Ab initio molecular orbital study of 1‐fluorosilatrane

G. Csonka, P. Hencsei

Research output: Contribution to journalArticle

29 Citations (Scopus)

Abstract

The molecular geometry of 1‐fluorosilatrane was optimized fully by restricted Hartree–Fock (HF) calculations using the 3‐21G, 3‐21G(d) and 6‐31G(d) basis sets, with the aim of locating the positions of the local minima on the energy hypersurface. The optimized geometries were compared with available experimental (X‐ray and ED) and semiempirical data. The ab initio calculations using polarized basis sets are in good agreement with those of previously reported semiempirical calculations, giving a slightly longer equilibrium SiN distance (∼ 256 pm) in the case of the endo minimum. However, the exo minimum predicted by the semiempirical methods is not supported. There was no experimental evidence for the existence of this exo minimum, and the present ab initio calculations suggest that it is highly unstable. There is considerable disagreement among the experimental results in the CN and CC bond lengths in various silatranes, their differences being as large as 13 pm. The present calculations predict that these differences may appear because the silatrane skeleton is flexible with low‐energy, large‐amplitude internal motions which introduce considerable uncertainties into the position of ring carbon atoms. © 1994 by John Wiley & Sons, Inc.

Original languageEnglish
Pages (from-to)385-394
Number of pages10
JournalJournal of Computational Chemistry
Volume15
Issue number4
DOIs
Publication statusPublished - 1994

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Molecular orbitals
Ab Initio Calculations
p.m.
Skeleton
Local Minima
Hypersurface
Carbon
Unstable
Geometry
Internal
Uncertainty
Ring
Bond length
Predict
Motion
Experimental Results
Energy
Atoms
silatrane

ASJC Scopus subject areas

  • Chemistry(all)
  • Computational Mathematics

Cite this

Ab initio molecular orbital study of 1‐fluorosilatrane. / Csonka, G.; Hencsei, P.

In: Journal of Computational Chemistry, Vol. 15, No. 4, 1994, p. 385-394.

Research output: Contribution to journalArticle

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