Electron stimulated desorption from condensed benzene.

The electron induced dissociation of condensed benzene (C6H6) in thin films deposited on a Pt substrate is investigated by electron stimulated desorption (ESD) of anions and cations. The desorbed yields are recorded as a function of incident electron energy in the range of 10 to 950 eV for a fixed film thickness of 2 monolayers (ML) and for a fixed energy of 950 eV, as well as a function of film thickness from 0.5 to 8 monolayers (ML) for anions, and from 0.5 to 12ML for cations. Both energy and thickness dependencies are discussed in terms of the three main mechanisms yielding positively and/or negatively charged fragments: dissociative electron attachment (DEA), dipolar dissociation (DD) and dissociative ionization (DI) processes. At the probed energies, DD is the major mechanism, while DEA is predominantly induced by secondary electrons from the Pt substrate. Desorption of the parent positive ion is strongly suppressed. Similar qualitative behaviours are observed for the energy dependence of both anion and cation ESD yields, while some discrepancies exist in the thickness dependence, including a very significant systematic magnitude difference found between such ions formation. An estimation of the effective DD cross-section including the desorption probability is obtained. Feasible mechanisms behind the observed energy and thickness dependences for anion and cation yields are proposed. These results highlight the need for further investigations to better understand the underlying processes of electron induced dissociation in condensed matter.

Low energy (6-18 eV) electron scattering from condensed thymidine (dT) III: absolute electronic excitation cross sections.

Absolute cross sections (CSs) for electronic excitation by low-energy electron (LEE) scattering, from condensed thymidine (dT) in the 6-18 eV incident energy range, were measured by high-resolution electron energy loss spectroscopy (HREELS). Various electron energy loss (EEL) spectra were acquired using 1 ML of dT condensed on a multilayer film of Ar held at about 20 K under ultra-high vacuum (∼1 × 10-11 Torr). dT is one of the most complex DNA constituents to be studied by HREELS and these spectra provide the first LEE energy-loss data for electronic excitation of a nucleoside. CSs for transitions to the states 13A', 13A'', 23A', 21A', 33A', 23A'', 43A', 33A'', 53A' and 51A' of dT were extracted from the EEL spectra. These states correlate to those previously measured for the thymine moiety. Two broad resonances are observed in the energy dependence of the CSs at around 8 and 10 eV; these energies are close to those found in earlier gas- and solid-phase studies on the interaction of LEEs with dT, thymine and related molecules. A quantitative comparison between the electronic CSs of dT and those of thymine and tetrahydrofuran indicates that no variation is induced in the electronic CSs of thymine upon chemically binding to a deoxyribose group.

Low energy (1-19 eV) electron scattering from condensed thymidine (dT) I: absolute vibrational excitation cross sections.

Absolute cross sections (CSs) for vibrational excitation by electrons of energy between 1-19 eV scattering from condensed thymidine (dT) were measured by means of high-resolution electron energy loss spectroscopy (HREELS). The CSs were extracted from electron energy loss spectra of dT condensed on multilayers film of Ar held at about 20 K under ultra-high vacuum (∼1 × 10-11 Torr). dT is one of the most complex molecules to be studied in condensed phase by HREELS. The magnitudes of the vibrational CSs lie within the 10-17 cm2 range. Structures observed in the energy dependence of the vibrational CSs under 3 eV and around 4 eV were compared with previous results of gas- and solid-phase studies on dT and related molecules (e.g., thymine and tetrahydrofuran). These structures were attributed to the formation of shape resonances.

Low energy (1-19 eV) electron scattering from condensed thymidine (dT) II: comparison of vibrational excitation cross sections with those of tetrahydrofuran and the recalibrated values of thymine.

