FLUOROSULFATE RADICAL ROTATIONAL ANALYSIS OF 5160-A SYSTEM AND MOLECULAR GEOMETRY

Empirical analysis of the rotational structure of the origin band of the 5160 Å absorption transition of the fluorosulfate radical shows that it can be treated as two separate vibronic transitions to Jahn-Teller/spin orbit split potential surfaces of an 2E excited electronic state. The transition (+000) to the upper surface appears to consist of a series of prominent PQ sub-bands with underlying RQ sub-bands, and series of prominent PPK(J) lines. Similar structure is observed for other bands in the system. For the molecule in the v1 = v2 = ⋯ = 0 level associated with the upper potential surface in the excited state, the derived rotational constants are A0′ = 0.1720cm-1, and B0′ = 0.1579cm-1; the latter is almost identical with the value of B0″ in the ground state. The electronic orbital angular momentum is partially quenched in this upper state level by the C3v potential symmetry of the molecule, the electronic Coriolis coefficient ζe being about 0.45. The proposed excited state geometry, on the assumption of C3v symmetry is; r(SO) = 1.49 A ̊, r(SF) = 1.64 A ̊, angle OSF = 106°. © 1969.