Abstract
Recent MOMRIE (microwave optical magnetic resonance induced by electrons) experiments on the d (3p) 3Πu state of ortho- and para-H2 and D2 have revealed discrepancies in measured fine structure parameters (spin-orbit and spin-spin coupling constants, etc.) which are inexplicable in terms of the Born-Oppenheimer approximation. A general theory is developed to account for the effect of homogeneous and heterogeneous perturbations, both regular and irregular, upon the measured fine structure constants of a 3Π electronic state. In particular the various perturbations' mass and symmetry dependences are determined. To make the theory applicable to an analysis of the experimental results for the d(3p) 3Πu states of H2 and D2, other mass dependent effects-adiabatic, Born-Oppenheimer isotope, and vibrational-which alter fine structure are also considered.
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