Lower Rydberg series of methane : A combined coupled cluster linear response and molecular quantum defect orbital calculation
Vertical excitation energies as well as related absolute photoabsorption oscillator strength data are very scarce in the literature for methane. In this study, we have characterized the three existing series of low-lying Rydberg states of CH4 by computing coupled cluster linear response (CCLR) vertical excitation energies together with oscillator strengths in the molecular-adapted quantum defect orbital formalism from a distorted Cs geometry selected on the basis of outer valence green function calculations. The present work provides a wide range of data of excitation energies and absolute oscillator strengths which correspond to the Rydberg series converging to the three lower ionization potential values of the distorted methane molecule, in energy regions for which experimentally measured data appear to be unavailable.
VELASCO, A.M. ; PITARCH RUIZ, J.V. ; SANCHEZ DE MERÁS, A. ; SANCHEZ MARÍN, J. ; MARTÍN, I. Lower Rydberg series of methane: A combined coupled cluster linear response and molecular quantum defect orbital calculation. En: Journal of Chemical Physics, 2006, vol. 124