Diagrammatic Separation of Different Crystal Structures of A₂BX₄ Compounds Without Energy Minimization: A Pseudopotential Orbital Radii Approach

Abstract The A₂BX₄ family of compounds manifest a wide range of physical properties, including transparent conductivity, ferromagnetism, and superconductivity. A 98% successful diagrammatic separation of the 44 different crystal structures of 688 oxide A₂BX₄ compounds (96% for 266 oxide‐only) is described by plotting the total radius of the A atom R_A versus the radius of the B atom R_B for many A₂BX₄ compounds of known structure types and seeking heuristically simple, straight boundaries in the R_A versus R_B plane that best separate the domains of different structure types. The radii are sums R_A = R_s(A) + R_p(A) of the quantum‐mechanically calculated “orbital radii” R_s(R_p), rather than empirical radii or phenomenological electronegativity scales. These success rates using first‐principles orbital radii uniformly exceed the success rates using classic radii. Such maps afford a quick guess of the crystal structure of a yet unmade A₂BX₄ compound by placing its atomic orbital radii on such maps and reading off its structure type.