Double-Exchange Magnetic Interactions in High-Temperature Ferromagnetic Iron Chalcogenide Monolayers.

Smythite ( <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"> <mml:mrow> <mml:msub><mml:mrow><mml:mi>F</mml:mi> <mml:mi>e</mml:mi></mml:mrow> <mml:mn>3</mml:mn></mml:msub> <mml:msub><mml:mi>S</mml:mi> <mml:mn>4</mml:mn></mml:msub> </mml:mrow> </mml:math> ) is an iron-based chalcogenide with a lamellar structure, different from the compositionally identical mineral greigite. Owing to their natural abundance, such transition metal chalcogenides are promising materials for low-cost spintronic-based devices. Herein, we discuss the charge transfer processes and complex magnetic ordering in a two-dimensional (2D) smythite lattice. We find that <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>F</mml:mi> <mml:msup><mml:mrow><mml:mi>e</mml:mi></mml:mrow> <mml:mrow><mml:mn>2</mml:mn> <mml:mo>+</mml:mo></mml:mrow> </mml:msup> <mml:mo>/</mml:mo> <mml:mi>F</mml:mi> <mml:msup><mml:mrow><mml:mi>e</mml:mi></mml:mrow> <mml:mrow><mml:mn>3</mml:mn> <mml:mo>+</mml:mo></mml:mrow> </mml:msup> </mml:mrow> </mml:math> redox couple and complex magnetic ordering are governing factors in the charge transfer processes. A very strong ferromagnetic in-lattice coupling is also observed, which is attributed to the presence of three Fe-centres. To describe the magnetic behaviour molecular and periodic approaches have been considered. We found a substantial increase in Curie temperature with applied mechanical stress due to opening of the double exchange interaction angle. We also observe an in-plane Jahn-Teller distortion, which is further confirmed by the spin-orbit counter plot. Our study thus provides an insight into the double exchange mechanism favoured by the <mml:math xmlns:mml="http://www.w3.org/1998/Math/MathML"><mml:mrow><mml:mi>F</mml:mi> <mml:msup><mml:mrow><mml:mi>e</mml:mi></mml:mrow> <mml:mrow><mml:mn>2</mml:mn> <mml:mo>+</mml:mo></mml:mrow> </mml:msup> <mml:mo>/</mml:mo> <mml:mi>F</mml:mi> <mml:msup><mml:mrow><mml:mi>e</mml:mi></mml:mrow> <mml:mrow><mml:mn>3</mml:mn> <mml:mo>+</mml:mo></mml:mrow> </mml:msup> </mml:mrow> </mml:math> redox couple and results in a strong ferromagnetic ordering.