RESUMO
The exothermic F + H(2)O â HF + OH reaction has a decidedly "early" or "reactant-like" barrier. According to a naïve interpretation of the Polanyi's rules, translational energy would be more effective than vibrational energy in promoting such reactions. However, we demonstrate here using both quasi-classical trajectory and full-dimensional quantum wave packet methods on an accurate global potential energy surface that excitations in the H(2)O vibrational degrees of freedom have higher efficacy in enhancing the reactivity of the title reaction than the same amount of translational energy, thus providing a counter-example to Polanyi's rules. This enhancement of reactivity is analyzed using a vibrational adiabatic model, which sheds light on the surprising mode selectivity in this reaction.
Assuntos
Flúor/química , Ácido Fluorídrico/síntese química , Hidróxidos/síntese química , Teoria Quântica , Água/química , Ácido Fluorídrico/química , Hidróxidos/química , VibraçãoRESUMO
The ionic liquid 1-ethyl-3-methylimidazolium fluoride hydrofluoride, [C2mim][F] x xHF, has been synthesized through a new, solventless route that excludes halogen metathesis. The byproducts are salts, alcohols, and carbon dioxide.