Low-energy Electron Capture Research Articles

Low-Energy Shape Resonances of a Nucleobase in Water.

When high-energy radiation passes through aqueous material, low-energy electrons are produced which cause DNA damage. Electronic states of anionic nucleobases have been suggested as an entrance channel to capture the electron. However, identifying these electronic resonances have been restricted to gas-phase electron-nucleobase studies and offer limited insight into the resonances available within the aqueous environment of DNA. Here, resonance and detachment energies of the micro-hydrated uracil pyrimidine nucleobase anion are determined by two-dimensional photoelectron spectroscopy and are shown to extrapolate linearly with cluster size. This extrapolation allows the corresponding resonance and detachment energies to be determined for uracil in aqueous solution as well as the reorganization energy associated with electron capture. Two shape resonances are clearly identified that can capture low-energy electrons and subsequently form the radical anion by solvent stabilization and internal conversion to the ground electronic state. The resonances and their dynamics probed here are the nucleobase-centered doorway states for low-energy electron capture and damage in DNA.

Effect of Microhydration on the Temporary Anion States of Pyrene.

The influence of incremental hydration (≤4) on the electronic resonances of the pyrene anion is studied using two-dimensional photoelectron spectroscopy. The photoexcitation energies of the resonances do not change; therefore, from the anion’s perspective, the resonances remain the same, but from the neutral’s perspective of the electron–molecule reaction, the resonances decrease in energy by the binding energy of the water molecules. The autodetachment of the resonances shows that hydration has very little effect, showing that even the dynamics of most of the resonances are not impacted by hydration. Two specific resonances do show changes that are explained by the closing of specific autodetachment channels. The lowest-energy resonance leads to efficient electron capture as observed through thermionic emission and evaporation of water molecules (dissociative electron attachment). The implications of low-energy electron capture in dense molecular interstellar clouds are discussed.

Ion fragmentations via photoelectron activated radical relays and competed hole oxidization on semiconductor nanoparticles for mass spectrometry

Structural identification is challenging in mass spectrometric imaging because of inadequate sample quantities and limited sampling time in each pixel for tandem mass spectrometry (MS/MS) experiments, which are usually used for the generation of fragment ions. We report herein the observation of a cascade of highly specific chemical bond cleavages via a low-energy photoelectron activated radical relays and a competed hole oxidization on surfaces of (Bi2O3)0.07(CoO)0.03(ZnO)0.9 semiconductor nanoparticles irradiated with the 3rd harmonic (355 nm) of the Nd3+: YAG laser. Distinguished from high energy electron impact (EI), this approach generates gaseous radical anions through the exothermic capture of low-energy tunneling electrons that are not able to cause extensive vibrational excitations. It was found not only original radical center but also secondary or even tertiary radical centers cause specific bond cleavages exclusively on α positions. The original radical center directly activates the cleavages of α-positioned chemical bonds that cause the formation of secondary radical centers. Ion fragmentations proceed along the newly formed radical centers that further activate the cleavages of their α-positioned chemical bonds. Using 8 compounds, we have demonstrated various radical reactions involved in desulfonation, cyclization, and ring contraction reactions as well as competed hole oxidization-generated hydroxyl radical substitution reactions. The interpretable fragment ions provide unambiguous experimental evidences for structural elucidation of drug residues and metabolites in mass spectrometric imaging of tissue slices without tandem mass spectrometry (MS/MS).

Negative ion adsorption by the ion source surface as a factor influencing ion lifetime measurements

It is well known that negative ions formed in the gas phase through low-energy electron capture by molecules show a scatter in the measured lifetimes of their autodetachment states. In considering this question, it was found that, when using a static sector magnetic mass spectrometer, some of the ions formed on the ionization chamber walls are adsorbed and stabilized there, then joining the registered ion flux and thereby distorting their measured lifetime. Because the number of the adsorbed ions depends on the experimental conditions, their contribution to the total flux is to some extent uncontrollable—hence, the scatter.

