Templating Structural Progessions in Intermetallics: How Chemical Pressure Directs Helix Formation in the Nowotny Chimney Ladders.

Abstract

In the structural diversity of intermetallic phases, hierarchies can be perceived relating complex structures to relatively simple parent structures. One example is the Nowotny Chimney Ladder (NCL) series, a family of transition metal-main group (T-E) compounds in which the T sublattices trace out helical channels populated by E-atom helices. A sequence of structures emerges from this arrangement because the spacing along the channels of the E atoms smoothly varies relative to that of the T framework, dictated largely by optimization of the valence-electron concentration. In this Communication, we show how this behavior is anticipated and explained by the Density Functional Theory-Chemical Pressure (DFT-CP) schemes of the NCLs. A CP analysis of the RuGa2 parent structure reveals CP quadrupoles on the Ga atoms (telltale signs of soft atomic motion) that arise from overly short Ru-Ga contacts along one axis and underutilized spaces in the perpendicular directions. In their placement and orientation, the CP quadrupoles highlight a helical path of facile movement for the Ga atoms that avoids further compression of the already strained Ru-Ga contacts. The E atoms of a series of NCLs (in their DFT-optimized geometries) are all found to lie along this helix, with the CP quadrupole character being a persistent feature. In this way, the T sublattice common to the NCLs encodes helical paths by which the E-atom spacing can be varied, creating a mechanism to accommodate electronically driven compositional changes. These results illustrate how CP schemes can be combined with electron-counting rules to create well-defined structural sequences, potentially guiding the discovery of new intermetallic phases.