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Nature of the chemical bonding in D 3 h [MH 3 M] + cations (M = Be, Mg)
Author(s) -
Penotti Fabio E.,
Cooper David L.,
Karadakov Peter B.,
Ponec Robert
Publication year - 2020
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.26183
Subject(s) - chemical bond , chemistry , atomic orbital , metal , three center two electron bond , valence (chemistry) , natural bond orbital , atomic physics , triple bond , valence electron , electron localization function , crystallography , computational chemistry , electron , bond length , bond order , density functional theory , physics , crystal structure , double bond , organic chemistry , quantum mechanics , polymer chemistry
Motivated by the particularly short metal‐metal distance that has been predicted for the D 3 h [BeH 3 Be] + cation, comparable to those anticipated for triple bonds, we investigate the nature of the bonding interactions in the D 3 h [MH 3 M] + cations (M = Be, Mg). CCSD(T)/cc‐pVQZ calculations are used to determine optimized geometries for all of the various species, including those “capped” by He or Ne atoms (as proxies for an inert gas matrix). The primary tools that are then used to investigate the nature of the chemical bonding are spin‐coupled generalized valence bond calculations and the analysis of localized natural orbitals and of domain‐averaged Fermi holes. The various results for all of the systems considered indicate the presence of highly polar three‐center two‐electron M─H─M bonding character instead of any significant direct metal‐metal bonding.