Advanced search
1 file | 1.95 MB Add to list

Atomic charges and the electrostatic potential are ill-defined in degenerate ground states

Author
Organization
Project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
Abstract
A system in a spatially degenerate ground state responds in a qualitatively different way to positive and negative point charges. This means that the molecular electrostatic potential is ill-defined for degenerate ground negative point charges. This means that the molecular states due to the ill-defined nature of the electron density. It also means that it is impossible, in practice, to define fixed atomic charges for molecular mechanics simulations of molecules with (quasi-)degenerate ground states. Atomic-polarizability-based models and electronegativity-equalization-type models for molecular polarization also fail to capture this effect. We demonstrate the ambiguity in the electrostatic potential using several molecules of different degree of degeneracy, quasi-degeneracy, and symmetry.
Keywords
MOLECULES, FUKUI FUNCTIONS, ELECTRONEGATIVITY EQUALIZATION, DENSITY

Downloads

  • (...).pdf
    • full text
    • |
    • UGent only
    • |
    • PDF
    • |
    • 1.95 MB

Citation

Please use this url to cite or link to this publication:

MLA
Bultinck, Patrick, Carlos Cardenas, Patricio Fuentealba, et al. “Atomic Charges and the Electrostatic Potential Are Ill-defined in Degenerate Ground States.” JOURNAL OF CHEMICAL THEORY AND COMPUTATION 9.11 (2013): 4779–4788. Print.
APA
Bultinck, P., Cardenas, C., Fuentealba, P., Johnson, P., & Ayers, P. W. (2013). Atomic charges and the electrostatic potential are ill-defined in degenerate ground states. JOURNAL OF CHEMICAL THEORY AND COMPUTATION, 9(11), 4779–4788.
Chicago author-date
Bultinck, Patrick, Carlos Cardenas, Patricio Fuentealba, Paul Johnson, and Paul W Ayers. 2013. “Atomic Charges and the Electrostatic Potential Are Ill-defined in Degenerate Ground States.” Journal of Chemical Theory and Computation 9 (11): 4779–4788.
Chicago author-date (all authors)
Bultinck, Patrick, Carlos Cardenas, Patricio Fuentealba, Paul Johnson, and Paul W Ayers. 2013. “Atomic Charges and the Electrostatic Potential Are Ill-defined in Degenerate Ground States.” Journal of Chemical Theory and Computation 9 (11): 4779–4788.
Vancouver
1.
Bultinck P, Cardenas C, Fuentealba P, Johnson P, Ayers PW. Atomic charges and the electrostatic potential are ill-defined in degenerate ground states. JOURNAL OF CHEMICAL THEORY AND COMPUTATION. 2013;9(11):4779–88.
IEEE
[1]
P. Bultinck, C. Cardenas, P. Fuentealba, P. Johnson, and P. W. Ayers, “Atomic charges and the electrostatic potential are ill-defined in degenerate ground states,” JOURNAL OF CHEMICAL THEORY AND COMPUTATION, vol. 9, no. 11, pp. 4779–4788, 2013.
@article{4213992,
  abstract     = {A system in a spatially degenerate ground state responds in a qualitatively different way to positive and negative point charges. This means that the molecular electrostatic potential is ill-defined for degenerate ground negative point charges. This means that the molecular states due to the ill-defined nature of the electron density. It also means that it is impossible, in practice, to define fixed atomic charges for molecular mechanics simulations of molecules with (quasi-)degenerate ground states. Atomic-polarizability-based models and electronegativity-equalization-type models for molecular polarization also fail to capture this effect. We demonstrate the ambiguity in the electrostatic potential using several molecules of different degree of degeneracy, quasi-degeneracy, and symmetry.},
  author       = {Bultinck, Patrick and Cardenas, Carlos and Fuentealba, Patricio and Johnson, Paul and Ayers, Paul W},
  issn         = {1549-9618},
  journal      = {JOURNAL OF CHEMICAL THEORY AND COMPUTATION},
  keywords     = {MOLECULES,FUKUI FUNCTIONS,ELECTRONEGATIVITY EQUALIZATION,DENSITY},
  language     = {eng},
  number       = {11},
  pages        = {4779--4788},
  title        = {Atomic charges and the electrostatic potential are ill-defined in degenerate ground states},
  url          = {http://dx.doi.org/10.1021/ct4005454},
  volume       = {9},
  year         = {2013},
}

Altmetric
View in Altmetric
Web of Science
Times cited: