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Title: Dissociation dynamics of high-v Rydberg states of molecular hydrogen

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.464495· OSTI ID:6585759

A high-resolution, state-selective investigation of the decay of (X ²Σ⁺g)np, v'≥9 Rydberg states of H2 into the H(1s)+H(3I) and H(1s)+H(4I) dissociation continua has been performed. The (X ²Σ⁺g)np Rydberg states were excited by double-resonance excitation via the E,F ¹Σg⁺, v=6, J=0 and 1 states, and the H(3I) and H(4I) dissociation products were detected by monitoring the energy-resolved photoelectrons produced by nonresonant photoionization of the fragments. The energy region of interest (138 800--140 000 cm⁻¹) includes the X ²Σ⁺g, v⁺=9, N⁺=0--3 ionization thresholds, the H(1s)+H(4I) dissociation threshold, and the H⁺+H⁻ ion-pair threshold. Evidence of both direct and indirect dissociation involving both singly and doubly excited electronic states is observed. Comparisons to the previously observed X ²Σ⁺g, v⁺=8 constant-ionic-state photoelectron spectrum and the ion-pair spectrum observed in the same energy region reveal strong competition between the ionization and dissociation processes through both rovibrational and electronic interactions.

Research Organization:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Organization:
USDOE; Office of Energy Research (OER); Office of Health and Environmental Research (OHER)
DOE Contract Number:
W-31-109-ENG-38
OSTI ID:
6585759
Journal Information:
Journal of Chemical Physics, Vol. 98, Issue 11; ISSN 0021-9606: JCPSA6
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English