William J. Jackson, Tyler M. Fromm, and Eric D. Glendening, glendening@indstate.edu. Department of Chemistry, Indiana State University, Terre Haute, IN 47809 |
| Reaction pathways for the conversion of methane to methanol on the metal oxide cations (MO+, M=Cr, Mn, Fe, Co, Ni, and Cu) are examined using density functional theory (DFT) B3LYP methods with all-electron valence double-zeta basis sets. Both high-spin and low-spin surfaces were characterized. The surfaces typically reveal spin-inversion crossings in the entrance and exit channels that allow the reactions to proceed via lower energy transition states than would be available if spin were conserved. Natural bond orbital analysis of selected points along the reaction pathways yields a qualitative description of the orbital interactions that facilitate bond rearrangements. |