A two-color (1+1′)+1 multiphoton ionization study of CS2 in the 61 000–65 600 cm−1 energy region

Abstract

The (1+1′)+1 resonance enhanced multiphoton ionization (REMPI) spectrum of jet-cooled CS2 has been recorded in the 61 000–65 600 cm−1 excitation energy range. Four prominent band groups are observed that can be assigned to Δν2=−1 and Δν2=1 sequences of the two-photon electronically forbidden 4p 1,3Δu←X̃ 1Σ+g transitions. Weak bands to higher energy appear to be associated with the 310, 230 and 110210 bands and corresponding sequence bands. The results show that the upper states are not 3d Rydberg states as has been previously supposed, and are consistent with a recent reinvestigation of the corresponding (3+1) REMPI spectrum. Further experimental information is obtained on the anomalous vibrational band structure of transitions to the 3Δu state. The 201 and 212 bands of the 4p 1Πu←X̃ 1Σ+g transition are also observed, but are much weaker, suggesting that vibronic interactions are less important in this state compared to the 4p 1,3Δu states.