Photofragment Imaging, Spectroscopy, and Theory of MnO.

Density functional and ab initio calculations, along with photodissociation spectroscopy and ion imaging of MnO+ from 21,300 to 33,900 cm-1, are used to probe the photodissociation dynamics and bond strength of the manganese oxide cation (MnO+). These studies confirm the theoretical ground state (5Π) and determine the spin-orbit constant ( A' = 14 cm-1) of the dominant optically accessible excited state (5Π) in the region. Photodissociation via this excited 5Π state results in ground state Mn+ (7S) + O (3P) products. At energies above 30,000 cm-1, the Mn+ (5S) + O (3P) channel is energetically accessible and becomes the preferred dissociation pathway. The bond dissociation energy ( D0 = 242 ± 5 kJ/mol) of MnO+ is measured from several images of each photofragmentation channel and compared to theory, resolving a disagreement in previous measurements. MRCI+Q calculations are much more successful in predicting the observed spectrum than TD-DFT or EOM-CCSD calculations.