Abstract
A (2+1) resonance-enhanced multiphoton-ionization photoelectron spectroscopy study of the sulfur atom was performed in the one-photon energy region between 260 and 240 nm. Some 20 previously unobserved even-parity Rydberg states of the sulfur atom are reported, which were accessed by two-photon transitions from the $^{3}$P ground state of the atom, prepared by in situ photodissociation of ${\mathrm{H}}_{2}$S. The ${(}^{4}$${\mathit{S}}^{\mathit{o}}$)np${\mathrm{}}^{3}$P series could be followed up to n=25. This series is perturbed around n=7 by an interloping Rydberg state converging to the first excited ionic limit $^{2}$${\mathit{D}}^{\mathit{o}}$. A two-channel quantum defect theory analysis was performed in order to estimate the composition of the wave functions of the perturbed series members, which is compared with the ionic state branching ratios obtained from photoelectron spectra. This analysis, moreover, enabled the determination of the ionization energy of the lowest ionic state $^{4}$${\mathit{S}}^{\mathit{o}}$ with an improved accuracy as compared to the previously reported value. \textcopyright{} 1996 The American Physical Society.
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