Bonding, Thermodynamics, and Spectroscopy of the Metal Borides UB0/+/- and WB0/+/.

ABSTRACT

The bonding and spectroscopy of the UB0/+/- and WB0/+/- molecules were examined by performing high-level electronic structure calculation on their low-lying electronic states. The calculations were performed at the SO-CASPT2 level to obtain the low-lying excited states and at the FPD level to calculate the adiabatic electronic affinities (AEA), ionization energies (IE), and bond dissociation energies (BDE). Compared to UC and UN, UB has a much denser manifold of states below 1.7 eV. The ground state of UB is predicted to be 8I5/2, and that of WB is 6Π7/2. The calculated IEs of UB and WB are 6.241 and 7.314 eV, respectively, and the corresponding AEAs are 1.160 and 1.422 eV. The BDE of UB is predicted to be 223.1 kJ/mol, which is considerably lower than those predicted for UC and UN and ∼35 kJ/mol lower than the BDE of WB. NBO calculations show that the U and B are connected by two 1-electron π bonds and one 1-electron σ bond with substantial ionic character and a bond order of 1.5. There are three unpaired electrons in the 5f on U. WB has less ionic character than UB with a doubly occupied π bond and a singly occupied σ bond for a bond order of ∼1.5. The results show that the U in UB behaves more like an actinide and the W in WB more like a transition metal.