C.R. Ponciano

A Theoretical and Experimental Study of Positive and Neutral LiF Clusters Produced by Fast Ion Impact on a Polycrystalline LiF Target

The positive and neutral clusters produced by the impact of approximately 60 MeV (252)Cf fission fragments on a LiF polycrystalline target are analyzed. The positive ion spectrum is dominated by the (LiF)(n)Li(+) series, n = 0-7, exhibiting a total yield 2 orders of magnitude higher than that of the (LiF)(n)(+) series. The yield for the dominant (LiF)(n)Li(+) series decreases roughly as exp(-kn), where k approximately 0.9 for n = 0-3 and k approximately 0.6 for the heavier clusters (n = 4-9), while the yield of the (LiF)(n)(+) series also decreases exponentially as n increases with k approximately 0.6. Theoretical calculations were performed for the (LiF)(n)Li(0), (LiF)(n)Li(+), and (LiF)(n)(0) series for n up to 9. For the smaller clusters the structures first obtained with a genetic algorithm generator were further optimized at the DFT/B3LYP/6-311+G(3df), DFT/B3LYP/LACV3P*, and MP2/LACV3P* levels of theory. An energy criterion is used for a proper taxonomic description of the optimized cluster isomers. Cluster properties such as fragmentation energy and stability are discussed for the proposed configurations. The results show that for all three series the most stable isomers present a linear structure for small cluster size (n = 1-3), while cubic cells or polyhedral structures are preferred for larger cluster sizes (n = 4-9). Fragmentation energy results suggest that a desorbed excited (LiF)(n)Li(+) ion preferentially dissociates via a cascade of (LiF)(n)(0) units, in agreement with the slope modification in the exponential decay of the (LiF)(n)Li(+) ion abundances for n > or = 3.

The Influence of Crystallinity Degree on the Glycine Decomposition Induced by 1 MeV Proton Bombardment in Space Analog Conditions

Glycine is the simplest proteinaceous amino acid and is present in all life-forms on Earth. In aqueous solutions, it appears mainly as zwitterion glycine (+NH3CH2COO-); however, in solid phase, it may be found in amorphous or crystalline (α, β, and γ) forms. The crystalline forms differ from each other by the packing of zwitterions in the unitary cells and by the number of intermolecular hydrogen bonds. This molecular species has been extensively detected in carbonaceous meteorites and was recently observed in the cometary samples returned to Earth by NASAs Stardust spacecraft. In space, glycine is exposed to several radiation fields at different temperatures. We present an experimental study on the destruction of zwitterionic glycine crystals at room temperature by 1 MeV protons, in which the dependence of the destruction rates of the α-glycine and β-glycine crystals on bombardment fluence is investigated. The samples were analyzed in situ by Fourier transform infrared spectrometry at different proton fluences. The experiments occurred under ultrahigh vacuum conditions at the Van de Graaff accelerator lab at the Pontifical Catholic University at Rio de Janeiro (PUC-Rio), Brazil. For low fluences, the dissociation cross section of α-glycine was observed to be 2.5×10(-14) cm2, a value roughly 5 times higher than the dissociation cross section found for β-glycine. The estimated half-lives of α-glycine and β-glycine zwitterionic forms extrapolated to the Earth orbit environment are 9×10(5) and 4×10(6) years, respectively. In the diffuse interstellar medium the estimated values are 1 order of magnitude lower. These results suggest that pristine interstellar β-glycine is the one most likely to survive the hostile environments of space radiation. A small feature around 1650-1700 cm(-1), tentatively attributed to an amide functional group, was observed in the IR spectra of irradiated samples, suggesting that cosmic rays may induce peptide bond synthesis in glycine crystals. Combining this finding with the fact that this form has the highest solubility among the other glycine polymorphs, we suggest that β-glycine is the one most likely to have produced the first peptides on primitive Earth.

Theoretical and experimental study of negative LiF clusters produced by fast ion impact on a polycrystalline 7LiF target.