Dissociative electron attachment to 3-bromopyruvic acid

SynopsisFragmentation of gas phase 3-bromopyruvic acid (BrCH2COCO2H) caused by capture of low energy electrons (0-12 eV) was studied. Ion yields of negative ions formed via dissociative electron attachment were recorded.

Role of Resonance Electron Attachment in Phytoremediation of Halogenated Herbicides.

This study is aimed to point out the important role played by resonance electron attachment in reductive dehalogenation, in particular in phytoremediation of organic pollutants under conditions of excess negative charge. To model enzymatic reactions occurring in reductive conditions, low-energy electron capture by the halogenated herbicides atrazine and bromoxynil was studied in vacuo using electron transmission spectroscopy. A variety of decay channels of the temporary molecular negative ions was discovered by means of dissociative electron attachment spectroscopy. The experimental results were interpreted with the support of quantum-chemical calculations. Dehalogenation of atrazine and bromoxynil was found to be the dominant decay of the molecular negative ions formed at thermal energies of the incident electrons. It is concluded that formation of negative ions by electron donation in enzymatic active centers followed by their dissociation along the σ bond can be considered as the main mechanism of reductive dehalogenation.

Formation of negative ions via resonant low-energy electron capture by cysteine and cystine methyl esters

The processes of resonance low-energy free electron attachment to methyl esters of some sulfur-containing amino acids were studied. The long-lived molecular negative ions of cystine dimethyl ester formed in the valence state via the Feshbach nuclear excited resonance mechanism were detected by mass spectrometry. The reactions of disulfide bond dissociation were identified in an electron energy range of 0—1 eV. They can be considered as model reactions regarding processes of peptide decomposition due to the resonance interaction with low-energy electrons. Predissociation of short-lived molecular ions of cysteine methyl ester formed by capture of electrons with energies of ~1.6 eV is accompanied by the intra-ionic transfer of negative charge from the carbonyl group to the sulfur atom leading to the elimination from the latter of hydrogen atom.

Mechanistic Study on Electronic Excitation Dissociation of the Cellobiose-Na(+) Complex.

The recent development of electron activated dissociation (ExD) techniques has opened the door for high-throughput, detailed glycan structural elucidation. Among them, ExD methods employing higher-energy electrons offer several advantages over low-energy electron capture dissociation (ECD), owing to their applicability towards chromophore-labeled glycans and singly charged ions, and ability to provide more extensive structural information. However, a lack of understanding of these processes has hindered rational optimization of the experimental conditions for more efficient fragmentation as well as the development of informatics tools for interpretation of the complex glycan ExD spectra. Here, cellobiose-Na(+) was used as the model system to investigate the fragmentation behavior of metal-adducted glycans under irradiation of electrons with energy exceeding their ionization potential, and served as the basis on which a novel electronic excitation dissociation (EED) mechanism was proposed. It was found that ionization of the glycan produces a mixture of radical cations and ring-opened distonic ions. These distonic ions then capture a low-energy electron to produce diradicals with trivial singlet-triplet splitting, and subsequently undergo radical-induced dissociation to produce a variety of fragment ions, the abundances of which are influenced by the stability of the distonic ions from which they originate. Graphical Abstract ᅟ.

Examination of the calorimetric spectrum to determine the neutrino mass in low-energy electron capture decay

Background: The standard kinematic method for determining neutrino mass from the $\ensuremath{\beta}$ decay of tritium or other isotope is to measure the shape of the electron spectrum near the endpoint. A similar distortion of the ``visible energy'' remaining after electron capture is caused by neutrino mass. There has been a resurgence of interest in using this method with $^{163}\mathrm{Ho}$, driven by technological advances in microcalorimetry. Recent theoretical analyses offer reassurance that there are no significant theoretical uncertainties.Purpose: The theoretical analyses consider only single vacancy states in the daughter $^{163}\mathrm{Dy}$ atom. It is necessary to consider configurations with more than one vacancy that can be populated owing to the change in nuclear charge.Method: The shakeup and shake-off theory of Carlson and Nestor is used as a basis for estimating the population of double-vacancy states.Results: A spectrum of satellites associated with each primary vacancy created by electron capture is presented.Conclusions: The theory of the calorimetric spectrum is more complicated than has been described heretofore. There are numerous shakeup and shake-off satellites present across the spectrum, and some may be very near the endpoint. The spectrum shape is presently not understood well enough to permit a sensitive determination of the neutrino mass in this way.

