Photoelectron spectroscopic studies of multiphoton processes in molecular chlorine involving the 2 1∏g Rydberg state

Abstract

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

Photodissociation–ionization dynamics of molecular chlorine Rydberg states using velocity map imaging

“…Very good agreement was found for the angular and kinetic-energy distributions measured in the two different laboratories using velocity map imaging. Good agreement is also found for the photoelectron kinetic-energy distributions obtained from the images and those reported by Koenders et al 5 for the same intermediate states.…”

“…The goal of this study is to experimentally determine how Cl ϩ is formed and in the process gain more information on the photodynamics of Cl 2 and Cl 2 ϩ . Koenders et al 5 have determined the primary photophysical processes for the most common REMPI detection scheme for Cl 2 , which takes place using two-photon excitation through the vϭ0 -15 vibrational levels of the 2 1 ⌸ g (4s) Rydberg state. Following their discussion, the Cl 2 excitation process and the relevant electronic states involved are shown schematically in Fig.…”

Mass-resolved multiphoton ionization spectroscopy of jet-cooled Cl2. I. Bound-free-bound spectroscopy

“…The strong progression is due to the ͓ 2 ⌸ 1/2 ͔ c 4s; 1 g Rydberg state. Isotopic shifts confirm the previous assignment 12,13 of the origin at 64 026 cm Ϫ1 . Vibrational levels up to vЈϭ19 were observed ͑see also Fig.…”

“…Koenders et al 13 simulated the bandhead contours of the ͑2,0͒ and ͑5,0͒ bands of the ͓ 2 ⌸ 1/2 ͔ c 4s; 1 g Rydberg state in the ͑2ϩ1͒ REMPI spectrum of Cl 2 . B values were obtained, from which ␣ e , B e , and R e were estimated.…”

“…Previous REMPI spectra 12,13 have shown a second very unusual feature in the energy range 64 000-74 000 cm Ϫ1 . Transitions are seen from vЉϭ0 of the ground state to vЈϭ0-15 of the ͓ 2 ⌸ 1/2 ͔ c 4s; 1 g Rydberg state.…”