Gregory Grieves

Guanine, adenine, and hypoxanthine production in UV-irradiated formamide solutions: relaxation of the requirements for prebiotic purine nucleobase formation.

Here, we show for the first time that gua-nine, adenine, and hypoxanthine can be produced from forma-mide in a single model prebiotic reaction at lower tempera-tures than previously reported, if formamide is subjected to UVirradiation during heating; this observation relaxes the require-ments for prebiotic purine nucleobase formation. The yieldand diversity of purines produced in heated/UV-irradiated for-mamide are further enhanced by the presence of inorganiccatalysts, as solids or as dissolved ions. We also analyzed theproducts of formamide solutions to which specific hydrogencyanide (HCN) condensation products

Production of oxygen by electronically induced dissociations in ice

A solid-state chemical model is given for the production of O2 by electronic excitation of ice, a process that occurs on icy bodies in the outer solar system. Based on a review of the relevant available laboratory data, we propose that a trapped oxygen atom-water complex is the principal precursor for the formation of molecular oxygen in low-temperature ice at low fluences. Oxygen formation then occurs through direct excitation of this complex or by its reaction with a freshly produced, nonthermal O from an another excitation event. We describe a model for the latter process that includes competition with precursor destruction and the effect of sample structure. This allows us to put the ultraviolet photon, low-energy electron, and fast-ion experiments on a common footing for the first time. The formation of the trapped oxygen atom precursor is favored by the preferential loss of molecular hydrogen and is quenched by reactions with mobile H. The presence of impurity scavengers can limit the trapping of O, leading to the formation of oxygen-rich molecules in ice. Rate equations that include these reactions are given and integrated to obtain an analytic approximation for describing the experimental results on the production and loss of molecular oxygen from ice samples. In the proposed model, the loss rate varies, roughly, inversely with solid-state defect density at low temperatures, leading to a yield that increases with increasing temperature as observed. Cross sections obtained from fits of the model to laboratory data are evaluated in light of the proposed solid-state chemistry.

Photodissociation of methyl iodide adsorbed on low-temperature amorphous ice surfaces

Photodissociation dynamics of methyl iodide (CH3I) adsorbed on both amorphous solid water (ASW) and porous amorphous solid water (PASW) has been investigated. The ejected ground-state I((2)P3∕2) and excited-state I((2)P1∕2) photofragments produced by 260- and 290-nm photons were detected using laser resonance-enhanced multiphoton ionization. In contrast to gas-phase photodissociation, (i) the I((2)P3∕2) photofragment is favored compared to I((2)P1∕2) at both wavelengths, (ii) I((2)P3∕2) and I((2)P1∕2) have velocity distributions that depend upon ice morphology, and (iii) I2 is produced on ASW. The total iodine [I((2)P3∕2)+I((2)P1∕2)+I2] yield varies with substrate morphology, with greater yield from ASW than PASW using both 260- and 290-nm photons. Temperature-programmed desorption studies demonstrate that ice porosity enhances the trapping of adsorbed CH3I, while pore-free ice likely allows monomer adsorption and the formation of two-dimensional CH3I clusters. Reactions or collisions involving these clusters, I atomic fragments, or I-containing molecular fragments at the vacuum-surface interface can result in I2 formation.

Probing the Interaction of Hydrogen Chloride with Low-Temperature Water Ice Surfaces Using Thermal and Electron-Stimulated Desorption

The interaction and autoionization of HCl on low-temperature (80-140 K) water ice surfaces has been studied using low-energy (5-250 eV) electron-stimulated desorption (ESD) and temperature programmed desorption (TPD). There is a reduction of H(+) and H(2)(+) and a concomitant increase in H(+)(H(2)O)(n=1-7) ESD yields due to the presence of submonolayer quantities of HCl. These changes are consistent with HCl induced reduction of dangling bonds required for H(+) and H(2)(+) ESD and increased hole localization necessary for H(+)(H(2)O)(n=1-7) ESD. For low coverages, this can involve nonactivated autoionization of HCl, even at temperatures as low as 80 K; well below those typical of polar stratospheric cloud particles. The uptake and autoionization of HCl is supported by TPD studies which show that for HCl doses ≤0.5 ± 0.2 ML (ML = monolayer) at 110 K, desorption of HCl begins at 115 K and peaks at 180 K. The former is associated with adsorption of a small amount of molecular HCl and is strongly dependent on the annealing history of the ice. The latter peak at 180 K is commensurate with desorption of HCl via recombinative desorption of solvated separated ion pairs. The activation energy for second-order desorption of HCl initially in the ionized state is 43 ± 2 kJ/mol. This is close to the zero-order activation energy for ice desorption.