Optical–optical double resonance spectroscopy of Cl2: Analysis of the 1g(3P1)–A 3Π(1u) system

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Abstract
The 1 g (3 P 1)–A 3Π(1 u ) transition is analyzed by optical–optical double resonance using the 1 g (3 P 1)–A 3Π(1 u )–X 1Σ+ g photoexcitationsequence. The analysis of the 409 transitions in the v’=0–14 and J’=2–51 range of 35Cl2isotope species yields a set of molecular parameters for the 1 g (3 P 1) state in a Dunham‐type expansion: Y 00=59 295.651(5), Y 10=256.6412(30), Y 20=−1.205 36(48), Y 30=3.724(22)×10−3, Y 01=0.114 313 8(60),Y 11=−7.507(15) ×10−4, Y 21=1.96(13)×10−6, and Y 02=−8.10(22)×10−8 with the Ω‐type doubling constant, q v =B (f) v −B (e) v =[3.176(31)−0.0660(50)×(v+1/2)]×10−4 (all in cm−1 and σ in parentheses). An empirical model is given to interpret the spin–orbit couplings between the nascent six ion‐pair states of g‐type symmetry correlating to Cl−(1 S)+Cl+(3 P).