A rotationally-resolved Rydberg transition of I2 |
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| Authors: | A.R. Hoy S.M. Jaywant J.C.D. Brand |
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| Affiliation: | Department of Chemistry , The University of Western Ontario , London, Ontario, Canada , N6A 5B7 |
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| 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, νF ≈ 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, ωe = 209.29, ωe x e = 0·859, B e = 0·03842 and αe = 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/ωe ≈ 0·5, corresponding to ‘intermediate’ coupling. Energy considerations indicate that R should be assigned to the 0 u + state of either the configuration (2430 Π1/2g )6pσ u , or of (2421 4Σ u -)6sσ g . This state is the first extra-valence state of I2 to be rotationally analysed. |
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