A multi-reference CI study of the low-lying valence and Rydberg states of CF₃ radical

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) < 3p_π (8.72 eV) < 3p_z (8.73 eV). MR-CISD results indicate transitions of similar intensities from the ground to the following three final states, in the following order: 3p_π > 3p_z > 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.

GRAPHICAL ABSTRACT

Keywords:

• CF₃ radical
• Rydberg states
• absorption
• fluorescence

Additional information

Funding

The authors are grateful to the CNPq (Conselho Nacional de Desenvolvimento Científico e Tecnológico) (grant number: 309785/2015-4), CAPES and FINEP (Brazilian agencies) for financial support.