%0 Journal Article %1 doi:10.1021/ct4005454 %A Bultinck, Patrick %A Cardenas, Carlos %A Fuentealba, Patricio %A Johnson, Paul A. %A Ayers, Paul W. %D 2013 %J Journal of Chemical Theory and Computation %K mechanics physics quantum unread %N 11 %P 4779-4788 %R 10.1021/ct4005454 %T Atomic Charges and the Electrostatic Potential Are Ill-Defined in Degenerate Ground States %U http://pubs.acs.org/doi/abs/10.1021/ct4005454 %V 9 %X 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 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.

@article{doi:10.1021/ct4005454, 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 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. }, added-at = {2013-11-20T01:41:24.000+0100}, author = {Bultinck, Patrick and Cardenas, Carlos and Fuentealba, Patricio and Johnson, Paul A. and Ayers, Paul W.}, biburl = {https://www.bibsonomy.org/bibtex/2eaa20abe865d1d0b9ef70bd953b76faf/drmatusek}, doi = {10.1021/ct4005454}, eprint = {http://pubs.acs.org/doi/pdf/10.1021/ct4005454}, interhash = {2b78bfc31034c3a2688d3ad89ecc54b9}, intrahash = {eaa20abe865d1d0b9ef70bd953b76faf}, journal = {Journal of Chemical Theory and Computation}, keywords = {mechanics physics quantum unread}, month = nov, number = 11, pages = {4779-4788}, timestamp = {2013-11-20T01:41:24.000+0100}, title = {Atomic Charges and the Electrostatic Potential Are Ill-Defined in Degenerate Ground States}, url = {http://pubs.acs.org/doi/abs/10.1021/ct4005454}, volume = 9, year = 2013 }