Frustrated and Allowed Structural Transitions: The Theory-Guided Discovery of the Modulated Structure of IrSi.

Abstract

To the experienced molecular chemist, predicting the geometries and reactivities of a system is an exercise in balancing simple concepts such as sterics and electronics. In this Article, we illustrate how recent theoretical developments can give this combination of concepts a similar predictive power in intermetallic chemistry through the anticipation and discovery of structural complexity in the nominally MnP-type compound IrSi. Analysis of the bonding scheme and DFT-Chemical Pressure (CP) distribution of the reported MnP-type structure exposes issues pointing toward new structural behavior. The placement of the Fermi energy below an electronic pseudogap indicates that this structure is electron-poor, an observation that can be traced via the 18-n rule to the structure's Ir-Ir connectivity. In parallel with this, the structure's CP scheme highlights facile paths of atomic motion that could enable a structural response to this electronic deficiency. Combined, these analyses suggest that IrSi may adopt a more complex structure than previously recognized. Through synthesis and detailed structural investigation of this phase, we confirm this prediction: single-crystal X-ray diffraction reveals an incommensurately modulated structure with the (3+1)D superspace group P21/n(0βγ)00 and q ≈ -0.22b* + 0.29c*. The structural modulations increase the average number of Ir-Ir bonds to nearly match the 18-n expectations of the phase through Ir-Ir trimerization along negative CPs with the incommensurability arising from the difficulty of contracting and stretching the Ir-Ir contacts in a regular pattern without expanding the structure along directions of negative Si-Si CP. Integrating these results with prior analyses of related systems points to a simple guideline for materials design, the Frustrated and Allowed Structural Transitions (FAST) principle: the ease with which competing structural phenomena can be experimentally realized is governed by the degree to which they are supported by the coordination of the atomic packing and electronic factors.