The Intermetallic Reactivity Database: Compiling Chemical Pressure and Electronic Metrics toward Materials Design and Discovery

Buskirk, Jonathan S. Van; Kraus, Joseph D.; Fredrickson, Daniel C.

doi:10.1021/acs.chemmater.3c00214

Cited by 9 publications

(14 citation statements)

References 65 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The general applicability of the sc-DFT-CP method is tested through the analysis of electronic structure data for 206 structures obtained from the Intermetallic Reactivity Database (IRD). 59 The ibH charges calculated for this dataset correlate with those obtained in QTAIM analysis, but with more realistic values in some cases. We also compare the Ewald partitioning in the original and sc-DFT-CP method, with the parent structures to the MgCu 2 -type/ CaCu 5 -type intergrowth series appearing as points where the new approach has particularly large differences.…”

Section: Introductionsupporting

confidence: 54%

“…To explore the properties of the ibH charges over a broader range of systems, we calculated them for the full series of entries in the Intermetallic Reactivity Database (IRD). 59 In testing the method on this diverse series of compounds, one issue that comes quickly to the foreground is the difficulty of obtaining converged electronic structures for free anions with sufficiently large negative charges, e.g., the As atom in InAs. Indeed, such anions are normally not encountered in isolation but as part of an ionic crystal structure where positively charged counterions serve to stabilize the anions.…”

Section: The Self-consistent Dft-cp Methodsmentioning

confidence: 99%

“…16,27 However, carrying out this procedure requires a significant number of auxiliary calculations, while an analysis of the IRD entries suggests that the necessary information for the localized electron count determination is present within the equilibrium volume CP scheme. 59 The previous section's definition of binary Hirshfeld atomic volumes that intersect the Hirshfeld-inspired contact volumes opens the path to a straightforward assignment of these parameters without additional DFT calculations, or assumptions about equality between the atomic pressures of different sites. We simply note that using the free ion electron densities, there are two separate ways of calculating a net atomic pressure: one could integrate the pressure map within an atom's binary Hirshfeld cell to obtain the pressure within that atom's region or one could integrate the pressures within the contact volumes for which that atom participates, yielding the average pressure from its interatomic interactions.…”

Section: The Self-consistent Dft-cp Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Self-Consistent Chemical Pressure Analysis: Resolving Atomic Packing Effects through the Iterative Partitioning of Space and Energy

Sanders

Buskirk

Hilleke

et al. 2023

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

While planewave DFT methods offer capabilities to calculate the relative stabilities and many physical properties exhibited by solid state structures, their detailed numerical output does not easily map onto the often empirical concepts and parameters used by synthetic chemists or materials scientists. The DFT-chemical pressure (CP) method is an approach to bridging this divide by explaining or anticipating a variety of structural phenomena in terms of atomic size and packing effects, but its reliance on adjustable parameters has limited the method’s predictive potential. In this article, we present the self-consistent (sc)-DFT-CP analysis, in which the criterion of self-consistency is used to automatically solve these parameterization issues. We begin by illustrating the need for this improved method with the results for a series of CaCu5-type/MgCu2-type intergrowth structures, where unphysical trends emerge that have no clear structural origin. To address these challenges, we derive iterative treatments for assigning ionicity and for the partitioning of the E Ewald + E α terms in the DFT total energy into homogeneous and localized terms. In this method, self-consistency is achieved between the input and output charges from a variation of the Hirshfeld charge scheme, while the partitioning of the E Ewald + E α terms is adjusted to create equilibrium between the net atomic pressures calculated within atomic regions and from the interatomic interactions. The behavior of the sc-DFT-CP method is then tested using electronic structure data for several hundred compounds from the Intermetallic Reactivity Database. Finally, we return to the CaCu5-type/MgCu2-type intergrowth series with the sc-DFT-CP approach, showing that trends in the series are now easily traced to changes in the thicknesses of the CaCu5-type domains and lattice mismatch at the interface. Through this analysis and the complete update to the CP schemes in the IRD, the sc-DFT-CP method is demonstrated as a theoretical tool for the investigation of atomic packing issues across intermetallic chemistry.

show abstract

Section: Introductionsupporting

confidence: 54%

Section: The Self-consistent Dft-cp Methodsmentioning

confidence: 99%

Section: The Self-consistent Dft-cp Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Self-Consistent Chemical Pressure Analysis: Resolving Atomic Packing Effects through the Iterative Partitioning of Space and Energy

Sanders

Buskirk

Hilleke

et al. 2023

J. Chem. Theory Comput.

Self Cite

View full text Add to dashboard Cite

show abstract

“…It remains unclear, however, why under certain conditions the IrIn 3 -type is preferred. Here, we combine DFT-reversed approximation Molecular Orbital (DFT-raMO) analysis and DFT-Chemical Pressure (DFT-CP) analysis − to determine how the electronic structure and atomic packing interact to shape the structural preferences in these systems. We will see that the different ( n , m ) configurations for the two polymorphs have distinct spatial requirements and are adapted for different T/E atomic size ratios.…”

Section: Introductionmentioning

confidence: 99%

Entropic Control of Bonding, Guided by Chemical Pressure: Phase Transitions and 18-n+m Isomerism of IrIn₃

Lim

Fredrickson

2023

Inorg. Chem.

