Relativisticab InitioAccurate Atomic Minimal Basis Sets: Quantitative LUMOs and Oriented Quasi-Atomic Orbitals for the Elements Li–Xe

Citations Over Time

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.

Related Papers

• → Molecule intrinsic minimal basis sets. I. Exact resolution of ab initio optimized molecular orbitals in terms of deformed atomic minimal-basis orbitals(2004)171 cited
• → Uniform Localization of Atomic and Molecular Orbitals. I(1967)177 cited
• → A systematic preparation of new contracted Gaussian-type orbital basis sets. II. Test basis set for Cu2 molecule with and without splitting of the outer orbitals(1980)97 cited
• → Optimization of numerical orbitals in molecular MO‐LCAO calculations(2003)16 cited
• → Invariant atomic orbitals by radial moment analysis of accurate molecular orbitals(2009)1 cited