Polymorphism and electronic structure of polyimine and its potential significance for prebiotic chemistry on Titan

The chemistry of hydrogen cyanide (HCN) is believed to be central to the origin of life question. Contradictions between Cassini–Huygens mission measurements of the atmosphere and the surface of Saturn’s moon Titan suggest that HCN-based polymers may have formed on the surface from products of atmospheric chemistry. This makes Titan a valuable “natural laboratory” for exploring potential nonterrestrial forms of prebiotic chemistry. We have used theoretical calculations to investigate the chain conformations of polyimine (pI), a polymer identified as one major component of polymerized HCN in laboratory experiments. Thanks to its flexible backbone, the polymer can exist in several different polymorphs, which are relatively close in energy. The electronic and structural variability among them is extraordinary. The band gap changes over a 3-eV range when moving from a planar sheet-like structure to increasingly coiled conformations. The primary photon absorption is predicted to occur in a window of relative transparency in Titan’s atmosphere, indicating that pI could be photochemically active and drive chemistry on the surface. The thermodynamics for adding and removing HCN from pI under Titan conditions suggests that such dynamics is plausible, provided that catalysis or photochemistry is available to sufficiently lower reaction barriers. We speculate that the directionality of pI’s intermolecular and intramolecular =N–H…N hydrogen bonds may drive the formation of partially ordered structures, some of which may synergize with photon absorption and act catalytically. Future detailed studies on proposed mechanisms and the solubility and density of the polymers will aid in the design of future missions to Titan.

Resonant Inelastic Soft X-ray Scattering Studies of U(VI) Reduction on Iron Surfaces

ABSTRACTWe report on the spectroscopic analysis of several samples relevant to the processes governing the behavior of oxidized uranium species in groundwater solutions under anoxic conditions. Both Fe samples with different times of exposure to the U(IV) solution and Fe metal-solution inetrfaces in the liquid cell ex-situ and in-situ, respectively. Resonant inelastic soft x-ray scattering is shown to be sensitive to the chemical state of uranium. The measurements were performed at a number of energies of the primary photon beam across the U 5d absorption edge. The results unambiguously indicate the reduction of U(VI) to U(IV) on the Fe surface.