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

Spectra of Ba autoionizing Rydberg states (n = 60-80) in a varying external electric field, keeping the classical scaled energy ε constant, have been measured. Series converging to the 5d 3/2-as well as to the 5d 5/2-limit have been studied for three values of the scaled energy: ε = −2.94, −2.35 and −1.76, deep in the n-mixing regime around the classical field ionization limit (ε = −2.0). The experiments are interpreted using semiclassical closed-orbit theory by taking the Fourier transform of the experimental spectra. High resolution is obtained using CW laser excitation and large frequency scans. Effects of the large non-hydrogenic core of Ba are investigated by comparing the experimental Fourier spectra with hydrogenic closed-orbit theory for m l = 0-3 incorporating the 5d 2 1 G 4 metastable ground-state wavefunction and assuming only 5d-nf excitation.

Weakly autoionising 5d nf Rydberg states of barium around n"60 have been studied in the presence of a static electric field. The experiment has been carried out in a CW laser-atomic-beam setup. In between the overlapping n"60 and 61 angular momentum manifolds broad 5d63d resonances interact with the manifold states resulting in pronounced interferences. These interferences (anti-crossings) have been analysed by a direct diagonalisation procedure neglecting interactions with the continuum, and by a Multichannel Quantum Defect Theory (MQDT) analysis including continuum interactions.

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