The Capture of Low-Energy Electrons by PNA versus DNA

This study provides insight into the mechanism of capturing low energy electrons by peptide nucleic acid (PNA) and the role of the oligonucleotide backbone in the capture of low energy electrons. We studied by photoemission self-assembled monolayers of two types of oligonucleo- tides, DNA and PNA. PNA is a synthetic analogue of DNA that has a pseudopeptide backbone and which may have important medical and biotechological applications. We found that in both PNA and DNA, the guanine nucleobases capture the electrons more efficiently than thymines. In PNA, once the electrons are captured, their state is at least partially localized on the nucleobases, and the PNA molecule undergoes structural changes that stabilize the electron. This situation is in contrast to DNA, in which the captured electrons are transferred very efficiently to the backbone, and the final state of captured electron is base independent.

Spontaneous electric fields in solid films: spontelectrics☆

When dipolar gases are condensed at sufficiently low temperature onto a solid surface, they form films that may spontaneously exhibit electric fields in excess of 108 V/m. This effect, called the ‘spontelectric effect’, was recently revealed using an instrument designed to measure scattering and capture of low energy electrons by molecular films. In this review it is described how this discovery was made and the properties of materials that display the spontelectric effect, so-called ‘spontelectrics’, are set out. A discussion is included of properties that differentiate spontelectrics from ferroelectrics and other species in which spontaneous polarisation may be found. Spontelectric films may be composed of a number of quite mundane dipolar molecules that involve such diverse dipolar species as propane, nitrous oxide or methyl formate. Experimental results are presented for spontelectrics illustrating that the spontelectric field generally decreases monotonically with increasing deposition temperature, with the exception of methyl formate that shows an increase beyond a critical range of deposition temperature. Films of spontelectric material show a Curie temperature above which the spontelectric effect disappears. Heterolayers may also be laid down creating potential wells on the nanoscale. A model is put forward based upon competition between dipole alignment and thermal disorder, which is successful in reproducing the variation of the degree of dipole alignment and the spontelectric field with deposition temperature, including the behaviour of methyl formate. This model and associated data lead to the conclusion that the spontelectric effect is new in solid-state physics and that spontelectrics represent a new class of materials.

Measurement of laser activated electron tunneling from semiconductor zinc oxide to adsorbed organic molecules by a matrix assisted laser desorption ionization mass spectrometer

Measurement of light induced heterogeneous electron transfer is important for understanding of fundamental processes involved in chemistry, physics and biology, which is still challenging by current techniques. Laser activated electron tunneling (LAET) from semiconductor metal oxides was observed and characterized by a MALDI (matrix assisted laser desorption ionization) mass spectrometer in this work. Nanoparticles of ZnO were placed on a MALDI sample plate. Free fatty acids and derivatives were used as models of organic compounds and directly deposited on the surface of ZnO nanoparticles. Irradiation of UV laser (λ=355nm) with energy more than the band gap of ZnO produces ions that can be detected in negative mode. When TiO2 nanoparticles with similar band gap but much lower electron mobility were used, these ions were not observed unless the voltage on the sample plate was increased. The experimental results indicate that laser induced electron tunneling is dependent on the electron mobility and the strength of the electric field. Capture of low energy electrons by charge-deficient atoms of adsorbed organic molecules causes unpaired electron-directed cleavages of chemical bonds in a nonergodic pathway. In positive detection mode, electron tunneling cannot be observed due to the reverse moving direction of electrons. It should be able to expect that laser desorption ionization mass spectrometry is a new technique capable of probing the dynamics of electron tunneling. LAET offers advantages as a new ionization dissociation method for mass spectrometry.