Recent measurements of absolute vibrational cross sections (CSs) for low-energy electron (LEE) scattering from condensed thymidine (dT) allows comparison with CSs of its constituents; thymine and tetrahydrofuran (THF). To facilitate this comparison, the vibrational CSs of condensed thymine were remeasured at six electron incident energies and a correction was applied to the earlier thymine CS values measured by Lévesque et al. [Nucl. Instrum. Methods Phys. Res., Sect. B, 2003, 208, 225]. The incident energy dependence of the CS of each vibrational mode of dT is compared with the corresponding modes in thymine and/or THF. It is found that the magnitude of the CSs of the thymine breathing mode and the C-C stretch mode of THF are greatly attenuated in dT. Finally, the magnitudes of the total vibrational CSs of each molecule are compared. Below 4 eV, the total vibrational CSs of dT is greater than each of its two constituents. Interestingly, at higher energy (>6 eV), the magnitude of the total vibrational CS of dT is roughly equal to that of THF and is greater than thymine by only 15% at 10 eV, showing that the CSs of dT cannot be approximated by the addition of the CSs of its constituents over the entire energy range. These comparisons are discussed in terms of the basic principles involved in the formation and decay of shape resonances, which are known to be responsible for major enhancements of LEE-induced vibrational excitation at low electron energies.

Absolute cross section for DNA damage induced by low-energy (10 eV) electrons: Experimental refinements and sample characterization by AFM.

This work describes multiple experimental improvements for measuring absolute cross sections of DNA damage induced by low-energy electrons in nanometer-thick films in vacuum. Measurements of such cross sections are particularly sensitive to film thickness and uniformity. Using atomic force microscopy in 70% ethanol, we present a novel and effective method to determine plasmid DNA film thickness and uniformity that combines height histograms and force-distance curves. We also investigate film deposition with DNA intercalated with 1,3-diaminopropane (Dap) on tantalum-coated substrates as a convenient and cost-effective alternative to the previously-used graphite substrate. The tantalum substrate permits deposition of films very similar to those formed on graphite. Using these refinements and further optimizations of the experimental procedure, we measure an absolute cross section of (7.4 ± 2.3) × 10-18 cm2 per nucleotide for conformational damage to a 3197 base-pair plasmid, induced by 10 eV electrons, which we believe should be considered as a reference value.

Absolute vibrational excitation cross sections for 1-18 eV electron scattering from condensed dimethyl phosphate (DMP).

Absolute cross sections (CSs) for vibrational excitation by 1-18 eV electrons incident on condensed dimethyl phosphate (DMP) were measured with a high-resolution electron energy loss (EEL) spectrometer. Absolute CSs were extracted from EEL spectra of DMP condensed on multilayer film of Ar held at about 20 K under ultra-high vacuum (∼1 × 10-11 Torr). Structures observed in the energy dependence of the CSs around 2, 4, 7, and 12 eV were compared with previous results of gas- and solid-phase experiments and with theoretical studies on dimethyl phosphate and related molecules. These structures were attributed to the formation of shape resonances.

Electron stimulated desorption from condensed pyrimidine and pyridazine.

Low energy electron (LEE) interactions and the formation of transient negative ions play a dominant role in radiation-induced dissociation of condensed-phase biomolecules (e.g. in radiotherapy). Here we present data on the LEE-induced dissociation and desorption of the DNA/RNA-base and radiosensitizing agent analogues pyrimidine and pyridazine. Vapors of each molecule were condensed on either a Pt or Ar substrate to form a multilayer film or a submonolayer molecular target, respectively. These were irradiated with electrons of 0-80 eV and the desorbing anionic and cationic fragments analysed via time of flight mass spectrometry. The detected cations are the same species seen in gas-phase mass spectra, albeit of differing relative intensity. Anion yield functions exhibit strong maxima, indicating that transient negative ions contribute significantly, via dissociative electron attachment (DEA), to molecular dissociation below 20 eV. For both molecules, the <5 eV shape resonances, seen experimentally and predicted by theory, do not result in fragment desorption. The main anionic fragments are H- and CN- for both molecules, additionally the fragments C-, CH- C2H- and CHN- desorb from pyrimidine and C- and C2H- from pyridazine, with some resonances lying above the ionization limit. Pyrimidine shows higher anion desorption yields than pyridazine for all species except H-. The anion signal also comprises dipolar dissociation (DD), investigated in both anionic and cationic yield functions. From analysis of anion and cation yields, fragmentation pathways are suggested. The direct ionization pathway provides information on the appearance energies for cations and their production processes in condensed phase.

Absolute cross sections for electronic excitation of condensed tetrahydrofuran (THF) by 11-16 eV electrons.

