relevant role of the electron donor in the vicinity of the temporary negative ion formed allowing access to reactions which are not thermodynamically attained in DEA experiments. The electronic state spectroscopy of such negative ions, was obtained from potassium cation energy loss spectra in the forward scattering direction at 205 eV impact energy, showing a prevalent Feshbach resonance at 9.36±0.10 eV with character, while a less pronounced contribution assigned to a shape resonance has been obtained at 3.16±0.10 eV. Quantum chemical calculations for the lowest-lying unoccupied molecular orbitals in the presence of a potassium atom have been performed to support the experimental findings.

<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.

Fundamental data for modeling electron-induced processes in plasma remediation of perfluoroalkyl substances.

Plasma treatment of per- and polyfluoroalkyl substances (PFAS) contaminated water is a potentially energy efficient remediation method. In this treatment, an atmospheric pressure plasma interacts with surface-resident PFAS molecules. Developing a reaction mechanism and modeling of plasma-PFAS interactions requires fundamental data for electron-molecule reactions. In this paper, we present results of electron scattering calculations, potential energy landscapes and their implications for plasma modelling of a dielectric barrier discharge in PFAS contaminated gases, a first step towards modelling of plasma-water-PFAS intereactions. It is found that the plasma degradation of PFAS is dominated by dissociative electron attachment with the importance of other contributing processes varying depending on the molecule. All molecules posses a large number of shape resonances - transient negative ion states - from near-threshold up to ionization threshold. These states lie in the region of the most probable electron energies in the plasma (4-5 eV) and consequently are expected to further enhance the fragmentation dynamics in both dissociative attachment and dissociative excitation.

Elementary processes triggered in curcumin molecule by gas-phase resonance electron attachment and by photoexcitation in solution.

Electron-driven processes in isolated curcumin (CUR) molecules are studied by means of dissociative electron attachment (DEA) spectroscopy under gas-phase conditions. Elementary photostimulated reactions initiated in CUR molecules under UV irradiation are studied using the chemically induced dynamic nuclear polarization method in an acetonitrile solvent. Density functional theory is applied to elucidate the energetics of fragmentation of CUR by low-energy (0-15eV) resonance electron attachment and to characterize various CUR radical forms. The adiabatic electron affinity of CUR molecule is experimentally estimated to be about 1eV. An extra electron attachment to the π1* LUMO and π2* molecular orbitals is responsible for the most intense DEA signals observed at thermal electron energy. The most abundant long-lived (hundreds of micro- to milliseconds) molecular negative ions CUR- are detected not only at the thermal energy of incident electrons but also at 0.6eV, which is due to the formation of the π3* and π4* temporary negative ion states predicted to lie around 1eV. Proton-assisted electron transfer between CUR molecules is registered under UV irradiation. The formation of both radical-anions and radical-cations of CUR is found to be more favorable in its enol form. The present findings shed some light on the elementary processes triggered in CUR by electrons and photons and, therefore, can be useful to understand the molecular mechanisms responsible for a variety of biological effects produced by CUR.

Possible evidence for the production of Ar2∗-\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$_2^{*-}$$\\end{document} metastable negative molecular ions in gaseous argon of two-phase detectors for dark matter searches

Our recent studies of electroluminescence (EL) properties in two-phase argon detectors for dark matter searches have revealed the presence of unusual delayed pulses in the EL signal in the form of two slow components with time constants of about 5 and 50 μs\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\upmu \ ext {s}$$\\end{document}. These components were shown to be present in the charge signal itself, which clearly indicates that drifting electrons are temporarily trapped on two states of metastable negative argon ions which have never been observed before. In this work, using the pressure dependence of the ratio of slow component contributions measured in experiment, it is deduced that these states are those of two types of metastable negative molecular ions, Ar2∗-(b4Σu-)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\ extrm{Ar}}}_2^{*-}(b \\ ^4\\varSigma _u^-)$$\\end{document} and Ar2∗-(a4Σg+)\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$${{\ extrm{Ar}}}_2^{*-}(a \\ ^4\\varSigma _g^+)$$\\end{document} for the higher and lower energy level respectively.

Resonance States of Negative Hydrogen-like Ions in Quantum Plasmas

We studied the 1Se and 1,3Po resonance states of negative hydrogen-like ions immersed in quantum plasmas. The exponential cosine screened Coulomb potential was considered to model the quantum plasma environment. The correlated exponential wave functions in which the exponents were generated by a pseudo-random technique were applied to represent the correlation effects between the charged particles. The stabilization method was used to calculate the resonance parameters (position and width). The resonance parameters (position and width) for Ps−, Mμ−, π−, 1H−, D−, T− and ∞H− embedded in quantum plasmas are reported for various screening parameters. The 1Se resonance parameters for Mμ−, π−, 1H−, D−, T− ions and 1,3 Po states for Ps−, Mμ−, π−, 1H−, D−, T− and ∞H− of the proposed systems are reported for the first time in the literature.

