Population Of The P-3(2,1,0) Fine-Structure States In The 3S And 3P Photoionization Of Atomic Chlorine

In a high-resolution photoelectron-spectrometry study of the photoionization of chlorine atoms in both the 3s and 3p subshells, we were able to resolve contributions from ionic states with specific J values and measure the relative populations of these fine-structure components. Our photoelectron spectra, recorded at hnu = 29.2 eV, give ratios of P-3(2):P-3(1):P-3(0) = 100:40.5:9.5 for 3p photoionization and P-3(2):P-3(1) = 100:31 for 3s photoionization. While the results for 3p ionization are in ar-cord with predictions based on a simple geometric analysis, the contribution of the P-3(1) state in 3s photoionization is larger than that predicted by this simple model. The geometric predictions are also compared with results from a similar measurement of the population of the 4p-1(3p(J)) states produced in the 4p ionization of Br and with earlier work on the production of 3D2,1,0 states in d-shell photoionization of Cu and Ag