Activation barriers for series of exothermic homologous reactions. III. Reactions of s 2 metal atoms with N2O and O2

• Published in: The Journal of chemical physics 1993-05, Vol.98 (9), p.7004-7011
• Main Authors: Futerko, Peter M., Fontijn, Arthur
• Format: Article
• Language: English
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.464743

Potential energy curves are derived for the rate-limiting channels of reactions of s2 metal atoms with N2O and O2, for which both reactants are in their ground electronic states. Activation barriers and rate coefficients are derived from these curves and are compared with the available experimental data. The importance of contributions by spin-forbidden channels to the rate coefficients of N2O reactions is evaluated using the Landau–Zener–Stuckelberg probability of potential-curve switching. Calculated rate coefficients thus obtained are in good agreement with the available experimental data. It is established that for the Mg, Ca, and Ba+N2O reactions the interaction energy of the lowest singlet and triplet states increases as the mass of the metal atom increases. Spin-forbidden channels are thus more important for the Ca and Ba+N2O reactions than for the Mg+N2O reaction. Calculated activation barriers for reactions of s2 metal atoms with O2 are found to be in agreement with the available experimental data, the only exception being that for the Zr+O2 reaction. The activation barriers, with the exception of those for the Ni and Zr+O2 reactions, are seen to correlate with the s–p promotion energies plus the ionization potentials of the atoms. Explanations for these disagreements are given.