Molecular and all solid DFT studies of the magnetic and chemical bonding properties within KM[Cr(CN)$_6$] (M = V, Ni) complexes

TL;DR

This study uses DFT to analyze the magnetic and chemical bonding properties of KM[Cr(CN)$_6$] complexes with M = V, Ni at molecular and solid levels, confirming magnetic ground states and exploring bonding characteristics.

Contribution

It provides a combined molecular and solid-state DFT analysis of magnetic interactions and bonding in KM[Cr(CN)$_6$] complexes, including isomerism aspects.

Findings

V complex is antiferromagnetic with J = -296.5 cm$^{-1}$

Ni complex is ferromagnetic with J = +40.5 cm$^{-1}$

Solid state calculations confirm magnetic ground states and J magnitudes

Abstract

A study at both the molecular and extended solid level in the framework DFT is carried out for KM[Cr(CN)$_6$] (M = V, Ni). From molecular calculations, the exchange parameters J are obtained, pointing to the expected magnetic ground states, i.e., antiferromagnetic for M = V with J = -296.5 cm$^{-1}$ and ferromagnetic for M = Ni with J = +40.5 cm$^{-1}$. From solid state computations the same ground states and J magnitudes are confirmed from energy differences. Furthermore an analysis of the site projected density of states and of the chemical bonding is developed in which the cyanide ion linkage is analyzed addressing some isomerism aspects.