Much of chemistry is about bonds, but sometimes it can also be about anti-bonds. It is also true that the simplest of molecules can have quite subtle properties. Thus most undergraduate courses in chemistry deal with how to describe the bonding in the diatomics of the first row of the periodic table.
The triplet and singlet potential curves of Be2 generated by single and double excitations from 2σu into 3σg and (or) 1πu are studied with a multireference configuration interaction (MRD-CI) method. Relative to X1Σg+(2σg2 σu2) with Re = 4.72 bohr and ωe = 258 cm−1 (calculated here), these antibonding MO → bonding MO excitations lead to average decreases in bond distance (in bohr) of 0.55 (2σu → 3σg), 0.88 (2σu → 1πu), 0.93 (2σu2 → 3σg1πu), and 1.22 (2σu2 → 1πu2). The increase in vibrational frequencies ranges from 240 to 600 cm−1. The 3σg MO is found to be less bonding than 1πu, confirming predictions made by Bader et al. The experimental states A1Πu and B1Σu+ correspond to doubly excited 11Πu (2σu2 → 3σg1πu) and singly excited 11Σu+(2σu → 3σg), respectively. The 13Σg− and 11Δg states, both 2σu2 → 1πu2, preserve their doubly excited structure up to dissociation. Within the Franck–Condon region, 13Πu changes from bound (2σu2 → 3σg1πu) to repulsive (mixed 2σu → 1πg/2σg → 1πu), thereby creating the unusual situation of a strongly bound potential (short Re, high ωe) with an adiabatic dissociation energy near zero. The singlet counterpart 11Πu, however, behaves regularly as its doubly excited character is maintained up to large R(Be—Be). Key words: ab initio calculations, beryllium dimer, doubly excited states, electronic transitions, potential curves.