Revisiting Mulliken’s Concepts about Rydberg States and Rydberg−Valence Interactions from Large-Scale Ab Initio Calculations on the Acetylene Molecule

Abstract

A quantitative characterization of the Rydberg and valence singlet electronic states of acetylene lying in the 5-10.7 eV region is performed by using large-scale ab initio calculations. A special attention is paid on the comparison between the present calculations and Mulliken's concepts for Rydberg states, based on single-electron and single-configuration description. Most of the properties of the Rydberg states have been qualitatively understood via this comparison, mainly shown by the shape and size of the outer Rydberg molecular orbital. More quantitatively, Rydberg-valence mixing has been evaluated in several excited energy regions, as for instance, the interaction between the ' (1pig)2 1Ag doubly excited valence state and the manifold of electronic components of the np series, or the interaction between the 1pig 1Bu valence state and the 3dpig 1Sigma(u)+ Rydberg state. The rapid predissociation of the lowest 3s(sigma) 1Piu Rydberg state has been interpreted as a case of Rydbergization, earlier predicted by Mulliken.