The electronic spectrum of SiH4: Jahn-Teller Rydberg series.

The aim of the present theoretical work is to provide data necessary for a better understanding of the electronic spectrum of the silane molecule, which is affected by the Jahn-Teller effect. By selecting an adequate distorted C2v geometry of SiH4, the three lower Koopmans ionization potentials are evaluated with the equation of motion coupled cluster of singles and doubles method. Vertical excitation energies for the different Rydberg series converging to the three Jahn-Teller components are inferred from ab initio coupled cluster linear response calculations. Absorption oscillator strengths for dipole-allowed electronic transitions are also determined with the molecular-adapted quantum defect orbital methodology. Predictions of new spectroscopic data on SiH4 are reported. [ABSTRACT FROM AUTHOR]