Upper vibrational states of the B″3Πu state of 32S2

Abstract

Spectra and lifetime measurements of the strongly mixed B″ ³ Π _u and B ³ Σ _u ⁻ states of ³² S ₂ are presented covering v′ = 710 of the B state and v′ = 1221 of the B″ state. This extends our earlier work (M. E. Green and C. M. Western, J. Chem. Phys., 1996, 104, 848) to just above the first dissociation limit ( ³ P + ³ P) of S ₂ . This includes several previously unobserved vibrational states and components of the B″ state. A model for these states is presented that accounts for the B/B″ perturbations, though it is clear that mixing with other states in the same region is significant. Our spectra suggest that at least some components of the B″ state converge to the ³ P ₂ + ³ P ₀ limit, though the states at this energy are almost certainly strongly mixed with other states.