New REMPI observations and analyses for Rydberg and ion-pair states of HI

Photofragmentation, state interaction, and energetics of Rydberg and ion-pair states: Resonance enhanced multiphoton ionization of HI

“…17,25 It should be noted that the original assignment of the H(1) state by Ginter et al 25,33 to the E 1 + (ν = 0) state was reassigned recently. 17 All the major types of spectral perturbations (line-shift (LS), line-intensity (LI), and line-width (LW)-effects) are observed in the spectra. In particular, severe LS-effects are seen in the Q line series for the H(1) and O(0) spectra, where irregular orders of J quantum numbers are observed (see 1(a) and 1(b)).…”

“…It should be noted that the Rydberg parentage of all of the states mentioned in this paper has been addressed before. 17 It was noted that this Rydberg state was experiencing some perturbation effects due to interactions with the V (m + 7) ion-pair state. 17 Here, we will clarify, qualitatively and quantitatively, the nature of this interaction.…”

“…17 It was noted that this Rydberg state was experiencing some perturbation effects due to interactions with the V (m + 7) ion-pair state. 17 Here, we will clarify, qualitatively and quantitatively, the nature of this interaction. Furthermore, we will consider evidences for a possible interaction involvement of the k 3 1 (ν = 1) state, which is close in energy.…”

“…5 The UV, VUV, and multiphoton excitation spectroscopy of these compounds is very rich in structure showing clearly resolved rotational bands due to excitation to Rydberg and ion-pair states. [6][7][8][9][10][11] Spectral perturbations showing as line shifts 7,8,10,[12][13][14][15][16][17][18][19][20] and/or as line intensity fluctuations 7,8,10,[12][13][14][15][16][17][18][19][21][22][23] are frequently observed as effects of state interactions and/or predissociation processes. 7-9, 12, 13, 18, 21 These are seen both in absorption 22,[24][25][26][27][28][29] and REMPI spectra.…”

“…[18][19][20] Whereas most of the studies of hydrogen iodide (HI) have focused on the spectral assignments and the energetics of the Rydberg and ion-pair states, little emphasis has been placed on spectral perturbations for HI. Apart from statements concerning perturbation observations, 17,25,33 no detailed analyses of the spectral perturbations for HI have been reported. In this paper we will emphasize the perturbation effects, involving both homogenenous and heterogenenous state interactions, between the following Rydberg and ion-pair states: Ginter et al 25 have reported perturbation observations in the absorption spectra due to transitions to the V 1 + (ν = m + 6, m + 9) and k 3 1 (ν = 1) states and Pratt and Ginter 33 mention intensity anomalies in a REMPI spectrum for a resonance excitation to the I 1 2 (ν = 0) state.…”