Understanding of magnetic behavior of the pseudo-binary Co 2- x Ni x Zn 11 : in the light of crystal and electronic structures

• Published in: Dalton transactions : an international journal of inorganic chemistry Vol. 53; no. 34; pp. 14333 - 14346
• Main Authors: Mondal, Amit, Kuila, Sandip Kumar, Pan, Rahul, Patel, Shubham, Buxi, Krishnendu, Saha, Subhadip, Ghanta, Sivaprasad, Avdeev, Maxim, Jana, Partha Pratim
• Format: Journal Article
• Language: English
• Published: England 27.08.2024
• ISSN: 1477-9226; 1477-9234
• DOI: 10.1039/D4DT01498G

A high-temperature synthetic approach is used to prepare a series of pseudo-binary phases-Co Ni Zn . In the structures of Co Ni Zn , the statistical distribution between Co and Ni that is suggested by compositional analysis is confirmed by combined refinements of X-ray and neutron powder diffraction (NPD) experimental data. The aforementioned phases adopt a body-centered cubic lattice with a noncentrosymmetric space group 4̄3 (217). Their crystal structures comprise two 26-atom γ-brass clusters. Each γ-cluster is made of four sequential polyhedral shells: inner tetrahedron (IT), outer tetrahedron (OT), octahedron (OH), and distorted cuboctahedron (CO). Diffraction experiments and the computations endorse that the OT site is statistically distributed by Co and Ni atoms, while the other three sites (IT, OH, and CO) are occupied by Zn atoms. The density of states (DOS) curve for Co Ni Zn displays a similar feature as binary Co Zn , whereas the wide pseudo-gap is formed near as Ni-concentration increases in Co Ni Zn . Bonding analysis shows that this specific atomic distribution nearly optimizes heteroatomic Co/Ni-Zn contacts in the Co Ni Zn and Co Ni Zn . The Co Ni Zn exhibit paramagnetic behavior, whereas Co Ni Zn shows distinct diamagnetic behavior. With the increase in Ni concentration in the structure of Co Ni Zn , Ni atoms gradually substitute the Co atoms at OT sites; hence, magnetic characteristics change from para- to diamagnetism.