Sequential two-photon spectroscopy of some ion-pair states of IBr

Molecular constants of the first E 0⁺ ion-pair state of IBr vapor have been determined using polarization-labeling spectroscopy applied to the sequential transitions E 0⁺ ← B′ 0⁺ ← X 0⁺, while the second f 0⁺ ion-pair state is reported and characterized for the first time. A least-squares, simultaneous analysis of data for the I⁷⁹Br and I⁸¹Br isotopes gives the following constants (in cm^?1) for I⁷⁹Br:

$\text{E}\text{state}\text{: T}{}_{\mathrm{<mtext>e</mtext>}}\text{= 39487.32(12), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{= 119.518(21), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{ξ}{}_{\mathrm{<mtext>e</mtext>}}\text{= 0.2109(12)}$

,

$\text{ω}{}_{\mathrm{<mtext>e</mtext>}}\text{y}{}_{\mathrm{<mtext>e</mtext>}}\text{= ? 2.34(22) × 10}{}^{\mathrm{?4}}\text{, B}{}_{\mathrm{<mtext>e</mtext>}}\text{= 2.9701(14) × 10}{}^{\mathrm{?2}}$

,

$\text{α}{}_{\mathrm{<mtext>e</mtext>}}\text{= 5.43(59) × 10}{}^{\mathrm{?5}}\text{,}\text{and}\text{γ}{}_{\mathrm{<mtext>e</mtext>}}\text{= ? 6.8(16) × 10}{}^{\mathrm{?7}}$

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$\text{F}\text{state}\text{: T}{}_{\mathrm{<mtext>e</mtext>}}\text{= 45382.58(17), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{= 128.805(66), ω}{}_{\mathrm{<mtext>e</mtext>}}\text{ξ}{}_{\mathrm{<mtext>e</mtext>}}\text{= 0.3630(69)}$

,

$\text{ω}{}_{\mathrm{<mtext>e</mtext>}}\text{y}{}_{\mathrm{<mtext>e</mtext>}}\text{= ? 9.7(22) × 10}{}^{\mathrm{?4}}\text{, B}{}_{\mathrm{<mtext>e</mtext>}}\text{= 3.0073(30) × 10}{}^{\mathrm{?2}}\text{,}\text{and}\text{α}{}_{\mathrm{<mtext>e</mtext>}}\text{= 8.52(48) × 10}{}^{\mathrm{?5}}$

. Preliminary data for the first $\text{Ω}\text{= 1}$ ion-pair state, accessed in the sequence $\text{1(}{}^3\text{P}{}_2\text{) ← A(}\text{Ω}\text{= 1) ← X 0}{}^{\mathrm{+}}$, indicate that T_e is ?30 cm^?1 higher in energy than that of the E state.