Multiple Bonding in Rhodium Monoboride. Quasi-atomic Analyses of the Ground and Low-Lying Excited States

Abstract

The bonding structures of the ground state and the lowest five excited states of rhodium monoboride are identified by determining the quasi-atomic orbitals in full valence space MCSCF wave functions and the interactions between these orbitals. A quadruple bond, namely two π-bonds and two σ-bonds, is identified and characterized for the X¹Σ⁺ ground state, in agreement with a previous report (Cheung <i>J. Phys. Chem. Lett</i>. 2020, 11, 659-663). However, in all excited states, the bonding is predicted to be weaker because, in these states, one of the σ-bonding interactions has a small magnitude. In the a³Δ and A¹Δ states, the bond order is between a triple and quadruple bond. In the b³Σ⁺ state, the Rh-B linkage is a triple bond. In the c³Π and B¹Π states, the atoms are linked by a double bond due to an additional weakening of the two π-bonds. The decreases in the predicted bond strengths are reflected in the decreases of the predicted binding energies and in the increases of the predicted bond lengths from the X¹Σ⁺ ground state to the c³Π and the B¹Π excited states. Notably, the 5pσ orbital of rhodium, which is vacant in the ground state of the atom, plays a significant role in the molecule.