The enhancement and mechanism of the perception of saltiness by umami peptide from Ruditapes philippinarum and ham

To explore the saltiness enhancement effect and mechanism of umami peptides, umami peptides from Ruditapes philippinarum and ham were mixed with NaCl and determined using electronic tongue, sensory evaluation, and the aroma chicken model (ACM), then transmembrane channel-like protein 4(TMC4) receptor was constructed for molecular docking. The results showed that KEMQKN, NGKET, RGEPNND, AHSVRFY, LSERYP, NRTF, TYLPVH, EV, AGAGPTP, and GPAGPAGPR had saltiness enhancement effect, which could be increased to 0.4–0.6 % NaCl salty taste in 0.3 % NaCl. Under neutral conditions (pH6.5), most umami peptides were in negative ion state which may be the main reason that umami peptides could bind to the TMC4 receptor and enhance saltiness. The lowest docking energy was −113.325 kcal/mol among 10 peptides and the active sites Lys568, Trp145, Tyr565, Arg151, and Gln155 in TMC4 may play a key role. Thus, this study provides basic theory and data for salt-reduction strategies.

Anionic states of C6Cl6 probed in electron transfer experiments.

This is the first comprehensive investigation on the anionic species formed during collisions of fast neutral potassium (K) atoms with neutral hexachlorobenzene (C6Cl6) molecules in the laboratory frame range from 10 up to 100 eV. In such ion-pair formation experiments we also report a novel K+ energy loss spectrum obtained in the forward scattering giving evidence of the most accessible electronic states. The vertical electron affinity of (-3.76 ± 0.20) eV has been obtained and assigned to a purely repulsive transition from the C6Cl6 ground state to a state of the temporary negative ion yielding Cl- formation. These experimental findings are also supported by state-of-the art theoretical calculations on the electronic structure of C6Cl6 in the presence of a potassium atom and are used for analysing the lowest unoccupied molecular orbitals participating in the collision process. From the time-of-flight mass spectra recorded in the wide collision energy range, more than 80% of the total anion yield is due to the undissociated parent anion C6Cl6-, C6Cl5- and Cl- formation. Other fragment anions such as C6Cl4-, C3Cl2-, C2Cl- and Cl2- that undergo complex internal reactions with the temporary negative ion formed after electron transfer account for less than 20% of the total yield. The joint experimental and theoretical methodologies employed in these electron transfer studies provide the most comprehensive and unique assignments of the hexachlorobenzene anionic species and the role of C6Cl6 electronic states in collision induced dissociation to date.

Formation of negative and positive ions in the radiosensitizer nimorazole upon low-energy electron collisions.

A comprehensive investigation of low-energy electron attachment and electron ionization of the nimorazole radiosensitizer used in cancer radiation therapy is reported by means of a gas-phase crossed beam experiment in an electron energy range from 0 eV to 70 eV. Regarding negative ion formation, we discuss the formation of fifteen fragment anions in the electron energy range of 0 eV-10 eV, where the most intense signal is assigned to the nitrogen dioxide anion NO2 -. The other fragment anions have been assigned to form predominantly from a common temporary negative ion state close to 3 eV of the nitroimidazole moiety, while the morpholine moiety seems to act only as a spectator in the dissociative electron attachment event to nimorazole. Quantum chemical calculations have been performed to help interpreting the experimental data with thermochemical thresholds, electron affinities, and geometries of some of the neutral molecules. As far as positive ion formation is concerned, the mass spectrum at the electron energy of 70 eV shows a weakly abundant parent ion and C5H10NO+ as the most abundant fragment cation. We report appearance energy (AE) measurements for six cations. For the intact nimorazole molecular cation, the AE of 8.16 ± 0.05 eV was obtained, which is near the presently calculated adiabatic ionization energy.

Formation of Smaller Anions from CnN− (n = 1–3, 5–7) in the Circumstellar Medium

Abstract We probe a new pathway for the formation of smaller anions from the temporary negative ion states (anion resonances) of C n N− (n = 1–3, 5–7) in the circumstellar envelope of IRC+10216. C n N− (n = 1–3, 5–7) anions were collisionally excited to their resonance states and were observed to decay into a variety of smaller anions. The measured kinetic-energy-release distributions for the anionic fragments arising from each of the parent anions indicate a concerted manner of occurrence of these fragments, implying rich dissociation dynamics. and C2N− were found to be dominant fragments of these anions, suggesting their presence in the external layers of IRC+10216 where UV photons penetrate. C n N− (n = 1–3) were also observed to undergo dissociative and nondissociative double-electron detachments, with the former being dominant. The significance of this new pathway in determining the stability and abundance of anions in IRC+10216 is discussed.

