In‐Situ Electronegativity and the Bridging of Chemical Bonding Concepts

Racioppi, Stefano; Rahm, Martin

doi:10.1002/chem.202103477

Cited by 14 publications

(49 citation statements)

References 116 publications

(263 reference statements)

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“…The quantification of all these terms is possible through different methods (e.g., see ref. 127) and we will return to discuss their physical rationale and implications in detail, in future work.…”

Section: E Electronegativity Equilibrationmentioning

confidence: 99%

Electronegativity Equilibration

Sessa

Rahm

2022

Preprint

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Controlling the distribution of electrons in materials is the holy grail of chemistry and material science. Practical attempts at this feat are common but are often reliant on simple arguments based on electronegativity. One challenge is knowing when such arguments work, and which other factors may play a role. Ultimately, electrons move to equalize chemical potentials. In this work, we outline a theory in which chemical potentials of atoms and molecules are expressed in terms of reinterpretations of common chemical concepts and some physical quantities: electronegativity, chemical hardness, and the sensitivity of electronic repulsion and core levels with respect to changes in the electron density. At the zero-temperature limit, an expression of the Fermi level emerges that helps to connect several of these quantities to a plethora of material properties, theories and phenomena predominantly explored in condensed matter physics. Our theory runs counter to Sanderson’s postulate of electronegativity equalization and allows a perspective in which electronegativities of bonded atoms need not be equal. As chemical potentials equalize in this framework, electronegativities equilibrate.

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Section: E Electronegativity Equilibrationmentioning

confidence: 99%

Electronegativity Equilibration

Sessa

Rahm

2022

Preprint

Self Cite

View full text Add to dashboard Cite

show abstract

“…The quantification of all these terms is possible through different methods (e.g., see Ref. 133) and we will return to discuss their physical rationale and implications in detail, in future work.…”

Section: Electronegativity Equilibrationmentioning

confidence: 99%

Electronegativity Equilibration

Sessa

Rahm

2022

Preprint

Self Cite

View full text Add to dashboard Cite

Controlling the distribution of electrons in materials is the holy grail of chemistry and material science. Practical attempts at this feat are common but are often reliant on simplistic arguments based on electronegativity. One challenge is knowing when such arguments work, and which other factors may play a role. Ultimately, electrons move to equalize chemical potentials. In this work, we outline a theory in which chemical potentials of atoms and molecules are expressed in terms of reinterpretations of common chemical concepts and some physical quantities: electronegativity, chemical hardness, and the sensitivity of electronic repulsion and core levels with respect to changes in the electron density. At the zero-temperature limit, an expression of the Fermi level emerges that helps to connect several of these quantities to a plethora of material properties, theories and phenomena predominantly explored in condensed matter physics. Our theory runs counter to Sanderson’s postulate of electronega-tivity equalization and allows a perspective in which electronegativities of bonded atoms need not be equal. As chemical potentials equalize in this framework, electronegativities equilibrate.

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“…(5) The same concept also appears in the theoretical framework of moments of the electron distribution. (6) Our interest in 𝜒̅ is rooted in its association with electronegativity, (7)(8)(9)(10)(11) and to its relation with changes in the total energy as,…”

Section: Main Text: Introductionmentioning

confidence: 99%

A Physical Expression of Electrons in Density Functional Theory

Racioppi

Lolur

Hyldgaard

et al. 2022

Preprint

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We present a formally exact density functional theory (DFT) determination of the average electron energy. Our orbital-free theory, which is based on a different accounting of energy functional terms, partially solves one well known downside of Kohn-Sham (KS) DFT: that orbital energies have but tenuous connections to physical quantities. Our computed average electron energies are close to experimental ionization potentials in one-electron systems, demonstrating a surprisingly small effect of self-interaction and other exchange- correlation errors in established DFT methods. We argue for the use of the average electron energy as a physics condition on otherwise fictitious KS energy levels and as a design criterion for density functional approximations.

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In‐Situ Electronegativity and the Bridging of Chemical Bonding Concepts

Cited by 14 publications

References 116 publications

Electronegativity Equilibration

Electronegativity Equilibration

Electronegativity Equilibration

A Physical Expression of Electrons in Density Functional Theory

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