Photofragmentations, state interactions, and energetics of Rydberg and ion-pair states: Resonance enhanced multiphoton ionization via e and v (B) states of HCl and HBr

(2 + n) resonance enhanced multiphoton ionization mass spectra for resonance excitations to diabatic E¹Σ⁺ (v′) Rydberg and V ¹Σ⁺ (v′) ion-pair states (adiabatic B¹Σ⁺(v′) states) of HⁱCl (i = 35,37) and HⁱBr (i = 79,81) were recorded as a function of excitation wavenumber (two-dimensional REMPI). Simulation analyses of ion signal intensities, deperturbation analysis of line shifts and interpretations of line-widths are used to derive qualitative and quantitative information concerning the energetics of the states, off-resonance interactions between the E states and V states, closest in energy as well as on predissociation channels. Spectroscopic parameters for the E¹Σ⁺ (v′)(v′ = 1) for H³⁵Cl and v′ = 0 for H ⁷⁹Br states, interaction strengths for E - V state interactions and parameters relevant to dissociation of the E states are derived. An overall interaction and dynamical scheme, to describe the observations for HBr, is proposed.