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Bonding and metastability for Group 12 dications
Author(s) -
Sadjadi SeyedAbdolreza,
Matta Chérif F.,
Hamilton Ian P.
Publication year - 2021
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.26431
Subject(s) - delocalized electron , metastability , chemistry , excited state , density functional theory , atoms in molecules , bond dissociation energy , singlet state , electron density , atomic physics , electron localization function , dissociation (chemistry) , electron , quantum , crystallography , molecule , computational chemistry , physics , quantum mechanics , organic chemistry
Electronic structure and bonding properties of the Group 12 dications M 2 2+ (M = Zn, Cd, Hg) are investigated and electron density‐derived quantities are used to characterize the metastability of these species. Of particular interest are the complementary descriptions afforded by the Laplacian of the electron density ∇ 2 ρ ( r ) and the one‐electron Bohm quantum potential ( Q = ∇ 2ρ r/ 2 ρ r) along the bond path. Further, properties derived from the pair density including the localization‐delocalization matrices (LDMs) and the interacting quantum atoms (IQA) energies are analyzed within the framework of the quantum theory of atoms in molecules (QTAIM). From the crossing points of the singlet (ground) and triplet (excited) potential energy curves, the barriers for dissociation (BFD) are estimated to be 25.2 kcal/mol (1.09 eV) for Zn 2 2+ , 22.8 kcal/mol (0.99 eV) for Cd 2 2+ , and 26.4 kcal/mol (1.14 eV) for Hg 2 2+ . For comparison and benchmarking purposes, the case of N 2 2+ is considered as a texbook example of metastability. At the equilibrium geometries, LDMs, which are used here as an electronic fingerprinting tool, discriminate and group together Group 12 M 2 2+ from its isoelectronic Group 11 M 2 . While “classical” bonding indices are inconclusive in establishing regions of metastability in the bonding, it is shown that the one‐electron Bohm quantum potential is promising in this regard.