Enio Frota da Silveira

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.

Alkali Halide Nanotubes: Structure and Stability

Accurate density functional theory (DFT) and coupled-cluster (CCSD) calculations on a series of (LiF) n=2,36 neutral clusters suggest that nanotube structures with hexagonal and octagonal transversal cross sections show stability equal to or greater than that of the typical cubic form of large LiF crystals. The nanotube stability was further corroborated by quantum dynamic calculations at room temperature. The fact that stable nanotube structures were also found for other alkali halides (e.g., NaCl and KBr) suggests that this geometry may be widely implemented in material sciences.

Production of Oxidants by Ion Bombardment of Icy Moons in the Outer Solar System

Our groups in Brazil, France and Italy have been active, among others in the world, in performing experiments on physical-chemical effects induced by fast ions colliding with solids (frozen gases, carbonaceous and organic materials, silicates, etc.) of astrophysical interest. The used ions span a very large range of energies, from a few keV to hundreds MeV. Here we present a summary of the results obtained so far on the formation of oxidants (hydrogen peroxide and ozone) after ion irradiation of frozen water, carbon dioxide and their mixtures. Irradiation of pure water ice produces hydrogen peroxide whatever is the used ion and at different temperatures. Irradiation of carbon dioxide and water frozen mixtures result in the production of molecules among which hydrogen peroxide and ozone. The experimental results are discussed in the light of the relevance they have to support the presence of an energy source for biosphere on Europa and other icy moons in the outer Solar System.

Radiation effects in astrophysical ices

The interaction of heavy ions with astrophysical ices was studied at different beamlines of GANIL by infrared absorption spectroscopy. This allowed simulating in the laboratory the physico-chemical modifications induced in icy objects in space, exposed to radiation fields such as the solar wind, magnetospheric particles and interstellar cosmic rays. We briefly discuss sputtering, destruction and formation of molecules, amorphization and compaction, implantation, and finally the formation of organic molecules. This latter topic is related to the question of the initial conditions for the emergence of life.

Theoretical Investigation on the Stability of Negatively Charged Formic Acid Clusters

Recent experimental results on negatively charged formic acid clusters generated by the impact of (252)Cf fission fragments on icy formic acid target are compared to quantum mechanical calculations. Structures for the clusters series, (HCOOH)nOH(-), where 2 < or = n < or = 4, are proposed based on ab initio electronic structure methods. The results show that cluster growth does not have a regular pattern of nucleation. A stability analysis was performed considering the commonly defined stability function. Temporal behavior of the clusters was evaluated by Born-Oppenheimer molecular dynamics to check the mechanism that provides cluster stability. The evaluated temporal profiles indicate the importance of hydrogen atom migration between the formic acid moieties in maintaining the stability of the structures and the water formation due to hydrogen abstraction by the hydroxyl approach.

Theoretical Investigation on the Stability of Ionic Formic Acid Clusters

Recent experimental results on positive charged formic acid clusters generated by the impact of (252)Cf fission fragments (FF) on icy formic acid target are examined in this paper by quantum mechanical calculations. Structures for the clusters series, (HCOOH)(n)H(+) and (HCOOH)(n)H(3)O(+), where 2 < or = n < or = 4, are proposed based on ab initio electronic structure methods. Results show that cluster growth does not present a regular pattern of nucleation. A stability analysis was performed considering the commonly defined stability function, where E is the total electronic energy plus the zero point vibrational energy correction, including the BSSE correction. The stability analysis leads to a picture that is compatible with experimental observations, indicating a decay of the stability with the increase of cluster mass. Temporal behavior of the clusters was evaluated by Born-Oppenheimer molecular dynamics to check the mechanism that provides cluster stability. The evaluated temporal profiles indicate the importance of hydrogen atom migration between the formic acid moieties to maintain the stability of the structures.

Organic ion species sputtered from contaminated water ice by 1.5 MeV N2+ ions

Electronic sputtering of organic species being mixed to water ice by residual-gas condensation is analyzed by secondary ion time-of-flight mass spectrometry. The ice samples were prepared at 15 K by deposition from a H2O gas-flow and irradiated by 1.5 MeV N2+ ions while the temperature was raised up to 216 K. Desorption ion yields of positive H2O specific ions as of some organic ion species are measured as a function of temperature. Remarkably high desorption yield variations, mainly of the CnHm ions, were observed during the enrichment of organics hiding the emission of (H2O)nH3O+ cluster ions.

Evolutionary algorithms applied to elucidate ionic water cluster structure formation

In this work we present two evolutionary algorithms applied to look for positive water cluster structures. Both algorithms were applied in order to simulate the formation of the aggregates using the neutral clusters as a precursor. In other words, we are not looking for the global minima positive water cluster structures, but rather than trying to find the most stable structures formed from neutral stable clusters. To achieve our goal three steps were executed. In the first one we looked for the most stable structures for (<i>H</i>₂<i>O</i>)_<i>n</i>(<i>n</i> = 2 - 8), applying a genetic algorithm. In the second step we simulated that the found neutral clusters had lost one of their electrons, creating positive clusters (<i>H</i>₂<i>O</i>)+/<i>n</i>. Finally, in the last step we simulated the creation of positive cluster by the aggregation of one positive ion, forming (<i>H</i>₂<i>O</i>)_<i>n</i><i>H</i>₂<i>O</i>+ clusters. in the latter stage we applied a quantum inspired evolutionary algorithm for numerical optimization (QIEA-R). Results of our search present innovative positive water structures and was able to compare two different ways for ionic cluster formation.

Radiolysis of ammonia-containing ices by heavy cosmic rays inside dense molecular clouds

We present experimental studies on the interaction of heavy, highly charged and energetic ions (46 MeV 58Ni13+) with interstellar ammonia-containing (H2O:NH3:CO) ice analog in an attempt to simulate the physical chemistry induced by heavy ion cosmic rays inside dense astrophysical environments. The measurements were performed at the heavy ion accelerator GANIL in Caen, France. In-situ analysis have been performed by a Fourier transform infrared spectrometer. The averaged values for the dissociation cross section of water, ammonia and carbon monoxide are determined and the estimated half life for the studied species inside dense molecular clouds is 2-3 × 106 years. The IR spectra of organic residue produced by the radiolysis have revealed, at room temperature, five bands that are tentatively assigned to vibration modes of the zwitterionic glycine (NH3+CH2COO−).

Irradiation effects in CO and CO2 ices induced by swift heavy Ni ions at 46 MeV and 537 MeV

In order to simulate the effects of the heavy ion component of cosmic rays on ices in astrophysical environments, the CO and CO2 ices were irradiated with swift nickel ions in the electronic energy loss regime. The ices were prepared by condensing gas onto a CsI substrate at a temperature of 14 K and analyzed by means of infrared (FTIR) spectroscopy. The physical process of deposition by Ni ions is similar to more important and abundant heavy cosmic rays such as Fe ions. Dissociation of the ice molecules, and formation of new molecules were observed. Also, sputtering (leading to desorption of molecules from the solid surface to the gas phase) was observed. It was found that the sputtering yield due to heavy ions cannot be neglected with respect to desorption induced by weakly ionizing particles such as UV photons and protons.