Potential Energy Surfaces for the Reaction Al + O2 ?? AlO + O

摘要

Potential energy surfaces for the reaction Al + O2 ℃ AlO + O have been calculated with the multireference configuration interaction (MRCI) method using molecular orbitals derived from the complete active space selfconsistent field (CASSCF) calculations. The end-on geometry is the most favourable for the reaction to take place. The small reaction barrier in the present calculation (0.11 eV) is probably an artefact related to the ionicneutral avoided crossing. The charge analysis implies that the title oxidation reaction occurs through a harpooning mechanism. Along the potential energy surface of the reaction, there are two stable intermediates of AlO2 (C∧v and C2v) at least 2.74 eV below the energy of reactants. The calculated enthalpy of the reaction (?0.07 eV) is in excellent agreement with the experimental value (?0.155 eV) in part due to the fortuitous cancellation of errors in AlO and O2 calculations.