title: Theoretical study on the nitration of methane by acyl nitrate catalyzed by H-ZSM5 zeolite.
abstract: A theoretical study on the nitration of methane by acyl nitrate catalyzed by HZSM-5 zeolite is reported. The zeolite was represented by a "double ring" 20T cluster. The calculations were performed at the DFT/X3LYP/6-31G** and MP2/6-31G** levels. The first step of the mechanism involves the protonation of the acyl nitrate by the zeolite and the formation of a nitronium-like ion. The reaction proceeds through a concerted step with the attack of the methane molecule by the nitronium-like ion and the simultaneous transfer of a proton from the methane molecule to the zeolite, thus reconstructing the acidic site. The activation energies for the first and second steps of this reaction are, respectively, 14.09 and 10.14 kcal/mol at X3LYP/6-31G** level and 16.68 and 13.85 kcal/mol at the MP2/6-31G**.
authors.affiliation: Instituto de Química, Universidade Federal do Rio de Janeiro, Cidade Universitária, CT Bloco A sala 412, Rio de Janeiro, RJ 21949-900, Brazil.
authors.forename: Alexander Martins
authors.initials: AM
authors.lastname: Silva
authors.forename: Marco Antonio Chaer
authors.initials: MA
authors.lastname: Nascimento