Resonance-enhanced multiple-photon ionisation spectroscopy of excited sulphur atoms

Sulfur atoms are produced in the excited 3s ²3p ^{4 1} D ₂ and 3s ²3p ^{4 1} S ₀ levels by two-photon photodissociation of CS₂ in the gas phase in the region 285–305 nm. These excited atoms are detected by three-photon (two to resonance) ionisation at selected laser wavelengths. Many new transitions have been observed which have not been reported previously. The new dark states that have been accessed by two-photon absorption have been characterised and the energy levels with respect to the ground ³ P ₂ state have been determined. Configuration interaction between 6p ³ P ₁, 6p ⁵ P ₁, and 4p¹ P ₁ states, and also between 6p ³ P ₂, 6p ⁵ P ₂, and 4p¹ D ₂ states has been observed. It is found that intermediate states reached from the ¹ S ₀ level through two-photon absorption lie above the first ionisation potential of S⁺(⁴ S ⁰). It is proposed that autoionisation into the ⁴ S ⁰+e^– continuum is a dominant mechanism in the decay of these levels, although ionisation by a further photon absorption is not ruled out.