On the electronic structure and spin-orbit coupling of BiB from photoelectron imaging of cryogenically-cooled BiB- anion.

We report a study on the electronic structure and chemical bonding of the BiB molecule using high-resolution photoelectron imaging of cryogenically cooled BiB- anion. By eliminating all the vibrational hot bands, we can resolve the complicated detachment transitions due to the open-shell nature of BiB and the strong spin-orbit coupling. The electron affinity of BiB is measured to be 2.010(1) eV. The ground state of BiB- is determined to be 2Π(3/2) with a σ2π3 valence electron configuration, while the ground state of BiB is found to be 3Σ-(0+) with a σ2π2 electron configuration. Eight low-lying spin-orbit excited states [3Σ-(1), 1Δ(2), 1Σ+(0+), 3Π(2), 3Π(1), 1Π(1)], including two forbidden transitions, [3Π(0-) and 3Π(0+)], are observed for BiB as a result of electron detachment from the σ and π orbitals of BiB-. The angular distribution information from the photoelectron imaging is found to be critical to distinguish detachment transitions from the σ or π orbital for the spectral assignment. This study provides a wealth of information about the low-lying electronic states and spin-orbit coupling of BiB, demonstrating the importance of cryogenic cooling for obtaining well-resolved photoelectron spectra for size-selected clusters produced from a laser vaporization cluster source.