The nascent chlorine atom (2P) relative spin-orbit state population resulting from UV photolysis of HOCl has been measured by resonance-enhanced multiphoton ionization (REMPI) in single laser experiments. The ratio of (0.30 f 0.07) for CI* : CI has been obtained, indicating a stronger preference for production of ground-state C1 (2P, , , ) than expected from statistical weights. Also, the CI+ arrival-time spectra show that most of the energy available in the photolysis is converted into kinetic energy of the photofragments.
The (3dδ)1,3Φ and (4dδ)1,3Φ Rydberg states of NF have been investigated by multiphoton ionization (MPI) spectroscopy. These states were observed as two-photon resonances in an overall (2+1) MPI process from NF a1Δ produced from the F+N3 reaction. Ab initio calculations performed at the multireference double excitation configuration interaction level showed that the excited Φ states were of Rydberg character with configurations of ...1π45σ22π1(3dδ)1 and ...1π45σ22π1(4dδ)1. The 3Φ←a1Δ two-photon transitions were found to derive their intensities from spin–orbit and spin-uncoupling interactions in the 1Φ3, 3Φ4, 3Φ3, and 3Φ2 upper states. Analysis of the rotationally resolved bands, using a model which includes these factors, allowed the spin–orbit constant, aπ, for the 2π valence orbital to be derived as (159.0±1.0) cm−1. Rotationally resolved envelopes recorded for the (3dδ)1Φ, v′=0, 1←a1Δ, v″=0 and (3pπ)1Σ+, v′=0←a1Δ, v″=0 (2+1) NF MPI bands, could be simulated reasonably well assuming a Boltzmann rotational distribution for the a 1Δ state at ≊180 K. Experiments showed, however, that this was not a true measure of the initial state distribution because of predissociation or perturbation effects in the resonant intermediate state. Assignments for other two-photon resonant NF MPI bands observed in this work are also suggested.
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