Atomic charges and the electrostatic potential are ill-defined in degenerate ground states
- Author
- Patrick Bultinck (UGent) , Carlos Cardenas, Patricio Fuentealba, Paul Johnson (UGent) and Paul W Ayers
- Organization
- Project
- 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
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Please use this url to cite or link to this publication: http://hdl.handle.net/1854/LU-4213992
- MLA
- Bultinck, Patrick, et al. “Atomic Charges and the Electrostatic Potential Are Ill-Defined in Degenerate Ground States.” JOURNAL OF CHEMICAL THEORY AND COMPUTATION, vol. 9, no. 11, 2013, pp. 4779–88, doi:10.1021/ct4005454.
- 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. https://doi.org/10.1021/ct4005454
- 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): 4779–88. https://doi.org/10.1021/ct4005454.
- 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. doi:10.1021/ct4005454.
- 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://doi.org/10.1021/ct4005454}}, volume = {{9}}, year = {{2013}}, }
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