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Disproving a Silicon Analog of an Alkyne with the Aid of Topological Analyses of the Electronic Structure and Ab Initio Molecular Dynamics Calculations
Author(s) -
Pignedoli Carlo A.,
Curioni Alessandro,
Andreoni Wanda
Publication year - 2005
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.200500064
Subject(s) - silicon , ab initio , atoms in molecules , electron localization function , chemical bond , chemistry , chemical physics , triple bond , computational chemistry , topology (electrical circuits) , realization (probability) , molecule , bond order , density functional theory , electron , physics , bond length , double bond , quantum mechanics , organic chemistry , mathematics , statistics , combinatorics
Abstract A silicon compound has recently been synthesized that was claimed to exhibit the first realization of a silicon–silicon triple bond. We debate this classification on the basis of a thorough investigation of the nature of the chemical bond, using the rigorous topological analysis of the electron density as developed in Bader’s atoms‐in‐molecules theory, that of the electron localization function and the related orbital‐independent definitions of the bond order. Our results refer both to the ground‐state geometry and to nonequilibrium configurations, which are accessed by the system in a room‐temperature ab initio molecular dynamics simulation. We also use the reciprocal compliance force constant as an independent chemical descriptor. All the above procedures are in agreement and do not support the classification of the silicon–silicon central bond as triple. The characterization which consistently emerges from the present study is one in which two electron pairs participate in the bonding and the other pair belongs mainly to nonbonding regions.