Dipole-Guided Electron Capture Causes Abnormal Dissociations of Phosphorylated Pentapeptides

Electron transfer and capture mass spectra of a series of doubly charged ions that were phosphorylated pentapeptides of a tryptic type (pS,A,A,A,R) showed conspicuous differences in dissociations of charge-reduced ions. Electron transfer from both gaseous cesium atoms at 100 keV kinetic energies and fluoranthene anion radicals in an ion trap resulted in the loss of a hydrogen atom, ammonia, and backbone cleavages forming complete series of sequence z ions. Elimination of phosphoric acid was negligible. In contrast, capture of low-energy electrons by doubly charged ions in a Penning ion trap induced loss of a hydrogen atom followed by elimination of phosphoric acid as the dominant dissociation channel. Backbone dissociations of charge-reduced ions also occurred but were accompanied by extensive fragmentation of the primary products. z-Ions that were terminated with a deaminated phosphoserine radical competitively eliminated phosphoric acid and H(2)PO(4) radicals. A mechanism is proposed for this novel dissociation on the basis of a computational analysis of reaction pathways and transition states. Electronic structure theory calculations in combination with extensive molecular dynamics mapping of the potential energy surface provided structures for the precursor phosphopeptide dications. Electron attachment produces a multitude of low lying electronic states in charge-reduced ions that determine their reactivity in backbone dissociations and H- atom loss. The predominant loss of H atoms in ECD is explained by a distortion of the Rydberg orbital space by the strong dipolar field of the peptide dication framework. The dipolar field steers the incoming electron to preferentially attach to the positively charged arginine side chain to form guanidinium radicals and trigger their dissociations.

Complex fragmentation pathways of rhodanine and rhodanine-3-acetic acid upon resonant capture of low-energy electrons

A detailed gas-phase study of dissociative electron attachment (DEA) to rhodanine ( Rd) and its 3-acetic acid derivative ( Rdaa) in the 0–14 eV energy range has been carried out with a magnetic mass spectrometer under conditions of medium energy resolution (0.4 eV) of the incident electron beam, and high sensitivity. The DEA spectra reveal the occurrence of numerous and complex dissociative decay channels of the molecular anions formed by resonances, involving multiple bond cleavage and structural rearrangements. Along with a variety of anion fragments normally formed in the collision cell at incident electron energies <1 eV, dissociation of a series of metastable anion species (occurring in the time scale of microseconds) is also detected. The observation of these slow processes is consistent with the complexity of many dissociative channels, and allows to propose schemes for the fragmentation pathways. The DEA spectra of both Rd and Rdaa also display small yields of molecular anions at zero energy. Their lifetimes with respect to electron detachment are experimentally evaluated to be about 30 μs and 200 μs, respectively. These (vibrationally excited) ground anion states formed by capture of thermal electrons mainly into the ring π* (C S) LUMO survive long enough to redistribute their excess energy before undergoing different dissociation channels.

Validation of a new TDCR system at NPL

A new triple to double coincidence ratio (TDCR) system has been established at NPL. The system incorporates a spherical optical chamber, a manual sample changing facility and an integral light-tight housing. A 6 in diameter NaI(Tl) detector has been incorporated to allow 4pibeta-gamma coincidence measurements to be performed in parallel. Details of the detectors, the electronics and the overall TDCR system are given. Validation measurements using suitable low-energy beta and electron capture nuclides, i.e. (3)H and (55)Fe have been performed. The highest efficiency achieved with a (3)H solution in Ultima Gold AB in a glass vial was 53% and in a high-efficiency LS cocktail 65%. This indicates that the optical chamber is performing well. After varying the efficiency by de-focusing the PM tubes, the activity of the sources was determined. The activity concentration determined with TDCR agreed with certified values within the range of uncertainties. Further results from validation measurements and the corresponding uncertainty budgets are presented.

