The D′ → A′ transition in I2

A detailed vibrational analysis is given for the D′(2g) → A′(2u³Π) transition (3300–3460 Å) in I₂. The assignments include ～ 150 v′-v″ bands in ¹²⁷I₂ and ～100 in ¹²⁹I₂, spanning v′ levels 0–15 and v″ levels 4–30. These bands are mainly red-degraded but include some violet-degraded and line-like features. The analysis is corroborated by Franck-Condon and band profile calculations. The least-squares fit yields the following constants (cm^?1); ΔT_c = 30 340.8, ω′_e = 103.95, ω_eχ′_e = 0.206, ω″_e = 106.1, ω_eχ″_e = 0.81. Anomalous behavior in the vibrational level structure above v″ = 23 makes the extrapolation to the A′ dissociation limit uncertain, so the absolute energies of both states remain ill-defined. However there is a possibility that the D′ state is the state labeled α by King et al. Chem. Phys. 56, 145–156 (1981)], in which case the energies are known precisely. There is evidence of weak emission from at least two other electronic transitions in this spectral region, probably $\text{D(0}{}^{\mathrm{+}}\text{u) → X(}{}^1\text{Σ}{}_{\mathrm{g}}{}^{\mathrm{+}}\text{)}$ ($\text{λ}\text{< 3300}\text{A}\text{?}$) and β → A(1u³Π) ($\text{λ}\text{> 3300}\text{A}\text{?}$).