Far infrared laser magnetic resonance of singlet methylene: Singlet–triplet perturbations, singlet–triplet transitions, and the singlet–triplet splittinga)

We have observed and assigned a number of far infrared laser magnetic resonance spectra of CH2 arising from rotational transitions within the lowest vibrational state of the a 1A1 electronic excited state and from transitions between such singlet levels and vibrationally excited levels of the X 3B1 electronic ground state. The singlet–singlet transitions are magnetically active, and the singlet–triplet transitions have electric dipole intensity because of the spin‐orbit mixing of singlet levels with vibrationally excited levels of the triplet state. By identifying four pairs of singlet and triplet levels that perturb each other we can accurately position the singlet and triplet state relative to each other and determine the single–triplet energy splitting. We determine that T0(a 1A1)=3165±20 cm−1 (9.05±0.06 kcal/mol; 0.392±0.003 eV), and Te(a 1A1)=2994±30 cm−1 (8.56±0.09 kcal/mol; 0.371±0.004 eV). A new ab initio calculation of the spin‐orbit matrix element between these two states has been of assista...

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