Relativistic ab Initio Accurate Atomic Minimal Basis Sets: Quantitative LUMOs and Oriented Quasi-Atomic Orbitals for the Elements Li-Xe.

Abstract

Valence virtual orbitals (VVOs) are a quantitative and basis set independent method for extracting chemically meaningful lowest unoccupied molecular orbitals (LUMOs). The VVOs are formed based on a singular value decomposition (SVD) with respect to precomputed and internally stored ab initio accurate atomic minimal basis sets (AAMBS) for the atoms. The occupied molecular orbitals and VVOs together form a minimal basis set that can be transformed into orthogonal oriented quasi-atomic orbitals (OQUAOs) that provide a quantitative description of the bonding in a molecular environment. In the present work, relativistic AAMBS are developed that span the full valence orbital space. The impact of using full valence AAMBS for the formation of the VVOs and OQUAOs and the resulting bonding analysis is demonstrated with applications to the cuprous chloride, scandium monofluoride, and nickel silicide diatomic molecules.