Photodetachment spectroscopy of quasibound states of the negative ion of lanthanum

The negative ion of lanthanum, La$^-$, has one of the richest bound state spectra observed for an atomic negative ion and has been proposed as a promising candidate for laser-cooling applications. In the present experiments, La$^-$ was investigated using tunable infrared photodetachment spectroscopy. The relative signal for neutral atom production was measured with a crossed ion-beam--laser-beam apparatus over the photon energy range 590 - 920 meV (2100 - 1350 nm) to probe the continuum region above the La neutral atom ground state. Eleven prominent peaks were observed in the La$^-$ photodetachment cross section due to resonant excitation of quasibound transient negative ion states in the continuum which subsequently autodetach. In addition, thresholds were observed for photodetachment from several bound states of La$^-$ to both ground and excited states of La. The present results provide information on the excited state structure and dynamics of La$^-$ that depend crucially on multielectron correlation effects.

Combined Experimental and Theoretical Studies on Electron Transfer in Potassium Collisions with CCl4.

Negative ion formation in electron transfer experiments from fast neutral potassium (K) atom collisions with neutral tetrachloromethane (CCl4) molecules has been investigated in the laboratory frame range of 8-1000 eV. Comprehensive calculations on the electronic structure were performed for CCl4 in the presence of a potassium atom and used to help analyze the lowest unoccupied molecular orbitals participating in the collision process. Additionally, K+ energy loss produced in the forward direction has served to further our knowledge on the electronic state spectroscopy of CCl4. A vertical electron affinity of -0.79 ± 0.20 eV has been obtained and assigned to a purely repulsive transition from CCl4 ground state to the 2T2 state of the temporary negative ion yielding Cl- formation. Other features in the energy loss spectrum were observed for the first time and related to Cl2-, CCl2-, and CCl3- formation. Special attention is also given to the unresolved feature corresponding to a positive electron affinity of 0.24 ± 0.2 eV, assigned to a vibrationally hot transition from CCl4 ground state into the triply degenerate 2T2 excited state of the negative ion. The combined time-of-flight mass spectrometry together with K+ energy loss data represents the most comprehensive assignment of the tetrachloromethane anion yields and the role of CCl4 electronic states in collision induced dissociation to date.

Shape resonance of sulphur dioxide anion excited states using the CAP-CIP-FSMRCCSD method

We have studied the shape resonance of excited states of sulphur dioxide (SO2) anion by using the correlated independent particle Fock space multi-reference coupled cluster (CAP-CIP-FSMRCCSD) method augmented by complex absorption potential. These resonant states have been trapped experimentally in recent years by electron collision. In particular, we have investigated e–-SO2 scattering and computed the negative-ion resonance states of the anion responsible for the two resonances around 4.45 and 6.56 eV and compared the results with the existing experimental observations. From the computational results using the CAP-CIP-FSMRCCSD method, it has been observed that both the resonances near 4.45 and 6.56 eV result from A1 symmetries.

Electron attachment spectroscopy as a tool to study internal rotations in isolated negative ions

The paper shows that internal rotational motions can be excited in isolated triclosan molecules via low-energy (0-15 eV) resonance electron attachment followed by formation of temporary negative ions. Provided that some energetic and kinetic conditions are satisfied these rotations lead to dissociative decays of the negative ions. The authors show that the detection of so-formed fragment species by means of dissociative electron attachment spectroscopy can provide some information about internal rotations in negative ion states.

Probing functional group dependence in dissociative electron attachment using negative ion momentum imaging

SynopsisDissociative electron attachment (DEA) is the most efficient way to explore the structure and dynam-ics of excited states of molecular negative ions. More importantly, DEA has been shown to be a tool for chemical control. One crucial aspect of the chemical control using DEA is the functional group dependence present in this process. Here we present cases on the effect of delocalized electrons on DEA patterns observed in simple aromatic compounds.

