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Electronegativity-Based Computation of 29Si Chemical Shifts

Published online by Cambridge University Press:  25 February 2011

Henry. M ,
Gerardin. C  and
Taulelle. F
Henry. M
Affiliation:
Laboratoire de Chimie de la Matière Condensée, University Pierre et Marie Curie, T54–55 4, place Jussieu, 75252 PARIS Cedex 05, FRANCE
Gerardin. C
Affiliation:
Laboratoire de Chimie de la Matière Condensée, University Pierre et Marie Curie, T54–55 4, place Jussieu, 75252 PARIS Cedex 05, FRANCE
Taulelle. F
Affiliation:
Laboratoire de Chimie de la Matière Condensée, University Pierre et Marie Curie, T54–55 4, place Jussieu, 75252 PARIS Cedex 05, FRANCE
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Abstract

The Partial Charge Model has been modified to take into account the detailed structure of any molecular sol-gel precursors or inorganic solid networks. Starting from these structure-dependent partial charges, the classical theory of nuclear shielding is applied to compute the electronic cloud compacity <r-3>p, the population unbalance Pu and also the mean excitation energy ΔE. With these three parameters it is possible to explain the chemical shifts variations, spanning from +40 down to -140 ppm, of more than 50 precursors. Depending on the ligands, the well-known upside-down U-curves for series SiXnY4-n (n=0‥4) can be ascribed either to the population unbalance term Pu or to a competition between the two other terms <r-3>p and ΔE.

Type
Research Article
Information
MRS Online Proceedings Library (OPL) , Volume 271: Symposium N – Better Ceramics Through Chemistry V , 1992 , 243
Copyright
Copyright © Materials Research Society 1992

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References

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