Relating atomic energy, radius and electronegativity through compression

Rahm, Martin; Erhart, Paul; Cammi, Roberto

doi:10.1039/d0sc06675c

Cited by 32 publications

(35 citation statements)

References 66 publications

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“…The change in the average electron binding energy,

Δ \overline{χ}

, calculated over bond formation processes has been shown to be a potent indicator for covalent and ionic character in diatomic molecules [5] . Computation of

Δ \overline{χ}

has also brought insight into the variability of electronegativity as a function of pressure [57,58] . One expression for the average energy of electrons at a point r in a molecule is:

true \overset{χ}{true} ((), r) = - \frac{1}{ρ ((), r)} (() τ_{L} (boldr) + υ (boldr) ρ (boldr) + 2 \int \frac{P (boldr, r_{2})}{(|| r - {boldr}_{2})} d {boldr}_{2})

…”

Section: Introductionmentioning

confidence: 99%

In‐Situ Electronegativity and the Bridging of Chemical Bonding Concepts

Racioppi

Rahm

2021

Chemistry A European J

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One challenge in chemistry is the plethora of often disparate models for rationalizing the electronic structure of molecules. Chemical concepts abound, but their connections are often frail. This work describes a quantum‐mechanical framework that enables a combination of ideas from three approaches common for the analysis of chemical bonds: energy decomposition analysis (EDA), quantum chemical topology, and molecular orbital (MO) theory. The glue to our theory is the electron energy density, interpretable as one part electrons and one part electronegativity. We present a three‐dimensional analysis of the electron energy density and use it to redefine what constitutes an atom in a molecule. Definitions of atomic partial charge and electronegativity follow in a way that connects these concepts to the total energy of a molecule. The formation of polar bonds is predicted to cause inversion of electronegativity, and a new perspective of bonding in diborane and guanine−cytosine base‐pairing is presented. The electronegativity of atoms inside molecules is shown to be predictive of pKa.

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“…The change in the average electron binding energy,

Δ \overline{χ}

, calculated over bond formation processes has been shown to be a potent indicator for covalent and ionic character in diatomic molecules [5] . Computation of

Δ \overline{χ}

has also brought insight into the variability of electronegativity as a function of pressure [57,58] . One expression for the average energy of electrons at a point r in a molecule is:

true \overset{χ}{true} ((), r) = - \frac{1}{ρ ((), r)} (() τ_{L} (boldr) + υ (boldr) ρ (boldr) + 2 \int \frac{P (boldr, r_{2})}{(|| r - {boldr}_{2})} d {boldr}_{2})

…”

Section: Introductionmentioning

confidence: 99%

In‐Situ Electronegativity and the Bridging of Chemical Bonding Concepts

Racioppi

Rahm

2021

Chemistry A European J

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“…[65][66][67][68] . It has also been extended to high pressure conditions, 62,[69][70][71] allowing for the successful rationalization of unexpected phenomena, such as redox inversion in nitric sulfur hydrides. 72 How to formally separate core from valence in Eq.…”

Section: Introductionmentioning

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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“…So far, this quantity has been commonly employed for correlating several atomic/molecular properties. [9][10][11][12][13] Since electronegativity is not a directly measurable quantity, it cannot be determined through experiments. This has led to the development of a wide variety of formulations coexisting in the scientific praxis.…”

Section: Introductionmentioning

confidence: 99%

A Scale of Atomic Electronegativity Based on Floating Spherical Gaussian Orbital Approach

2021

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Electronegativity (χ) is an old yet valuable concept having multidisciplinary applications. To advance the understanding of this concept, an electronegativity model has been proposed based on polarizability within the context of Floating Spherical Gaussian Orbital (FSGO) approach. The model provides atomic electronegativity scale for 120 elements. The calculated electronegativity presents marked periodicity and relates well with other electronegativity scales. Further, Electronegativity Equalization Principle is validated by the computed electronegativity data. The proposed scale has also been successfully applied to compute Fermi energy for some metal oxides. In accordance with the literature, this is the first FSGO-polarizability based model of electronegativity.

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Relating atomic energy, radius and electronegativity through compression

Abstract: Trends in atomic properties are well-established tools for guiding the analysis and discovery of materials. Here, we show how compression can reveal a long sought-after connection between two central chemical...

Cited by 32 publications

References 66 publications

In‐Situ Electronegativity and the Bridging of Chemical Bonding Concepts

In‐Situ Electronegativity and the Bridging of Chemical Bonding Concepts

Electronegativity Equilibration

A Scale of Atomic Electronegativity Based on Floating Spherical Gaussian Orbital Approach

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