Abstract
The B (1/2) and C (3/2) ion-pair excited states of XeF are coupled by the rotational Hamiltonian, producing perturbations in the rotational structure of B → X(2Σ+) transitions involving υ‘ levels <5. Five υ‘ -υ‘ ‘ bands in the B → X emission spectrum of the single isotopomer 136Xe19F are analyzed by a deperturbation model to yield improved spectroscopic parameters (cm-1) for the low-υ regions of the B and C states: For B, ωe = 308.09, ωexe = 1.480, Be = 0.145 29, and αe = 0.000 675; for C, ωe = 345.1, ωexe = 2.10, Be = 0.165 42, and αe = 0.001 48. The C state lies 797 cm-1 below the B state, with Re = 2.473 Å. The electronic perturbative coupling element for B−C interactions is 1.632, which is 6% below the simple Hund's case c-based prediction ( ) and just 3% greater than an estimate obtained from a more elaborate case a approach.
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