Oddur Ingólfsson

THE REACTIVITY OF SLOW ELECTRONS WITH MOLECULES AT DIFFERENT DEGREES OF AGGREGATION : GAS PHASE, CLUSTERS AND CONDENSED PHASE

The interaction of free electrons in the energy range between 0 and 15 eV with molecules is reviewed. The studies include beam experiments with gas phase molecules under collision-free conditions and at higher pressures, homogeneous and heterogeneous clusters generated in supersonic beams, and molecules adsorbed and condensed on a cold metallic surface. In single molecules under collision-free conditions the usual relaxation process of a transient negative ion formed by free electron attachment is unimolecular decomposition into stable anionic and neutral fragments (dissociative attachment) with cross-sections exceeding 10−14 cm2. A remarkable exception is C60 which forms metastable anions C60− up to 14 eV electron energy. In clusters, intramolecular stabilization processes lead to the formation of stabilized molecular anions. In addition, intramolecular electron transfer processes can strongly contribute to anion formation in homogeneous and heterogeneous clusters. In condensed and adsorbed molecules, finally, effective desorption of negative fragment ions is observed when repulsive precursor ions are involved. The reactivity of transient anions formed by low energy attachment is generally strongly quenched with the degree of aggregation in favour of associative processes. In the case of core excited resonances, however, the reactivity can be enhanced by the surrounding medium. This effect is explained by the conversion of an open channel resonance in isolated molecules into a Feshbach resonance in clusters and condensed molecules.

Dissociative electron attachment to gas phase valine: a combined experimental and theoretical study.

Using a crossed electron/molecule beam technique the dissociative electron attachment (DEA) to gas phase L-valine, (CH(3))(2)CHCH(NH(2))COOH, is studied by means of mass spectrometric detection of the product anions. Additionally, ab initio calculations of the structures and energies of the anions and neutral fragments have been carried out at G2MP2 and B3LYP levels. Valine and the previously studied aliphatic amino acids glycine and alanine exhibit several common features due to the fact that at low electron energies the formation of the precursor ion can be characterized by occupation of the pi* orbital of the carboxyl group. The dominant negative ion (M-H)(-) (m/Z=116) is observed at electron energies of 1.12 eV. This ion is the dominant reaction product at electron energies below 5 eV. Additional fragment ions with m/Z=100, 72, 56, 45, 26, and 17 are observed both through the low lying pi* and through higher lying resonances at about 5.5 and 8.0-9.0 eV, which are characterized as core excited resonances. According to the threshold energies calculated here, rearrangements play a significant role in the formation of DEA fragments observed from valine at subexcitation energies.

Anion formation from gaseous and condensed CF3I on low energy electron impact

Anion formation following electron impact to CF3I is studied in the energy range 0–15 eV. The experiments include gas phase CF3I in the effusive molecular beam under single collision conditions, clusters in a supersonic molecular jet and CF3I condensed in the UHV in multilayer amounts onto a cold metallic substrate. In isolated molecules fragment anions are formed via dissociative attachment (DA) and dipolar dissociation (DD). The DA resonances are located at 0.0 and 3.8 eV and are assigned as single particle and two particle resonance, respectively. The low energy resonance exhibits an exceedingly high cross section for I− formation, while the higher energy resonance decomposes into CF3−, F−, and FI− with comparatively low intensity. Both resonances possess significant C–I antibonding character as apparent from their decomposition dynamics. In clusters the stabilized molecular anion CF3I− and larger complexes of the form (CF3I)n− and (CF3I)n⋅I− are observed. At higher energies anion formation is affected...

