Photodissociation of CS2 in the Vacuum Ultraviolet; Determination of D° (SC—S)

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Abstract
It has been shown that a major primary photochemical process of CS2 in the vacuum ultraviolet is the reaction, CS 2 → lim hν CS A 1 Π + S 3 P 2 , in apparent violation of the spin conservation rule. From the threshold energy of incident photons required to produce the fluorescence, CS A 1 Π ‐X 1 Σ, D 0 ° ( SC — S ) = 4.463± 0.014 eV or 102.9 ± 0.32 kcal/mole has been obtained in excellent agreement with the value derived previously from the photoionization of CS2. Other related thermochemical data are derived and are compared with those obtained by various methods. The fluorescence excitation spectrum shows peaks corresponding to Rydberg series I and II, indicating that the above reaction is mainly the result of predissociation from Rydberg states. The fluorescence efficiencies became quite small above incident photon energies corresponding to the first ionization potential of CS2. The CS A 1Π fluorescencespectrum produced by the 1236 Å line photolysis shows vibrational levels populated up to v′=5 . The absorption coefficient of CS2 has been measured in the region 1200–1400 Å.

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