A (2 + 1) REMPI-PES study of HCI has been carried out in t h e two-photon energy region between 77000 a n d 85500 cm-'. The observed 'A(2), 'A(2), 'II(l) and 'X-(O+) states are characterized as Rydberg states. The one-photon ionization of t h e B 'X+ state has been shown to be dominated by indirect processes involving competition between electronic autoionization and dissociation via superexcited states.
Articles you may be interested inRotationally resolved photoelectron spectra in resonance enhanced multiphoton ionization of HCl via the F 1Δ2 Rydberg state J. Chem. Phys. 95, 8718 (1991); 10.1063/1.461256 Rotational branching ratios and photoelectron angular distributions in resonance enhanced multiphoton ionization of HBr via the F 1Δ2 Rydberg state J. Chem. Phys. 95, 7872 (1991); 10.1063/1.461316 A study of some Rydberg states of CO2 by (3+1) multiphoton ionization spectroscopy J. Chem. Phys. 91, 7399 (1989); 10.1063/1.457264 Multiphoton ionization photoelectron spectroscopy study of OCS: Rydberg vibronic structure and ion state selection J. Chem. Phys. 89, 5527 (1988); 10.1063/1.455559Resonant multiphoton ionization photoelectron spectroscopic study of benzene. Evidence for fast intramolecular vibrational relaxation within the 1 E 1u state ~i~eti,: energy r~solv.ed. electron detection is used to study resonance enhanced multiphoton 10mzatIOn and dissociation of molecular chlorine via the 2 III g Rydberg state. In the twop,hoton ener~ regio? bet~e~n 63 ~ and 73 600 cm -I, a long vibrational progression up to v = 1.5 associated with this mtermedlate gerade Rydberg state is observed. The regularity and magmtude of the vibrational spacing indicate that the 2 IIIg state, converging to the ionic ground state, has virtually unperturbed Rydberg character. However, the molecular signals in the photoelectron spectra show strong deviations from Franck-Condon behavior. In addition intense electron signals arising from one-photon ionization of excited chlorine atoms are ' observed. An interpretation in terms of a competition between electronic autoionization and dissociation from core-excited molecular Rydberg states situated above the lowest ionization energy is ~resent~d. Some of t?e excited atomic states observed are indicative for Rydberg-Rydberg mteracttons at large mtemuclear distances in the dissociation channel.6042
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