Magnetic ligands in the $Pt_2(dta)_4I$ compound

TL;DR

This paper reinterprets the electronic structure of the $Pt_2(dta)_4I$ compound using ab initio calculations, revealing active ligand participation and challenging previous charge ordering assumptions, aligning better with experimental data.

Contribution

It provides a new electronic structure model for $Pt_2(dta)_4I$, emphasizing ligand involvement and disputing prior intra-dimer charge ordering assumptions.

Findings

Active participation of ligands in magnetic properties

Unrealistic intra-dimer charge ordering assumption

Rationalization of the 3:1 Pt^{2+}/Pt^{3+} ratio in XPS spectra

Abstract

We report a reinterpretation of the electronic structure of the $(Pt)_2I(dta)_4$ compound, based on {\em ab initio} embedded fragment calculations. Our major results are the following. First, the usually assumed electronic intra-dimer charge ordering is unrealistic. Second, the $(dta)$ ligands take part actively in the magnetic properties of the system. The proposed electronic structure is favorably confronted to experimental data. In particular, the unexplained $3:1$ $Pt^{2+}/Pt^{3+}$ abundances ratio of the XPS spectra is rationalized.