The emission of negative cluster ions produced by the impact of approximately 60 MeV (252)Cf fission fragments on a (7)LiF polycrystalline target is analyzed. The negative ion mass spectrum is dominated by the ((7)LiF)(n)F(-) series, n = 1 to approximately 30. The desorption yield distribution of the ((7)LiF)(n)F(-) members has a maximum at n = 2 and then decreases as the sum of two exponentials whose decay parameters are k(Fast) = 0.9 and k(Slow) = 0.08. These k values are the same as those observed for the positive series and close to others obtained for condensed gas targets. Relative cluster ion stabilities, deduced from the experimental ion abundances for the (LiF)(n)F(-) series, are proposed to be correlated with theoretical structures according to their internal energy by using the deviation plot (D-plot) methodology. A pool of candidate cluster structures was generated using a genetic algorithm and further analyzed and optimized using density functional theory (DFT) with the hybrid functional B3LYP (DFT/B3LYP) and Moller-Plesset perturbation theory (MP2). For the small clusters (n = 1 to 2), the most stable structures are found to be linear, whereas the larger clusters (n = 4 to 6) present cubic or polyhedral structures. Fragmentation energies, ionization potentials, and relative stabilities are reported for the most abundant families of the (LiF)(n)F(-) and (LiF)(n)(-) series.

Energies and yields of secondary ions ejected from alkali halides by a 0.18–6.0 MeV nitrogen beam

Abstract Nuclear and electronic sputtering was studied for the alkali halides LiF, CsI, NaF, NaCl, NaBr and NaI being vacuum evaporated on thin Al-foils and irradiated by 14 N ions having an energy loss of 20–190 eV/A. A double-grid time-of-flight technique was used to determine the yields and the axial energy distributions of the alkali and halide ions ejected from the sample surface. In case of LiF, the most carefully investigated compound, the dependence of ion yields on the energy loss and the shape of the energy distributions clearly mark the onset of collisional sputtering towards low beam energies. Apart from F − , for all other investigated alkali and halide ions electronic sputtering is the dominant ejection process. Above 1 MeV bombarding energy, their mean axial energies were found to range from 0.26 to 2.0 eV, their energy distributions fall off with E − n , n having values between 3.0 and 4.5. In cases, where the nuclear energy loss is relatively low, the ion yields scale with about the second power of the electronic energy loss; the mean axial energies and the yields change only little or not with the charge state of the incident ions. These observations lead to the general conclusion, that electronic sputtering from alkali halides is established by cooperative processes and that probably electron-hole production in deep layers contribute essentially to formation and ejection of ions at the surface. The results are discussed in terms of exciton production and migration.

Cluster emission and chemical reactions in oxygen and nitrogen ices induced by fast heavy-ion impact

Two ices, O2 and a mixture of O2 and N2, are bombarded by 252Cf fission fragments (FF) (approximately 65 MeV at target surface); the emitted positive and negative secondary ions are analyzed by time-of-flight mass spectrometry (TOF-SIMS). These studies shall enlighten sputtering from planetary and interstellar ices. Three temperature regions in the 28-42-K range are analyzed: (1) before N2 sublimation, in which hybrid chemical species are formed, (2) before O2 sublimation, in which the TOF mass spectrum is dominated by low-mass (O2)p cluster ions and (3) after O2 sublimation, in which (N2)p or (O2)p cluster ions are practically inexistent. In the first region, four hybrid ion series are observed: NOn-1+, N2On-2(+/-), and N4On-4(-). In the second region, two positive and negative ion series are identified: (O2)pO(+/-) and (O2)pO2(+/-). Their yield distributions are fitted by the sum of two decreasing exponentials, whose decay constants are the same for all series. It is observed that the cluster ion desorption from solid oxygen is very similar to that of other frozen gases, but its yield distribution oscillates with a three- or six-atom periodicity, suggesting O3 or 3O2 units in the cluster structure, respectively.

