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research article

An electronegativity-induced spin repulsion effect

Stirling, A.
•
Pasquarello, Alfredo  
2005
The Journal of Physical Chemistry A

We present a spin delocalization effect in radical Si-containing systems, featuring a heteroatom of high electronegativity (such as N, O, or Cl) bonded to the unsaturated Si atom. We find that the higher the electronegativity of the heteroatom, the more the localized spin shifts away from the unsaturated Si atom and the heteroatom toward saturated Si neighbors. We demonstrate that this spin repulsion toward saturated Si atoms is induced by the electronegativity difference between the Si atom and the heteroatoms. We present a simple molecular-orbital-based mechanism which fully explains the structural and electronic effects. We contrast the present spin delocalization mechanism with the classical hyperconjugation in organic chemistry. The most important consequences of this spin redistribution are the electron-spin-resonance activity of the saturated Si neighbors and the enhanced stability of the radical centers. We predict a similar effect for Ge radicals and discuss why organic systems based on carbon do not feature such spin repulsion.

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Type
research article
DOI
10.1021/jp053335h
Web of Science ID

WOS:000231920400023

Author(s)
Stirling, A.
Pasquarello, Alfredo  
Date Issued

2005

Published in
The Journal of Physical Chemistry A
Volume

109

Issue

37

Start page

8385

End page

8390

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
CSEA  
Available on Infoscience
October 8, 2009
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/43496
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