Theoretical calculations of spin-Hamiltonian parameters for the square planar Pd⁺ clusters in the γ-irradiated A₂PdCl₄ (A = K, NH₄) crystals

Abstract

The spin-Hamiltonian parameters (g factors g_//, and hyperfine structure constants A_//, ) for the square planar Pd⁺ clusters in the γ-irradiated A₂PdCl₄ (A = K, NH₄) crystals are calculated from the high-order perturbation formulas based on the cluster approach (in which the admixture between d orbitals of dⁿ ion and p orbitals of ligand ions via covalence effect is considered) for d⁹ ions in the tetragonal symmetry with the ground state In the calculations, the crystal-field parameters are estimated from the superposition model related to the square planar structure. The calculated results are in reasonable agreement with the experimental values.

Keywords:

• electron paramagnetic resonance
• spin-Hamiltonian parameters
• crystal- and ligand-field theory
• Pd⁺
• A₂PdCl₄ (A = K, NH₄)

Acknowledgements

This project is supported by the Natural Science Foundation Project of CQ CSTC (Grant No. CSTC2011jjA50015), the Key Project of Chinese Ministry of Education (No. 212139) and the Natural Science Foundation Project of CQ (Grant No. KJ120804, KJ120826).