Energy-resolved collision-induced dissociation of Cun+ (n=2–9): Stability and fragmentation pathways

Collision induced dissociation of Cun+ clusters (n=2–9) in collision with Xe is presented in the center-of-mass energy range from about 100 meV to above 15 eV. The collision energy dependence is measured for the total and the partial dissociation cross sections, and the dissociation thresholds for the dominating processes are derived. The threshold energies show pronounced odd–even alternations, reflecting a higher stability of the odd-numbered, Cu2n+1+, clusters. Further, the evaporation of a single neutral atom is found to be the energetically favorable process for the even-numbered clusters, while the loss of the neutral dimer is favorable in the case of the odd-numbered clusters. An exception is Cu9+, where the formation of Cun−1+ is energetically favorable, and the energetics of the Cun−2+ formation are in good agreement with sequential evaporation of two neutral monomers. Here we discuss the energy dependency of the total and partial dissociation cross sections, and try to give a consistent picture ...

MEDIUM ENHANCED, ELECTRON STIMULATED DESORPTION OF CF3- FROM CONDENSED CF3I

Abstract It is shown that (a) the cross-section for electron stimulated desorption of CF 3 − from condensed CF 3 I is enhanced by more than 2 orders of magnitude with respect to the corresponding gas-phase dissociative electron attachment cross-section and (b) CF 3 − is ejected from the CF 3 I film into vacuum with surprisingly high kinetic energy. These observations are explained by a preferential orientation of the molecule at the surface and a particular, medium enhanced, desorption mechanism which is based on the conversion of an open-channel resonance into a closed-channel (Feshbach) resonance when solvated.

NCO – , a Key Fragment Upon Dissociative Electron Attachment and Electron Transfer to Pyrimidine Bases: Site Selectivity for a Slow Decay Process

AbstractWe report gas phase studies on NCO– fragment formation from the nucleobases thymine and uracil and their N-site methylated derivatives upon dissociative electron attachment (DEA) and through electron transfer in potassium collisions. For comparison, the NCO– production in metastable decay of the nucleobases after deprotonation in matrix assisted laser desorption/ionization (MALDI) is also reported. We show that the delayed fragmentation of the dehydrogenated closed-shell anion into NCO– upon DEA proceeds few microseconds after the electron attachment process, indicating a rather slow unimolecular decomposition. Utilizing partially methylated thymine, we demonstrate that the remarkable site selectivity of the initial hydrogen loss as a function of the electron energy is preserved in the prompt as well as the metastable NCO– formation in DEA. Site selectivity in the NCO– yield is also pronounced after deprotonation in MALDI, though distinctly different from that observed in DEA. This is discussed in terms of the different electronic states subjected to metastable decay in these experiments. In potassium collisions with 1- and 3-methylthymine and 1- and 3-methyluracil, the dominant fragment is the NCO– ion and the branching ratios as a function of the collision energy show evidence of extraordinary site-selectivity in the reactions yielding its formation. Graphical abstractᅟ

Absolute cross sections for dissociative electron attachment and dissociative ionization of cobalt tricarbonyl nitrosyl in the energy range from 0 eV to 140 eV

We report absolute dissociative electron attachment (DEA) and dissociative ionization (DI) cross sections for electron scattering from the focused electron beam induced deposition (FEBID) precursor Co(CO)(3)NO in the incident electron energy range from 0 to 140 eV. We find that DEA leads mainly to single carbonyl loss with a maximum cross section of 4.1 × 10(-16) cm(2), while fragmentation through DI results mainly in the formation of the bare metal cation Co(+) with a maximum cross section close to 4.6 × 10(-16) cm(2) at 70 eV. Though DEA proceeds in a narrow incident electron energy range, this energy range is found to overlap significantly with the expected energy distribution of secondary electrons (SEs) produced in FEBID. The DI process, on the other hand, is operative over a much wider energy range, but the overlap with the expected SE energy distribution, though significant, is found to be mainly in the threshold region of the individual DI processes.

The role of low-energy electrons in focused electron beam induced deposition: four case studies of representative precursors.

