posted on 2018-10-02, 00:00authored byKaterina P. Hilleke, Daniel C. Fredrickson
The space requirements
of atoms are generally regarded as key constraints in the structures,
reactivity, and physical properties of chemical systems. However,
the empirical nature of such considerations renders the elucidation
of these size effects with first-principles calculations challenging.
DFT-chemical pressure (DFT-CP) analysis, in which the output of DFT
calculations is used to construct maps of the local pressures acting
between atoms due to lattice constraints, is one productive approach
to extracting the role of atomic size in the crystal structures of
materials. While in principle this method should be applicable to
any system for which DFT is deemed an appropriate treatment, so far
it has worked most successfully when semicore electrons are included
in the valence set of each atom to supply an explicit repulsive response
to compression. In this Article, we address this limiting factor,
using as model systems intermetallics based on aluminum, a key component
in many structurally interesting phases that is not amenable to modeling
with a semicore pseudopotential. Beginning with the Laves phase CaAl2, we illustrate the difficulties of creating a CP scheme that
reflects the compound’s phonon band structure with the original
method due to minimal core responses on the Al atoms. These deficiencies
are resolved through a spatial mapping of three energetic terms that
were previously treated as homogeneous background effects: the Ewald, Eα, and nonlocal pseudopotential components.
When charge transfer is factored into the integration scheme, CP schemes
consistent with the phonon band structure are obtainable for CaAl2, regardless of whether Ca is modeled with a semicore or valence-only
pseudopotential. Finally, we demonstrate the utility of the revised
method through its application to the La3Al11 structure, which is shown to soothe CPs that would be encountered
in a hypothetical BaAl4-type parent phase through the substitution
of selected Al2 pairs with single Al atoms. La3Al11 then emerges as an example of a more general phenomenon,
CP-driven substitutions of simple motifs.