A generalized formulation of electronegativity equalization from density‐functional theory

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

A generalized formulation of the electronegativity equalization principle is presented from the perspective of density‐functional theory. The resulting equations provide a linear‐response framework for describing the redistribution of electrons upon perturbation by an external density or applied field. The equations can be solved using a finite set of basis functions to model the density response. Applications demonstrate the method accurately reproduces dipole moments and chemical potentials obtained from density‐functional calculations. The method provides high accuracy in the presence of relatively strong perturbations such as those arising from interactions with other molecules or applied fields, and is “exact” in the limit that these interactions vanish. The method has the advantage that accuracy can be systematically improved by inclusion of more complete basis functions. The present formulation provides the foundation for a promising semiempirical model for polarization and charge transfer in molecular simulations. © 1995 John Wiley & Sons, Inc.

Original languageEnglish (US)
Pages (from-to)385-394
Number of pages10
JournalInternational Journal of Quantum Chemistry
Volume56
Issue number29 S
DOIs
StatePublished - Jan 1 1995

Fingerprint

Electronegativity
formulations
perturbation
Chemical potential
Dipole moment
Charge transfer
dipole moments
charge transfer
interactions
inclusions
Polarization
Molecules
Electrons
polarization
molecules
electrons
simulation

All Science Journal Classification (ASJC) codes

  • Condensed Matter Physics
  • Atomic and Molecular Physics, and Optics
  • Physical and Theoretical Chemistry

Cite this

@article{4b8d47aa1da34d849907a66f410e9bba,
title = "A generalized formulation of electronegativity equalization from density‐functional theory",
abstract = "A generalized formulation of the electronegativity equalization principle is presented from the perspective of density‐functional theory. The resulting equations provide a linear‐response framework for describing the redistribution of electrons upon perturbation by an external density or applied field. The equations can be solved using a finite set of basis functions to model the density response. Applications demonstrate the method accurately reproduces dipole moments and chemical potentials obtained from density‐functional calculations. The method provides high accuracy in the presence of relatively strong perturbations such as those arising from interactions with other molecules or applied fields, and is “exact” in the limit that these interactions vanish. The method has the advantage that accuracy can be systematically improved by inclusion of more complete basis functions. The present formulation provides the foundation for a promising semiempirical model for polarization and charge transfer in molecular simulations. {\circledC} 1995 John Wiley & Sons, Inc.",
author = "Darrin York",
year = "1995",
month = "1",
day = "1",
doi = "https://doi.org/10.1002/qua.560560842",
language = "English (US)",
volume = "56",
pages = "385--394",
journal = "International Journal of Quantum Chemistry",
issn = "0020-7608",
publisher = "John Wiley and Sons Inc.",
number = "29 S",

}

A generalized formulation of electronegativity equalization from density‐functional theory. / York, Darrin.

In: International Journal of Quantum Chemistry, Vol. 56, No. 29 S, 01.01.1995, p. 385-394.

Research output: Contribution to journalArticle

TY - JOUR

T1 - A generalized formulation of electronegativity equalization from density‐functional theory

AU - York, Darrin

PY - 1995/1/1

Y1 - 1995/1/1

N2 - A generalized formulation of the electronegativity equalization principle is presented from the perspective of density‐functional theory. The resulting equations provide a linear‐response framework for describing the redistribution of electrons upon perturbation by an external density or applied field. The equations can be solved using a finite set of basis functions to model the density response. Applications demonstrate the method accurately reproduces dipole moments and chemical potentials obtained from density‐functional calculations. The method provides high accuracy in the presence of relatively strong perturbations such as those arising from interactions with other molecules or applied fields, and is “exact” in the limit that these interactions vanish. The method has the advantage that accuracy can be systematically improved by inclusion of more complete basis functions. The present formulation provides the foundation for a promising semiempirical model for polarization and charge transfer in molecular simulations. © 1995 John Wiley & Sons, Inc.

AB - A generalized formulation of the electronegativity equalization principle is presented from the perspective of density‐functional theory. The resulting equations provide a linear‐response framework for describing the redistribution of electrons upon perturbation by an external density or applied field. The equations can be solved using a finite set of basis functions to model the density response. Applications demonstrate the method accurately reproduces dipole moments and chemical potentials obtained from density‐functional calculations. The method provides high accuracy in the presence of relatively strong perturbations such as those arising from interactions with other molecules or applied fields, and is “exact” in the limit that these interactions vanish. The method has the advantage that accuracy can be systematically improved by inclusion of more complete basis functions. The present formulation provides the foundation for a promising semiempirical model for polarization and charge transfer in molecular simulations. © 1995 John Wiley & Sons, Inc.

UR - http://www.scopus.com/inward/record.url?scp=84981621061&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84981621061&partnerID=8YFLogxK

U2 - https://doi.org/10.1002/qua.560560842

DO - https://doi.org/10.1002/qua.560560842

M3 - Article

VL - 56

SP - 385

EP - 394

JO - International Journal of Quantum Chemistry

JF - International Journal of Quantum Chemistry

SN - 0020-7608

IS - 29 S

ER -