Summary Focused electron beam induced deposition (FEBID) is a single-step, direct-write nanofabrication technique capable of writing three-dimensional metal-containing nanoscale structures on surfaces using electron-induced reactions of organometallic precursors. Currently FEBID is, however, limited in resolution due to deposition outside the area of the primary electron beam and in metal purity due to incomplete precursor decomposition. Both limitations are likely in part caused by reactions of precursor molecules with low-energy (<100 eV) secondary electrons generated by interactions of the primary beam with the substrate. These low-energy electrons are abundant both inside and outside the area of the primary electron beam and are associated with reactions causing incomplete ligand dissociation from FEBID precursors. As it is not possible to directly study the effects of secondary electrons in situ in FEBID, other means must be used to elucidate their role. In this context, gas phase studies can obtain well-resolved information on low-energy electron-induced reactions with FEBID precursors by studying isolated molecules interacting with single electrons of well-defined energy. In contrast, ultra-high vacuum surface studies on adsorbed precursor molecules can provide information on surface speciation and identify species desorbing from a substrate during electron irradiation under conditions more representative of FEBID. Comparing gas phase and surface science studies allows for insight into the primary deposition mechanisms for individual precursors; ideally, this information can be used to design future FEBID precursors and optimize deposition conditions. In this review, we give a summary of different low-energy electron-induced fragmentation processes that can be initiated by the secondary electrons generated in FEBID, specifically, dissociative electron attachment, dissociative ionization, neutral dissociation, and dipolar dissociation, emphasizing the different nature and energy dependence of each process. We then explore the value of studying these processes through comparative gas phase and surface studies for four commonly-used FEBID precursors: MeCpPtMe3, Pt(PF3)4, Co(CO)3NO, and W(CO)6. Through these case studies, it is evident that this combination of studies can provide valuable insight into potential mechanisms governing deposit formation in FEBID. Although further experiments and new approaches are needed, these studies are an important stepping-stone toward better understanding the fundamental physics behind the deposition process and establishing design criteria for optimized FEBID precursors.

Dissociative electron attachment to gas phase glycine: Exploring the decomposition pathways by mass separation of isobaric fragment anions

Dissociative electron attachment to gas phase glycine generates a number of fragment ions, among them ions observed at the mass numbers 15, 16 and 26 amu. From stoichiometry they can be assigned to the chemically rather different species NH(-)/CH(3)(-)(15 amu), O(-)/NH(2)(-)(16 amu) and CN(-)/C(2)H(2)(-)(26 amu). Here we use a high resolution double focusing two sector mass spectrometer to separate these isobaric ions. It is thereby possible to unravel the decomposition reactions of the different transient negative ions formed upon resonant electron attachment to neutral glycine in the energy range 0-15 eV. We find that within the isobaric ion pairs, the individual components generally arise from resonances located at substantial different energies. The corresponding unimolecular decompositions involve complex reaction sequences including multiple bond cleavages and substantial rearrangement in the precursor ion. To support the interpretation and assignments we also use (13)C labelling of glycine at the carboxylic group.

Substitution effects in elastic electron collisions with CH3X (X=F, Cl, Br, I) molecules

We report absolute elastic differential, integral, and momentum transfer cross sections for electron interactions with the series of molecules CH(3)X (X=F, Cl, Br, I). The incident electron energy range is 50-200 eV, while the scattered electron angular range for the differential measurements is 15 degrees-150 degrees. In all cases the absolute scale of the differential cross sections was set using the relative flow method with helium as the reference species. Substitution effects on these cross sections, as we progress along the halomethane series CH(3)F, CH(3)Cl, CH(3)Br, and CH(3)I, are investigated as a part of this study. In addition, atomic-like behavior in these scattering systems is also considered by comparing these halomethane elastic cross sections to results from other workers for the corresponding noble gases Ne, Ar, Kr, and Xe, respectively. Finally we report results for calculations of elastic differential and integral cross sections for electrons scattering from each of the CH(3)X species, within an optical potential method and assuming a screened corrected independent atom representation. The level of agreement between these calculations and our measurements was found to be quite remarkable in each case.