Premium
Laplacian of the Hamiltonian Kinetic Energy Density as an Indicator of Binding and Weak Interactions
Author(s) -
CarpioMartínez Pablo,
BarqueraLozada José E.,
Pendás Angel Martín,
CortésGuzmán Fernando
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.201900769
Subject(s) - kinetic energy , covalent bond , chemistry , intermolecular force , chemical physics , delocalized electron , molecule , chemical bond , electron localization function , atoms in molecules , binding energy , electron density , hamiltonian (control theory) , atomic physics , potential energy , computational chemistry , electron , physics , quantum mechanics , mathematical optimization , mathematics , organic chemistry
The kinetic energy is the center of a controversy between two opposite points of view about its role in the formation of a chemical bond. One school states that a lowering of the kinetic energy associated with electron delocalization is the key stabilization mechanism of covalent bonding. In contrast, the opposite school holds that a chemical bond is formed by a decrease in the potential energy due to a concentration of electron density within the binding region. In this work, a topographic analysis of the Hamiltonian Kinetic Energy Density (KED) and its laplacian is presented to gain more insight into the role of the kinetic energy within chemical interactions. This study is focused on atoms, diatomic and organic molecules, along with their dimers. In addition, it is shown that the laplacian of the Hamiltonian KED exhibits a shell structure in atoms and that their outermost shell merge when a molecule is formed. A covalent bond is characterized by a concentration of kinetic energy, potential energy and electron densities along the internuclear axis, whereas a charge‐shift bond is characterized by a fusion of external concentration shells and a depletion in the bonding region. In the case of weak intermolecular interactions, the external shell of the molecules merge into each other resulting in an intermolecular surface comparable to that obtained by the Non‐covalent interaction (NCI) analysis.