8 research outputs found
Adsorption of 1,3,5-Trinitrobenzene on the Siloxane Sites of Clay Minerals: Ab Initio Calculations of Molecular Models
No full textRevealing the Role of Water in the Acid−Base Interaction between the Phosphate Groups of DNA and the Amino Acid Side Chains of Proteins: A Density Functional Theory Study of Molecular Models
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Lattice Resistance to Hydrolysis of Si−O−Si Bonds of Silicate Minerals: Ab Initio Calculations of a Single Water Attack onto the (001) and (111) β-Cristobalite Surfaces
No full textReduction of Nitroaromatic Compounds on the Surface of Metallic Iron: Quantum Chemical Study
No full textAbstract: The initial reduction steps of nitroaromatic compounds on the surface of metallic iron have been studied theoretically using nitrobenzene (NB) as a representative of nitroaromatic compounds. The quantum chemical cluster approximation within the semiempirical Neglect of Diatomic Differential Overlap for Metal Compounds method was applied to model the Fe(110) crystallographic surface, taken as a representative reactive surface for granular iron. This surface was modeled as a 39-atom two-layer metal cluster with rigid geometry. The associative and dissociative adsorption of nitrobenzene was considered. Based on our quantum chemical analysis, we suggest that the direct electron donation from the metal surface into the À* orbital of NB is a decisive factor responsible for subsequent transformation of the nitro group. Molecularly adsorbed NB interacts with metal iron exclusively through nitro moiety oxygens which occupy tri-coordinated positions on surface The charge transfer from metal to NB of approximately 2 atomic units destablizes the nitro group. As a result, the first dissociation of the N-O bond goes through a relatively low activation barrier. The adsorbed nitrosobenzene is predicted to be a stable surface species, though still quiet labile