Laser induced formation of CsI ion clusters analyzed by delayed extraction time-of-flight mass spectrometry

(CsI)nCs+ (n = 1,2) cluster ion formation from polycrystalline CsI irradiated by pulsed-UV laser (337 nm) is analyzed by delayed extraction time-of-flight mass spectrometry technique. Measurements were performed for different laser intensities and for several delayed extraction times. Experimental data show that CsI laser ablation produces the emission of (CsI),Cs+ ions (n = 0, 1, 2), whose yields decrease exponentially with n and increase exponentially with the laser pulse energy. A quasi equilibrium evolution of the clusters is proposed to extract a parameter characteristic of the cluster recombination process. The delayed extraction method of initial velocity determination was improved to take into account collisions in the high density plasma close to the target. The new parameterization helps to describe the dynamics of secondary ions of different masses for laser irradiances above the ion desorption threshold in a collision regime. The initial velocity of the secondary ions [(CsI)nCs+ (n = 0, 1, 2)] as function of the laser irradiance was determined. The distance to the target when the free expansion process starts is reported as function of the secondary ions mass and of the laser irradiance. The collision regimes influence on the secondary ion dynamics is discussed.

Track electrostatic model for describing secondary ion emission of insulators

A model based on the nuclear track potential is described and used to predict trajectories and the energy distribution of secondary ions emitted by insulating targets. In this model, the electric field generated by each track pushes away the secondary ions formed on the target surface. The effects on the potential due to target thickness, track charge density, projectile incidence angle and secondary ion mass are analyzed. Predictions are compared with experimental data existing in the literature. It is found that the proposed model describes partially the behavior observed in the angular distribution of the emitted ions and new processes are proposed to be included in the model.

Analysis of metastable decay by time-of-flight coincidence and kinetics energy measurements

Abstract A procedure for fragmentation pattern analysis of metastable ions, emitted in photon or ion induced desorption processes, is described. The method is based on a combination of three well-established techniques, namely: time-of-flight (TOF), coincidence counting, and electrostatic energy analysis in reflectron mass spectrometers. The key improvement comes from a judicious selection of the electrostatic mirror voltages for running the coincidence measurements in the best signal/noise conditions. The TOFs of stable species, as well as those of the neutral and ion fragments produced by all expected unimolecular-binary decays occurring in the field-free region before the mirror, are calculated and plotted as a function of the mirror voltage. The mirror voltages for coincidence measurements are selected after comparison of these dynamics plots of reflected and nonreflected species with experimental noncoincidence TOF spectra. To illustrate this procedure, the (LiF) n Li + ∗ → (LiF) n−m Li + + (LiF) m 0 fragmentation pattern is analyzed.

Analysis of ion dynamics and peak shapes for delayed extraction time-of-flight mass spectrometers

The dependence of time-of-flight (TOF) peak shapes on time-dependent extraction electric fields is studied theoretically. Conditions for time focusing are analyzed both analytically and numerically for double-acceleration-region TOF spectrometers. Expressions for the spectrometer mass resolution and for the critical delay time are deduced. Effects due to a leakage field in the first acceleration region are shown to be relevant under certain conditions. TOF peak shape simulations for the delayed extraction method are performed for emitted ions presenting a Maxwellian initial energy distribution. Calculations are compared to experimental results of Cs+ emission due to CsI laser ablation.

Dissociation of fast ions analyzed by time-of-flight

The fragmentation of metastable ions, having keV of kinetic energy, is analyzed by time-of-flight technique. Assuming isotropic distribution of fragments in a free field region, it is deduced an analytical expression to describe the corresponding peak shapes in linear TOF spectrometers. Metastable ion mean-life and the kinetic energy release (Q-value) are the quantities extracted from data fitting. As an illustration, the dissociation of C8H10N+ metastable ions, desorbed by 252Cf ssion fragment impact on organic target, is studied.