Electron affinity of gallium and fine structure of Ga− : Experiment and theory

Binding energies of fine structure levels of the negative ion of gallium have been determined both experimentally and theoretically, resolving long-standing discrepancies for the electron affinity of gallium. The relative photodetachment cross section from ${\mathrm{Ga}}^{\ensuremath{-}}$ ($4{p}^{2}\phantom{\rule{0.16em}{0ex}}^{3}P_{0,1,2}$) was measured using tunable laser spectroscopy over the photon energy range 270--400 meV (4600--3100 nm). Observed photodetachment thresholds were used to measure the electron affinity of Ga to be 301.20(11) meV and the fine structure splittings of ${\mathrm{Ga}}^{\ensuremath{-}}$ to be 23.31(19) meV for $J=0\ensuremath{-}1$ and 62.4(5) meV for $J=0\ensuremath{-}2$. The binding energies of the negative ion states were independently calculated using the multireference extrapolated intermediate Hamiltonian relativistic Fock space coupled cluster method in large, converged four-component Gaussian-spinor basis sets. The Dirac-Fock-Breit Hamiltonian was used, and leading quantum electrodynamic effects were added. All calculations were carried out in spherical symmetry, correlating all electrons and fully including core effects. The calculated electron affinity is 302(3) meV, and the fine structure splittings are 22(2) meV for $J=0\ensuremath{-}1$ and 60(2) meV for $J=0\ensuremath{-}2$, which are all in excellent agreement with the present measurements. These results substantially improve both the accuracy and precision of the Ga electron affinity and provide a determination of the fine structure of ${\mathrm{Ga}}^{\ensuremath{-}}$.

Study of S− and SO− ion formation from dissociative electron attachment to SO2

A detailed experimental investigation of the dissociative electron attachment (DEA) process to sulfur dioxide molecules in the gas phase has been performed. The sulfur dioxide molecule is known to produce O−, S− and SO− ions, mainly forming two prominent resonant peaks at around 4.2 and 7.5 eV incident electron energies. The S− and SO− ions are studied over the second resonance around 7.5 eV incident electron energy in detail using the well-established velocity slice imaging (VSI) spectrometer. The time-sliced images, kinetic energy and angular distribution have been reported for the two ions over the second resonance for the first time. Both the ions are seen to be formed with very low kinetic energies with their respective neutral fragments being produced in internally excited states. The angular distribution data also signifies the presence of a linear combination of A1 and B2 temporary negative ion states responsible for the resonant peak at 7.5 eV incident electron energy.

Electron scattering from tin tetrachloride (SnCl4) molecules

Absolute grand-total cross section (TCS) for electron scattering from a tin tetrachloride, SnCl4, molecule was measured at electron-impact energies ranging from 0.6 to 300 eV, in the linear electron-transmission experiment. The measured TCS energy dependence shows two very pronounced enhancements peaking near 1.2 eV and around 9.5 eV, separated with a deep minimum centered close to 3 eV. The low energy structure is attributed to the formation of two short-living negative ion states. Additional weak structures in the TCS curve are also perceptible. We also calculated the integral elastic and ionization cross sections for SnCl4 up to 4 keV within the additivity rule approximation and the binary-encounter-Bethe approach, respectively. To examine the role of the central atom of tetrachloride target molecules in collisions with electrons, we compared the experimental TCS energy functions for XCl4 molecules (X = C, Si, Ge, Sn).

Resonance electron interaction with five-membered heterocyclic compounds: Vibrational Feshbach resonances and hydrogen-atom stripping

Low-energy (0--15 eV) resonance electron attachment to a series of five-membered heterocyclic rings (isoxazole, imidazole, pyrazole, pyrrole, 1-methyl-, and 2-methylimidazole) is studied under gas-phase conditions by means of electron transmission spectroscopy and dissociative electron attachment spectroscopy (DEAS). Experimental spectral features are assigned on the basis of Hartree-Fock and density functional theory calculations. Sharp features, with a width of less than 0.1 eV, observed in the electron transmission spectra of imidazole, pyrazole, and pyrrole close to 0.45 eV, i.e., well below the energy of their lowest-lying ${\ensuremath{\pi}}^{*}$ shape resonances detected at 1.90, 1.87, and 2.33 eV, respectively, are associated with formation of negative ion states bound by long-range electron-molecule interactions. Effective range theory calculations which include both dipolar and polarization interactions support this interpretation. In addition to the general observation of cleavage of the N--H bond at incident electron energies close to 2 eV, elimination of as many as three hydrogen atoms from the molecular negative ions is detected at higher energies by DEAS with the only exception of methylated imidazoles. This complex process is associated with ring opening and formation of diatomic hydrogen as one of the neutral fragments, as indicated by the calculations to satisfy the energetic requirements. The present results are of importance for understanding the basic mechanisms of damages caused in living tissues by high-energy radiations.