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Electrostatics and Polarization in σ‐ and π‐Hole Noncovalent Interactions: An Overview
Author(s) -
Politzer Peter,
Murray Jane S.
Publication year - 2020
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201900968
Subject(s) - electrostatics , polarization (electrochemistry) , non covalent interactions , chemical physics , chemistry , static electricity , electric field , electric potential energy , molecular physics , physics , quantum mechanics , molecule , hydrogen bond , organic chemistry , power (physics)
The energetics of σ‐ and π‐hole interactions can be described very well in terms of electrostatics and polarization, consistent with their Coulombic natures. When both of these components are taken into account, very good correlations with quantum‐chemically computed interaction energies are obtained. If polarization is only minor, as when the interactions are quite weak, then electrostatics can suffice, as represented by the most positive electrostatic potential associated with the σ‐ or π‐hole. For stronger interactions, the combination of electrostatics plus polarization is very effective even for interaction energies considerably greater in magnitude than what is normally considered noncovalent bonding. Several procedures for treating polarization are summarized, including the use of point charges and the direct inclusion of electric fields.