Photolytic spectroscopy of simple molecules. II. The production of 6P atoms from the X ¹Σ_g state of Cs₂

In this work the two-photon technique for the study of selective photolysis described in the preceding article was used for the measurement of the relative cross sections for the photolysis of Cs₂ into each of the energetically possible product channels that could have been reached at wavelengths in the range from 445 to 640 nm. The resulting dispersion curves showed three relatively broad absorption bands, each leading to a different distribution of population among the product states. A relatively broad band in the blue region of the spectrum was found to yield an inverted branching ratio for dissociation which favored the more highly excited product by a factor of better than 50 to 1. This particular result implied that continuous wave, stimulated emission should be obtained from the 5 ²D _3/2→6 ²P_1/2 transition of atomic cesium with adequate photolytic pumping of Cs₂ at blue wavelengths. An analysis of the complete photolysis spectrum obtained in this work indicated that both dissociation and predissociation mechanisms were involved. These results led to the construction of approximate potential curves for a new ³Σ_u state correlated with Cs(6 ²P _3/2) and new ¹Σ_u and ³Σ _u states correlated with the 5 ²D states of atomic cesium.