A rotationally-resolved Rydberg transition of I₂

Abstract

Rotationally-resolved bands leading to a Rydberg state R 0 _u ⁺ of molecular I₂ are observed in a two-stage, three-photon transition from the ground state. The R 0 _u ⁺ state interacts homogeneously with high vibrational levels, ν_F ≈ 200–250, of an ionic state F 0 _u ⁺, the perturbation being directed by the vibrational overlap integrals towards even-numbered vibrational levels of R. Spectral constants of R 0 _u ⁺ are (in cm^-1): T _e = 61665·15, ω_e = 209.29, ω_e x _e = 0·859, B _e = 0·03842 and α_e = 1·6 × 10^-4. The electronic matrix element for the R, F interaction (excluding one deviant result) is |W _e| = 107 ± 1 cm^-1; thus W _e/ω_e ≈ 0·5, corresponding to ‘intermediate’ coupling. Energy considerations indicate that R should be assigned to the 0 _u ⁺ state of either the configuration (2430 Π_1/2g )6pσ _u , or of (2421 ⁴Σ _u ^-)6sσ _g . This state is the first extra-valence state of I₂ to be rotationally analysed.

Notes

Contribution No. 366 from the Photochemistry Unit, The University of Western Ontario.