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Title: CLASSICAL AND NONCLASSICAL SILICON RADICAL CATIONS - H(N)SIX(CENTER-DOT+) SPECIES (X=N, O, F, P, S AND CL)
Authors: SANA, M ×
DECREM, M
LEROY, G
Nguyen, Minh Tho
VANQUICKENBORNE, LG #
Issue Date: 1994
Publisher: ROYAL SOC CHEMISTRY
Series Title: Journal of the Chemical Society. Faraday transactions vol:90 issue:23 pages:3505-3511
Conference: date:UNIV LOUVAIN,DEPT CHEM,B-3001 LOUVAIN,BELGIUM; UNIV CATHOLIQUE LOUVAIN,CHIM QUANT LAB,B-1348 LOUVAIN,BELGIUM
Abstract: A theoretical analysis of the classical and non-classical silicon radical cations, H(n)SiX(.+)C with X = N, O, F, P, S and Cl has been carried out. Heats of formation of the ions considered have been determined using ab initio molecular orbital (MO) calculations at the UMP4/6-31 + G(2df, p) level with UMP2/6-31G(d, p) optimized geometries plus vibrational and thermal corrections. No classical halogen radical cations (H3Si-X(.+) with X = F and Cl) could be found. In other cases, non-classical ions (H2Si-XH(n-2) (.+)) are consistently more stable than their classical counterparts (Hn-1SiH+ + I). The difference in stability between both isomers depends on the nature of X: it is large with N and O, but rather small with P and S. Interconversion between both isomeric forms has also been investigated. When X is a second-row atom, the energy of the transition structure for the 1,2-hydrogen shift is close to that of the fragments Hn-1SIH+ + H. When X is a third-row atom, the barrier height increases, but remains smaller than the dissociation energy. The potential-energy surface of the H,SiN'+ ions is reported in detail. Overall it has been shown that silicon-containing non-classical radical cations do not have a formal separation of both charge and radical centres as is the case in carbon analogues. Therefore they cannot properly be described as 'distonic radical cations' under the currently accepted definition.
ISSN: 0956-5000
Publication status: published
KU Leuven publication type: IT
Appears in Collections:Quantum Chemistry and Physical Chemistry Section
× corresponding author
# (joint) last author

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