Absolute cross section (CS) data on the interaction of low energy electrons with DNA and its molecular constituents are required as input parameters in Monte-Carlo type simulations, for several radiobiological applications. Previously [V. Lemelin et al., J. Chem. Phys. 144, 074701 (2016)], we measured absolute vibrational CSs for low-energy electron scattering from condensed tetrahydrofuran, a convenient surrogate for the deoxyribose. Here we report absolute electronic CSs for energy losses of between 6 and 11.5 eV, by electrons with energies between 11 and 16 eV. The variation of these CSs with incident electron energy shows no evidence of transient anion states, consistent with theoretical and other experimental results, indicating that initial electron capture leading to DNA strand breaks occurs primarily on DNA bases or the phosphate group.

Absolute vibrational cross sections for 1-19 eV electron scattering from condensed tetrahydrofuran (THF).

Absolute cross sections (CSs) for vibrational excitation by 1-19 eV electrons impacting on condensed tetrahydrofuran (THF) were measured with a high-resolution electron energy loss spectrometer. Experiments were performed under ultra-high vacuum (3 × 10(-11) Torr) at a temperature of about 20 K. The magnitudes of the vibrational CSs lie within the 10(-17) cm(2) range. Features observed near 4.5, 9.5, and 12.5 eV in the incident energy dependence of the CSs were compared to the results of theoretical calculations and other experiments on gas and solid-phase THF. These three resonances are attributed to the formation of shape or core-excited shape resonances. Another maximum observed around 2.5 eV is not found in the calculations but has been observed in gas-phase studies; it is attributed to the formation of a shape resonance.

Electron Resonance Decay into a Biological Function: Decrease in Viability of E. coli Transformed by Plasmid DNA Irradiated with 0.5-18 eV Electrons.

Transient negative ions (TNIs) are ubiquitous in electron-molecule scattering at low electron impact energies (0-20 eV) and are particularly effective in damaging large biomolecules. Because ionizing radiation generates mostly 0-20 eV electrons, TNIs are expected to play important roles in cell mutagenesis and death during radiotherapeutic cancer treatment, although this hypothesis has never been directly verified. Here, we measure the efficiency of transforming E. coli bacteria by inserting into the cells, pGEM-3ZfL(-) plasmid DNA that confers resistance to the antibiotic ampicillin. Before transformation, plasmids are irradiated with electrons of specific energies between 0.5 and 18 eV. The loss of transformation efficiency plotted as a function of irradiation energy reveals TNIs at 5.5 and 9.5 eV, corresponding to similar states observed in the yields of DNA double strand breaks. We show that TNIs are detectable in the electron-energy dependence of a biological process and can decrease cell viability.

Electron stimulated desorption of anions and cations from condensed allyl glycidyl ether.

We report measurements of the electron stimulated desorption (ESD) of anions and cations from thin films of allyl glycidyl ether (AGE), formed by condensation onto multilayer Kr and Pt substrates using a high sensitivity time of flight mass analyser. Measurements were performed as a function of film thickness, incident electron energy (E(i)) and effective incident current. Below incident electron energies of 20 eV the desorption of anions is dominated by the process of dissociative electron attachment (DEA) via several transient negative ions at E(i) between 5.5 and 16.5 eV. Comparisons between measurements for AGE and ethyl oxirane show that the ESD of anions is essentially that of the glycidyl (epoxide) ring, though DEA occurring at the ether, within the linear part of the AGE molecule is also observed. Cation yields are dominated by the desorption of small fragments formed via scission of the same ether bond.

Electron induced dissociation in the condensed-phase nitromethane: II. Desorption of neutral fragments.

Low energy electron induced dissociation in multilayer films of nitromethane (CD3NO2) was investigated by high resolution electron energy loss spectroscopy (HREELS) and by the electron stimulated desorption (ESD) of neutral species. HREELS measurements show that the lowest electronic states of the condensed molecule are very similar to those seen in the gas phase. Desorbed neutrals were detected using combined non-resonant multi-photon ionization at 355 nm and time of flight mass spectrometry. The most intense signals detected were those of CD3 (+) and NO (+) and are attributed primarily to the desorption of CD3 and NO2 fragments following molecular dissociation via low-lying electronic excited states of nitromethane (the detected NO (+) being the result of the dissociative ionization of NO2). By varying the time delay between the incident electron pulse and the ionizing laser pulse, it is possible to measure the kinetic energy distributions of desorbing fragments. The kinetic energy distributions above ∼ 5 eV appear invariant with incident electron energy, indicating that the same desorption process (dissociation via low-lying electronic states) operates at all the studied incident energies. Nevertheless, measurements of neutral yields as functions of incident electron energy demonstrate that excitation of the dissociative electronic states also proceeds via previously identified transient negative ions. At energies less than ∼ 5 eV, contributions from dissociative electron attachment are also observed in the yield of CD3 and other neutral fragments.

