ROTATIONAL AND HYPERFINE STRUCTURE IN THE $A^{6} \Sigma^{+} -X^{6} \Sigma^{+}$ ELECTRONIC TRANSITION OF MnO

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1980

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Ohio State University

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The (0,0), (0,1) and (1,0) bands of the A6Σ+X6Σ+ transition of MnO near 5500 {\AA} have been photographed at high dispersion, and partial rotational analyses carried out. The spectrum is unusaully complicated because of the high electron multiplicity, the manganese hyperfine structure and extensive rotational perturbations. It is found that hyperfine perturbations frequently accompany the rotational perturbations; these are a new type of perturbation, resulting from a mixing of the F3 and F4 electron spin components in the upper state through hyperfine matrix elements of the type ΔN=0,ΔJ=±1,ΔF=0 at the places where rotational perturbations occur. Extra lines, obeying the selection rules ΔJ=0,±2, are induced: these give the energy separations of the F3 and F4 electron spin components of the ground State. As a result it has been possible to determine the electron spin fine structure parameters for the two states despite the parallel polarization of the transition. The reason for the great complexity of the A6Σ+ v=0 level is the occurrence of a large avoided crossing near N=26 with a level which might possibly be a highly excited level of the ground state. The ground state Mn-O bond length is r0=1.648 {\AA}, and ΔG12(X6Σ+)=832.41 cm−1.

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