SUMMARYA direct numerical method for atomic electronic structure simulation of transition metals in matter is proposed in order to perform precise investigations of low-symmetry effects. Contrary to the spin-polarized unrestricted Hartree-Fock approach, well known as the different orbitals for different spins method, the radial orbitals are split in accordance with the site symmetry of the ion in the crystal and transformed under the irreducible representations of a given point group. In the frame of a free-atomic embedding scheme, the electronic structure of the transition metal ion is calculated with a non-spherical ab initio potential of nearest neighbours. An original procedure using a somewhat generalized Gram-Schmidt orthogonalization process is developed. Thus d-ion radial orbitals are orthogonalized to the appropriate ligand ones in a numerically self-consistent way. The theoretical content is illustrated by detailed calculations of transition metal d 9,10 configurations in a square planar Me : [O 2− ]4 system. To find the copper peculiarity a general picture of the electronic structure of such systems is given through a comparative study of Zn, Cu and Ni. The influence of small features in the radial electron distribution on spectra can be observed. Two types of excited electronic states recognized as susceptible to structure and overcontracted have been found. The comparison of calculations with free-atomic and 'embedded' ligand wave functions shows that an extremely large role is played by ligand spatial stretching in the close metal clusters. Also, some important features of high-Tc superconductivity are considered through calculations of d 9 -d 10 crossing revealed for copper in the cluster.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.