title: Atomic orientation following predissociation of the C 3Πg Rydberg state of molecular oxygen.
abstract: (2 + 1) resonance enhanced multiphoton ionization in combination with time-of-flight mass spectroscopy (TOF-MS) has been used to detect both the O((3)P) and O((1)D) fragments produced as a result of predissociation of the C (3)Πg (v = 0) and (v = 1) Rydberg states of O2, accessed via two-photon absorption from the ground X (3)Σg(-) state. In particular, TOF profiles have been recorded at various fixed two-photon absorption wavelengths within the two bands, with circular polarized probe laser light used to probe the angular momentum orientation of these photofragments. All photofragments are found to display coherent orientation resulting from interference between two possible two-photon absorption pathways. The measured orientation is affected by rotational depolarization due to the long lifetime of the excited C state; once this effect is accounted for the orientation is found to be nearly constant over all dissociation wavelengths. The origin of the coherent orientation is attributed to two-photon absorption to different spin-orbit components of the C state.
authors.affiliation: Department of Chemistry, The Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road, Oxford OX1 3QZ, United Kingdom.
authors.forename: A J
authors.initials: AJ
authors.lastname: Gilchrist
authors.forename: G A D
authors.initials: GA
authors.lastname: Ritchie