Multireference Wavefunction-Based Investigation of the Ground and Excited States of LrF and LrO

Complete active space self-consistent field (CASSCF) and multi-reference configuration interaction with Davidson correction (MRCI+Q) calculations have been carried out for lawrencium fluoride (LrF) and lawrencium oxide (LrO) molecules, detailing 19 and 20 electronic states for LrF and LrO, respectively. For LrF, two dissociation channels were considered, Lr(2P)+F(2P) and Lr(2D)+F(2P). However, due to the more complex electronic manifold of LrO, three dissociation channels were computed: Lr(2P)+O(3P), Lr(2D)+O(3P), and Lr(2P)+O(1D). In addition, equilibrium bond lengths, harmonic vibrational frequencies omega e, anharmo-nicity constants omega e chi e, Delta G1/2 values, and excitation energies Te for the ground and several excited electronic states were calculated for both molecules, for the first time. Bond dissociation energies (BDEs) were calculated for LrF and LrO using several different levels of theory: unrestricted coupled-cluster with single, double, and perturbative triple excitations (UCCSD(T)), density functional theory (B3LYP, TPSS, M06-L, and PBE), and the correlation-consistent composite approach developed for f-elements (f- ccCA).

Automated summary

In this study, CASSCF and MRCI+Q calculations were performed for LrF and LrO molecules, revealing 19 and 20 electronic states, respectively. Multiple dissociation channels were considered for both molecules, and various properties such as bond lengths, vibrational frequencies, anharmonicity constants, and excitation energies were calculated for the first time. Bond dissociation energies were also calculated using different levels of theory.