An electric field-based approach for quantifying effective volumes and radii of chemically affected space

Mroz, Austin; Davenport, Audrey M.; Sterling, Jasper; Davis, Joshua D.; Hendon, Christopher H.

doi:10.1039/d2sc00780k

Cited by 8 publications

(7 citation statements)

References 75 publications

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“…Defining atomic boundaries in open (e.g., molecular) systems is not trivial, but can, for instance, be done successfully using different cutoff criteria. The electron density , and properties of valence orbitals are some of the possibilities. ,− For crystals, there exist other options. ,− We here choose to attribute atomic volumes V A directly to the volume of electron energy basins Ω A . This choice is possible because the gradient field of the electron energy density exclusively separates space into nuclear-centered basins.…”

Section: Resultsmentioning

confidence: 99%

Quantifying Atomic Volume, Partial Charge, and Electronegativity in Condensed Phases

Racioppi,

Hyldgaard,

Rahm

2024

J. Phys. Chem. C

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The predictive and explanatory roles of atomic properties such as size, charge, and electronegativity are closely linked to their definitions. However, establishing suitable definitions becomes increasingly challenging when examining atoms within materials. This study presents a quantum-mechanical framework for the quantitative assessment of these atomic properties in crystalline structures. Our approach utilizes Kohn−Sham density functional theory to approximate the electron energy density. We then employ a quantum chemical topological analysis of this density to derive atomic properties. The average electron energy density is conceptually powerful because it can be interpreted as a product of the electron density and the average energy of occupied molecular orbitals (MOs). Our method therefore bridges descriptive and predictive theories of electronic structure, including the quantum theory of atoms in molecules and MO theory. The applicability of our methodology is demonstrated across various materials, including metals, ionic salts, semiconductors, and a hydrogen-bonded molecular crystal. This work provides insights into electronegativity inversion during bond formation. It also highlights the complementary roles of partial charge and electronegativity in electronic structure analysis, with one indicating spatial electron accumulation or depletion and the other reflecting average electron binding. Experimental ground state electronegativities of

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Section: Resultsmentioning

confidence: 99%

Quantifying Atomic Volume, Partial Charge, and Electronegativity in Condensed Phases

Racioppi,

Hyldgaard,

Rahm

2024

J. Phys. Chem. C

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“…This way we can observe the effect of functionalization on metal d -orbital energies relative to one another. Using our code STREUSEL 25 , we can align the MOF valence band to the vacuum level using a previously described method 26 . From there, we can plot a density of states, and use the density to direct us to the frontier metal orbitals.…”

Section: Resultsmentioning

confidence: 99%

Ligand field tuning of d-orbital energies in metal-organic framework clusters

2023

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Linker functionalization is a common route used to affect the electronic and catalytic properties of metal-organic frameworks. By either pre- or post-synthetically installing linkages with differing linker moieties the band gap, workfunction, and exciton lifetimes have been shown to be affected. One overlooked aspect of linker functionalization, however, has been the impact on the metal d-orbital energies to which they are bound. The ligand field differences should result in substantial changes in d-splitting. In this study we use density functional theory (DFT) to study the energetics of d-orbital energy tuning as a function of linker chemistry. We offer a general descriptor, linker pKa, as a tool to predict resultant band energies in metal-organic frameworks (MOFs). Our calculations reveal that simple functionalizations can affect the band energies, of primarily metal d lineage, by up to 2 eV and illustrate the significance of this band modularity using four archetypal MOFs: UiO-66, MIL-125, ZIF-8, and MOF-5. Together, we show that linker functionalization dramatically affects d-energies in MOF clusters and highlight that linker functionalization is a useful route for fine-tuning band edges centered on the metals, rather than linkers themselves.

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“…45 Note that the atomic radius of both Zn (2.01 Å) and Zn + (0.88 Å) 46 is smaller than that of Au (2.14 Å). 47 Table 1 shows calculated properties for pure Au 10 À and doped Au 9 Zn À clusters including the spin multiplicity (2S + 1), the Gibbs binding energy per particle, the average bond distances between external-external and external-central atoms (d ext-ext and d ext-cen , respectively), the HOMO-LUMO gap, and the vertical detachment energy (VDE). The average d ext-cen distance includes the first and second neighbors of the central atom; that is, those in the middle of the edges and those in the corners of the triangle.…”

Section: Resultsmentioning

confidence: 99%

“…45 Note that the atomic radius of both Zn (2.01 Å) and Zn + (0.88 Å) 46 is smaller than that of Au (2.14 Å). 47…”

Section: Resultsmentioning

confidence: 99%

Adsorption of multiple NO molecules on Au₁₀⁻and Au₉Zn⁻planar clusters. A comparative DFT study

Fernández

Balbás

2023

Phys. Chem. Chem. Phys.

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An electric field-based approach for quantifying effective volumes and radii of chemically affected space

Abstract: Chemical shape and size play a critical role in chemistry. The van der Waals (vdW) radii, a familiar manifold used to quantify size by assuming overlapping spheres, provides rapid estimates...

Cited by 8 publications

References 75 publications

Quantifying Atomic Volume, Partial Charge, and Electronegativity in Condensed Phases

Quantifying Atomic Volume, Partial Charge, and Electronegativity in Condensed Phases

Ligand field tuning of d-orbital energies in metal-organic framework clusters

Adsorption of multiple NO molecules on Au₁₀⁻and Au₉Zn⁻planar clusters. A comparative DFT study

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An electric field-based approach for quantifying effective volumes and radii of chemically affected space

Abstract: Chemical shape and size play a critical role in chemistry. The van der Waals (vdW) radii, a familiar manifold used to quantify size by assuming overlapping spheres, provides rapid estimates...

Cited by 8 publications

References 75 publications

Quantifying Atomic Volume, Partial Charge, and Electronegativity in Condensed Phases

Quantifying Atomic Volume, Partial Charge, and Electronegativity in Condensed Phases

Ligand field tuning of d-orbital energies in metal-organic framework clusters

Adsorption of multiple NO molecules on Au10−and Au9Zn−planar clusters. A comparative DFT study

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Adsorption of multiple NO molecules on Au₁₀⁻and Au₉Zn⁻planar clusters. A comparative DFT study