Ab initio investigation of the ground and excited states of MoO+,2+,- and their catalytic strength on water activation

作者：Ariyarathna Isuru R; Miliordos Evangelos^*

来源：Physical Chemistry Chemical Physics, 2018, 20(17): 12278-12287.

DOI：10.1039/c8cp01676c

The charged molybdenum monoxides, MoO+,2+,- were studied by multireference configuration interaction and coupled cluster calculations in conjunction with large basis sets. Full potential energy curves were constructed and bonding patterns were proposed for several electronic states of the three species. Our numerical results involve accurate equilibrium bond lengths, harmonic vibrational frequencies, anharmonicities, excitation energies, and binding energies. This is the first high-level theoretical investigation and our results compare favorably with the limited existing experimental data. Nine states of MoO2+ are bound with respect to the lowest energy fragments Mo+ + O+, while MoO- has five bound electronic states with respect to MoO + e(-). Energetics, including activation energies, are given for the reaction between the lowest lying electronic states of the titled species and water. It is shown that MoO- is clearly more efficient at activating an OH bond.

• 出版日期2018-5-7