The Σ− states of the molecular hydrogen
A class of doubly excited electronic states of the hydrogen molecule is reported. The states are of Σ− symmetry and are located ca. 200 000 cm−1 above the ground state and about 75 000 cm−1 above the ionization threshold. The electronic wave functions employed to described these states have been expanded in the basis of exponentially correlated Gaussian (ECG) functions with the nonlinear parameters variationally optimized. The lowest 3Σ−g and 1Σ−u states dissociate into hydrogen atoms in the n = 2 state, whereas the lowest 3Σ−u and 1Σ−g states have H(n = 2) and H(n = 3) as the dissociation products. All the four states are attractive and accommodate vibrational levels. The location of the vibrational energy levels has been determined by solving the radial Schrödinger equation within the Born–Oppenheimer approximation.
- This article is part of the themed collection: Explicit-r12 correlation methods and local correlation methods