Electron stimulated desorption of anionic fragments from films of pure and electron-irradiated thiophene.

The electron stimulated desorption (ESD) of anions is used to explore the effects of electron irradiation on a thiophene film and we report measurements for electron impact on multilayer thiophene condensed on a polycrystalline platinum substrate. Below 22 eV and at low electron dose, desorbed anions include H- (the dominant signal) as well as S-, CH2-, SH- and SCH2-. Yield functions show that anions are desorbed both by dissociative electron attachment (DEA) with resonances observed at 9.5, 11, and 16 eV, and for energies >13 eV, by dipolar dissociation (DD). An increase in the S- signal from electron irradiated (beam-damaged) thiophene films and the appearance of a new DEA resonance in the S- yield function at 6 eV are linked to rupture of the thiophene ring and the formation of sulfur-terminated products within the film. The threshold energy for ring rupture is 5 eV. The desorption of new anions such as C4H3S- (Thiophene-H)- is also observed from electron irradiated films and these likely arise from the decomposition of large radiation product molecules synthesized in the film. The yield functions of H-, S-, SH-, (Thiophene-H)-, and (Thiophene+H)- anions from irradiated thiophene films that have been annealed to 300 K, each exhibit a single resonant feature centered around 5.1 eV, suggesting that all signals derive from DEA to the same molecular radiation product. In contrast, only H- and S- are observed to desorb from films of 2-2-bithiophene and no resonance is seen below approximately 10 eV in the anion yield functions. These data suggest that electron irradiation causes formation of ring-opened oligomers, and that closed-ring or 'classical" oligomers, (similar to bithiophene) if formed, contribute little to the ESD of anions.

Superinelastic electron transfer: electron trapping in H2O ice via the N-2((2)Pi(g)) resonance.

We present measurements on the trapping of 0-3 eV electrons in H2O ice films covered with a submonolayer of N2 molecules. At the energy of the N-2((2)Pi(g)) shape resonance, the absolute cross section for electron trapping in ice is approximately 5.5 x 10(-16) cm(2), similar to that for vibrational excitations of gaseous N2 via the resonance. This result, indicating that nearly all electrons from autoionization of N-2((2)Pi(g)) are transferred to electron traps in ice, is explained by superinelastic electron transfer from N-2((2)Pi(g)) into preexisting traps in polar ice, leaving N2 in high vibrational excited states.

Absolute and effective cross-sections for low-energy electron-scattering processes within condensed matter.

Within the last two decades, a number of experimental techniques have been developed to measure mean free paths and absolute and effective cross-sections for various processes related to the interaction of low-energy electrons with condensed matter. In all of the experiments, a monochromatic electron beam impinges on a thin multilayer film composed of atoms and/or molecules condensed on a metal or semiconductor substrate held at cryogenic temperatures in an ultra-high-vacuum system. Depending on the apparatus, cross-sections are obtained from low-energy electron transmission (LEET), high-resolution electron energy loss (HREEL), x-ray photoelectron (XPS) spectroscopy, electron-stimulated desorption (ESD) of neutral and ions, or a combination of these techniques. Quasi-elastic and inelastic mean free paths have been extracted from LEET data. This method has also served to generate absolute cross-sections for electron trapping and fragment production from the dissociation of transient molecular anions. In amorphous ice, a complete set of absolute cross-sections for all inelastic losses by 1-20 eV electrons has been obtained from HREEL data. Effective cross-sections for neutral and ionic radical formation were generated by desorption and XPS experiments. These various methods are briefly described in this article, and the corresponding cross-sections in the range 0-20 eV summarized.