Low-energy electron capture in collisions ofC3+with He

Charge transfer processes due to collisions of ground-state ${\text{C}}^{3+}(1{s}^{2}2s\text{ }^{2}S)$ ions with He atoms are studied using the quantum-mechanical molecular-orbital close-coupling method for energies in the range ${10}^{\ensuremath{-}4}--2\ifmmode\times\else\texttimes\fi{}{10}^{3}\text{ }\text{eV}/\text{u}$. The ab initio adiabatic potentials and radial couplings utilized in the calculations are obtained from the multireference single- and double-excitation configuration interaction approach. Total and state-selective single-electron capture cross sections and rate coefficients are calculated and compared with the available experimental and theoretical data. A good agreement is found between the measured cross sections and the present calculations. However, the previous calculations of total rate coefficients using the Landau-Zener model are one to two orders of magnitude smaller than the present results.

Characterization of the Superconducting Transition of Thin Ir Films for TES

We are currently producing iridium based TESs for a wide variety of applications such as single photon detection of the visible and infrared light, X-ray spectroscopy and low energy nuclear beta and electron capture spectroscopy for neutrino mass search experiment. We present a study of the TES performance related to the superconductivity properties of the Ir film as function of the production processes, that depend on substrate type: Si or SiN, and of the operating electrical parameters. Moreover we developed a finite element model of thin superconducting film, by which we obtain qualitative agreement between experimental and simulated data.

Comparison of collision‐ versus electron‐induced dissociation of sodium chloride cluster cations

The collision-induced dissociation (CID) and electron-induced dissociation (EID) spectra of the [(NaCl)(m)(Na)(n)](n+) clusters of sodium chloride have been examined in a hybrid linear ion trap Fourier transform ion cyclotron resonance mass spectrometer. For singly charged cluster ions (n = 1), mass spectra for CID and EID of the precursor exhibit clear differences, which become more pronounced for the larger cluster ions. Whereas CID yields fewer product ions, EID produces all possible [(NaCl)(x)Na](+) product ions. In the case of doubly charged cluster ions, EID again leads to a larger variety of product ions. In addition, doubly charged product ions have been observed due to loss of neutral NaCl unit(s). For example, EID of [(NaCl)(11)(Na)(2)](2+) leads to formation of [(NaCl)(10)(Na)(2)](2+), which appears to be the smallest doubly charged cluster of sodium chloride observed experimentally to date. The most abundant product ions in EID spectra are predominantly magic number cluster ions. Finally, [(NaCl)(m)(Na)(2)](+*) radical cations, formed via capture of low-energy electrons, fragment via the loss of [(NaCl)(n)(Na)](*) radical neutrals.

Site selective cleavage of purine derivatives by capture of low energy electrons

In the present study, we investigate site selectivity of (multiple) hydrogen loss induced by free electron attachment to purine derivatives. Like for the pyrimidines here efficient hydrogen release is also observed upon low-energy electron capture. By utilizing partially deuterated or methylated derivatives of adenine, we show that the formation of the dehydrogenated parent anion (M–H)− below 1.4 eV can be ascribed predominately to hydrogen loss from the N9 site. However, the (M–H)− ion yield shows a strong influence on the functional groups attached to the opposite site of the N9 position. By means of quantum chemical calculations, we ascribe this result to a change in the electrostatic potential distribution for the different compounds. We also present site selectivity for the formation of (M–2H)− and (M–3H)− anions formed upon electron attachment to adenine.

Electron attachment toSF6and lifetimes ofSF6−negative ions

We study the process of low-energy electron capture by the SF6 molecule. Our approach is based on the model of Gauyacq and Herzenberg [J. Phys. B 17, 1155 (1984)] in which the electron motion is coupled to the fully symmetric vibrational mode through a weakly bound or virtual s state. By tuning the two free parameters of the model, we achieve an accurate description of the measured electron attachment cross section and good agreement with vibrational excitation cross sections of the fully symmetric mode. An extension of the model provides a limit on the characteristic time of intramolecular vibrational relaxation in highly-excited SF6-. By evaluating the total vibrational spectrum density of SF6-, we estimate the widths of the vibrational Feshbach resonances of the long-lived negative ion. We also analyse the possible distribution of the widths and its effect on the lifetime measurements, and investigate nonexponential decay features in metastable SF6-.