Chemical bonding in crystalline silver halides: Wannier-type atomic functions approach

A method for chemical bonding analysis based on the minimal basis of Wannier-type atomic orbitals (WTAOs) is suggested. WTAOS are formed by the Bloch states of upper valence and lower conduction bands. They are centered on atoms and have the symmetry of atomic-like functions. A variational procedure is formulated for WTAOs generation. This procedure is equally applied to Bloch states in a basis of LCAO, plane waves, or any other set of functions. The proposed approach is used in analysis of the local properties of the electronic structure (atomic charges, bona orders, covalencies, and valencies) in silver halides AgF, AgCl, and AgBr obtained by the Hartree-Fock LCAO method. The advantages of WTAOs population analysis in comparison to the traditional LCAO Mulliken and Lowdin ones are discussed. (C) 2003 Wiley Periodicals, Inc.