A multi-reference CI study of the low-lying valence and Rydberg states of CF3 radical |
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Authors: | Vanessa Cristina de Medeiros Railton Barbosa de Andrade Glauco Favilla Bauerfeldt |
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Institution: | 1. Departamento de Química, CCEN, Universidade Federal da Paraiba, Jo?o Pessoa, Brazil;2. Departamento de Química, Instituto de Ciências Exatas, UFRRJ, Seropédica, Brazil |
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Abstract: | Highly correlated calculations at the multi-reference configuration interaction levels including singles and doubles excitations (MR-CISD) and extensivity corrections (MR-CISD?+?Q) have been performed to study some low-lying valence and Rydberg states of the CF3 radical. Our highest level results (at the MR-CISD?+?Q level) yield the following energy ordering: 3s (7.90?eV)?12A2 (8.61?eV)?3pπ (8.72?eV)?3pz (8.73?eV). MR-CISD results indicate transitions of similar intensities from the ground to the following three final states, in the following order: 3pπ?>?3pz?>?3s. It has also been found that the aforementioned Rydberg states should be responsible for visible emissions and correspond to transitions between bound states. Therefore, it is suggested that the lack of vibrational structure in the visible band of parent systems (e.g. CF3Cl) may be due to a transition from a bound to an unbound state of the parent molecule. |
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Keywords: | CF3 radical Rydberg states absorption fluorescence |
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