A model of the B 1Σ+–D ’ 1Σ+ Rydberg–valence predissociating interaction in the CO molecule
| Autor: | F. Rostas, J.‐M. Robbe, C. Letzelter, W.‐Ü L. Tchang‐Brillet, P. S. Julienne |
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| Rok vydání: | 1992 |
| Předmět: | |
| Zdroj: | The Journal of Chemical Physics. 96:6735-6745 |
| ISSN: | 1089-7690 0021-9606 |
| DOI: | 10.1063/1.462561 |
| Popis: | The strong interaction between the B 3sσ 1Σ+ Rydberg state and the D’ 1Σ+ valence state of the CO molecule is shown to cause large changes in the vibrational and rotational constants of the B state, as well as predissociation of all rotational levels of B (v’=2) and a breaking off in the emission of B (v’=1) levels at J=36 in 12C 16O and J=37 in 13C 16O. A two‐state diabatic model of the Rydberg–valence interaction is constructed and vibrational term values, widths, and intensities are calculated by close coupling in order to account for the strong mixing. The model separates the differences between the spectroscopic constants of the B state and those of the ground state molecular ion into two components, one due to the R‐dependent quantum defect of the B state and another due to the strong Rydberg–valence perturbation. The perturbation is characterized by a constant coupling matrix element of 2900 cm−1 inside the crossing point of the two diabatic potentials, decaying to zero at long internuclear distanc... |
| Databáze: | OpenAIRE |
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