The electronic states of SeF: A reinterpretation of the chemiluminescent emission of the reaction of selenium with fluorine.
The low-lying doublet and quartet electronic states of the species SeF correlating with the first dissociation channel are investigated theoretically at a high-level of electronic correlation treatment, namely, the complete active space self-consistent field/multireference single and double excitations configuration interaction (CASSCF/MRSDCI) using a quintuple-zeta quality basis set including a relativistic effective core potential for the selenium atom. Potential energy curves for (Lambda+S) states and the corresponding spectroscopic properties are derived that allows for an unambiguous assignment of the only spectrum known experimentally as due to a spin-forbidden X (2)Pi-a (4) summation (-) transition, and not a A (2)Pi-X (2)Pi transition as assumed so far. For the bound excited doublets, yet unknown experimentally, this study is the first theoretical characterization of their spectroscopic properties. Also the spin-orbit coupling constant function for the X (2)Pi state is derived as well as the spin-orbit coupling matrix element between the X (2)Pi and a (4) summation (-) states. Dipole moment functions and vibrationally averaged dipole moments show SeF to be a very polar species. An overview of the lowest-lying spin-orbit (Omega) states completes this description.
Hermoso
Willian
W
Departamento de Química Fundamental, Instituto de Química, Universidade de São Paulo, Brazil.
Ornellas
Fernando R
FR