Combined computational and experimental investigation of the La-Cu-S-O quaternary system

TL;DR

This study combines computational modeling and in situ experimental techniques to understand and predict reaction pathways in the La-Cu-S-O system, aiding the discovery of new superconducting materials.

Contribution

It introduces a novel integrated approach using in situ X-ray diffraction and theoretical calculations to elucidate reaction mechanisms in complex inorganic systems.

Findings

Reactions involve redox processes with Cu(II) and S(2-) ions.

Computations confirm favored synthetic pathways.

Experiment and theory show consistency in reaction energetics.

Abstract

The lack of a mechanistic framework for chemical reactions forming inorganic extended solids presents a challenge to accelerated materials discovery. We demonstrate here a combined computational and experimental methodology to tackle this problem, in which in situ X-ray diffraction measurements monitor solid state reactions and deduce reaction pathways, while theoretical computations rationalize reaction energetics. The method has been applied to the La-Cu-S-O quaternary system, following an earlier prediction that enhanced superconductivity could be found in these of new lanthanum copper(II) oxysulfide compounds. In situ diffraction measurements show that reactants containing Cu(II) and S(2-) ions undergo redox reactions, leaving their ions in oxidation states that are incompatible with forming the desired new compounds. Computations of the reaction energies confirm that the observed synthetic pathways are indeed favored over those that would hypothetically form the suggested compounds. The consistency between computation and experiment in the La-Cu-S-O system suggests a new role for predictive theory: to identify and to explicate new synthetic routes for forming predicted compounds.