First-principles definition of ionicity and covalency in molecules and solids

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First-principles definition of ionicity and covalency in molecules and solids. / Anisimov, Vladimir; Oganov, Artem; Korotin, Dmitry et al.
In: The Journal of chemical physics, Vol. 160, No. 14, 144113, 14.04.2024.

Research output: Contribution to journal › Article › peer-review

Author

Anisimov, Vladimir ; Oganov, Artem ; Korotin, Dmitry et al. / First-principles definition of ionicity and covalency in molecules and solids. In: The Journal of chemical physics. 2024 ; Vol. 160, No. 14.

BibTeX

@article{823b3d715ccd44f7a8a423141a20816e,

title = "First-principles definition of ionicity and covalency in molecules and solids",

abstract = "The notions of ionicity and covalency of chemical bonds, effective atomic charges, and decomposition of the cohesive energy into ionic and covalent terms are fundamental yet elusive. For example, different approaches give different values of atomic charges. Pursuing the goal of formulating a universal approach based on firm physical grounds (first-principles or non-empirical), we develop a formalism based on Wannier functions with atomic orbital symmetry and capable of defining these notions and giving numerically robust results that are in excellent agreement with traditional chemical thinking. Unexpectedly, in diamond-like boron phosphide (BP), we find charges of +0.68 on phosphorus and −0.68 on boron atoms, and this anomaly is explained by the Zintl–Klemm nature of this compound. We present a simple model that includes energies of the highest occupied cationic and lowest unoccupied anionic atomic orbitals, coordination numbers, and strength of interatomic orbital overlap. This model captures the essential physics of bonding and accurately reproduces all our results, including anomalous BP.",

author = "Vladimir Anisimov and Artem Oganov and Dmitry Korotin and Dmitry Novoselov and Alexey Shorikov and Alexander Belozerov",

year = "2024",

month = apr,

day = "14",

doi = "10.1063/5.0202481",

language = "English",

volume = "160",

journal = "The Journal of chemical physics",

issn = "0021-9606",

publisher = "American Institute of Physics Publising LLC",

number = "14",

}

RIS

TY - JOUR

T1 - First-principles definition of ionicity and covalency in molecules and solids

AU - Anisimov, Vladimir

AU - Oganov, Artem

AU - Korotin, Dmitry

AU - Novoselov, Dmitry

AU - Shorikov, Alexey

AU - Belozerov, Alexander

PY - 2024/4/14

Y1 - 2024/4/14

N2 - The notions of ionicity and covalency of chemical bonds, effective atomic charges, and decomposition of the cohesive energy into ionic and covalent terms are fundamental yet elusive. For example, different approaches give different values of atomic charges. Pursuing the goal of formulating a universal approach based on firm physical grounds (first-principles or non-empirical), we develop a formalism based on Wannier functions with atomic orbital symmetry and capable of defining these notions and giving numerically robust results that are in excellent agreement with traditional chemical thinking. Unexpectedly, in diamond-like boron phosphide (BP), we find charges of +0.68 on phosphorus and −0.68 on boron atoms, and this anomaly is explained by the Zintl–Klemm nature of this compound. We present a simple model that includes energies of the highest occupied cationic and lowest unoccupied anionic atomic orbitals, coordination numbers, and strength of interatomic orbital overlap. This model captures the essential physics of bonding and accurately reproduces all our results, including anomalous BP.

AB - The notions of ionicity and covalency of chemical bonds, effective atomic charges, and decomposition of the cohesive energy into ionic and covalent terms are fundamental yet elusive. For example, different approaches give different values of atomic charges. Pursuing the goal of formulating a universal approach based on firm physical grounds (first-principles or non-empirical), we develop a formalism based on Wannier functions with atomic orbital symmetry and capable of defining these notions and giving numerically robust results that are in excellent agreement with traditional chemical thinking. Unexpectedly, in diamond-like boron phosphide (BP), we find charges of +0.68 on phosphorus and −0.68 on boron atoms, and this anomaly is explained by the Zintl–Klemm nature of this compound. We present a simple model that includes energies of the highest occupied cationic and lowest unoccupied anionic atomic orbitals, coordination numbers, and strength of interatomic orbital overlap. This model captures the essential physics of bonding and accurately reproduces all our results, including anomalous BP.

UR - http://www.scopus.com/inward/record.url?partnerID=8YFLogxK&scp=85190460843

UR - https://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcAuth=tsmetrics&SrcApp=tsm_test&DestApp=WOS_CPL&DestLinkType=FullRecord&KeyUT=001199854600005

U2 - 10.1063/5.0202481

DO - 10.1063/5.0202481

M3 - Article

VL - 160

JO - The Journal of chemical physics

JF - The Journal of chemical physics

SN - 0021-9606

IS - 14

M1 - 144113

ER -

ID: 55695490