Self Cite

View full text Add to dashboard Cite

As with other electron counting rules, the 18-n rule of transition metal–main group (T–E) intermetallics offers a variety of potential interatomic connectivity patterns for any given electron count. What leads a compound to prefer one structure over others that satisfy this rule? Herein, we investigate this question as it relates to the two polymorphs of IrIn3: the high-temperature CoGa3-type and the low-temperature IrIn3-type forms. DFT-reversed approximation Molecular Orbital analysis reveals that both structures can be interpreted in terms of the 18-n rule but with different electron configurations. In the IrIn3 type, the Ir atoms obtain largely independent 18-electron configurations, while in the CoGa3 type, Ir–Ir isolobal bonds form as 1 electron/Ir atom is transferred to In–In interactions. The presence of a deep pseudogap for the CoGa3 type, but not for the IrIn3 type, suggests that it is electronically preferred. DFT-Chemical Pressure (CP) analysis shows that atomic packing provides another distinction between the structures. While both involve tensions between positive Ir–In CPs and negative In–In CPs, which call for the expansion and contraction of the structures, respectively, their distinct spatial arrangements create very different situations. In the CoGa3 type, the positive CPs create a framework that holds open large void spaces for In-based electrons (a scenario suitable for relatively small T atoms), while in the IrIn3 type the pressures are more homogenously distributed (a better solution for relatively large T atoms). The open spaces in the CoGa3 type result in quadrupolar CP features, a hallmark of low-frequency phonon modes and suggestive of higher vibrational entropy. Indeed, phonon band structure calculations for the two IrIn3 polymorphs indicate that the phase transition between them can largely be attributed to the entropic stabilization of the CoGa3-type phase due to soft motions associated with its CP quadrupoles. These CP-driven effects illustrate how the competition between global and local packing can shape how a structure realizes the 18-n rule and how the temperature can influence this balance.

show abstract

The Zintl Concept Applied to Intergrowth Structures: Electron‐Hole Matching, Stacking Preferences, and Chemical Pressures in Pd₅InAs

Kraus,

Van Buskirk,

Fredrickson

2023

Zeitschrift anorg allge chemie

Self Cite

View full text Add to dashboard Cite

Enumerating the potential stacking sequences of layers is a fundamental way to account for the structure diversity of solid state compounds. In many cases, these stacking variations represent polymorphs with only small energetic differences. Here, we examine a compound for which the preferred stacking pattern instead reveals key aspects about its chemical bonding: Pd5InAs. Its structure is based on the intergrowth of slabs of the AuCu3 and PtHg2 (or alternatively, fluorite) structure types. Two basic stacking arrangements are available to this compound, represented by the Pd5TlAs and HoCoGa5 structure types. DFT total energy calculations reveal that the former outcompetes the latter by a staggering 0.65 eV/formula unit. Through a combination of DFT‐reversed approximation Molecular Orbital (DFT‐raMO) and DFT‐Chemical Pressure (DFT‐CP) analysis we trace this preference to two factors. First, with DFT‐raMO analysis, we derive a Zintl‐like bonding scheme of Pd5InAs. This scheme, along with the inspection of selected crystal orbitals, is then connected to preferred stacking through the coordination environments of the Pd atoms at the interface between the Pd−In and Pd−As layers. In the hypothetical HoCoGa5‐type and observed Pd5InAs‐type structures, different Pd coordination environments arise at the interfaces. The hypothetical structure features square planar PdIn2As2 units, in each of which the same 4d‐orbital serves in the Pd sublattice's role as both Lewis acid (for interactions with the As) and Lewis base (for interactions with the In). In the observed structure, tetrahedral PdIn2As2 units occur instead, so that these contradictory roles are distributed to separate 4d‐orbitals, leading to more effective bonding. DFT‐CP analysis illustrates that this driving force for the Pd5TlAs‐type arrangement is supplemented by a favorable alignment of the packing tensions in the parent structures. Altogether, the resulting picture demonstrates how the reaction of simple intermetallic structures to form intergrowths can be guided by recognizable chemical interactions.

show abstract

The Intermetallic Reactivity Database: Compiling Chemical Pressure and Electronic Metrics toward Materials Design and Discovery

Cited by 9 publications

References 65 publications

Self-Consistent Chemical Pressure Analysis: Resolving Atomic Packing Effects through the Iterative Partitioning of Space and Energy

Self-Consistent Chemical Pressure Analysis: Resolving Atomic Packing Effects through the Iterative Partitioning of Space and Energy

Entropic Control of Bonding, Guided by Chemical Pressure: Phase Transitions and 18-n+m Isomerism of IrIn₃

The Zintl Concept Applied to Intergrowth Structures: Electron‐Hole Matching, Stacking Preferences, and Chemical Pressures in Pd₅InAs

Contact Info

Product

Resources

About

The Intermetallic Reactivity Database: Compiling Chemical Pressure and Electronic Metrics toward Materials Design and Discovery

Cited by 9 publications

References 65 publications

Self-Consistent Chemical Pressure Analysis: Resolving Atomic Packing Effects through the Iterative Partitioning of Space and Energy

Self-Consistent Chemical Pressure Analysis: Resolving Atomic Packing Effects through the Iterative Partitioning of Space and Energy

Entropic Control of Bonding, Guided by Chemical Pressure: Phase Transitions and 18-n+m Isomerism of IrIn3

The Zintl Concept Applied to Intergrowth Structures: Electron‐Hole Matching, Stacking Preferences, and Chemical Pressures in Pd5InAs

Contact Info

Product

Resources

About

Entropic Control of Bonding, Guided by Chemical Pressure: Phase Transitions and 18-n+m Isomerism of IrIn₃

The Zintl Concept Applied to Intergrowth Structures: Electron‐Hole Matching, Stacking Preferences, and Chemical Pressures in Pd₅InAs