TY - JOUR
T1 - Correct electrostatic treatment of noncovalent interactions
T2 - the importance of polarization
AU - Clark, Timothy
AU - Politzer, Peter
AU - Murray, Jane S.
N1 - "This is the peer reviewed version of the following article: [Correct electrostatic treatment of noncovalent interactions: the importance of polarization, Clark, T., Politzer, P. & Murray, J. S. 1 Mar 2015 In : Wiley Interdisciplinary Reviews: Computational Molecular Science. 5, 2, p. 169-177], which has been published in final form at [10.1002/wcms.1210]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving."
PY - 2015/3/1
Y1 - 2015/3/1
N2 - The Hellmann–Feynman theorem assures us that the forces felt by the nuclei in a molecule or complex are purely classically electrostatic. Nevertheless, it is often claimed (incorrectly) that electrostatic considerations are not sufficient to explain noncovalent interactions. Such assertions arise largely from neglecting the polarization that is inherently part of the electrostatic interaction, and must be taken into account. Accordingly, we now outline the requirements for a correct electrostatic treatment and discuss the difference between physical observables and quantities that arise from mathematical models. Polarization and donor–acceptor charge transfer are shown to be equivalent for weak interactions. However, polarization is a physical observable while charge transfer, in this context, is mathematical modelling. We also discuss some popular schemes for analyzing noncovalent interactions.
AB - The Hellmann–Feynman theorem assures us that the forces felt by the nuclei in a molecule or complex are purely classically electrostatic. Nevertheless, it is often claimed (incorrectly) that electrostatic considerations are not sufficient to explain noncovalent interactions. Such assertions arise largely from neglecting the polarization that is inherently part of the electrostatic interaction, and must be taken into account. Accordingly, we now outline the requirements for a correct electrostatic treatment and discuss the difference between physical observables and quantities that arise from mathematical models. Polarization and donor–acceptor charge transfer are shown to be equivalent for weak interactions. However, polarization is a physical observable while charge transfer, in this context, is mathematical modelling. We also discuss some popular schemes for analyzing noncovalent interactions.
U2 - 10.1002/wcms.2015.5.issue-2
DO - 10.1002/wcms.2015.5.issue-2
M3 - Article
VL - 5
SP - 169
EP - 177
JO - Wiley Interdisciplinary Reviews: Computational Molecular Science
JF - Wiley Interdisciplinary Reviews: Computational Molecular Science
SN - 1759-0876
IS - 2
ER -