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The structure of 1‐chlorosilatrane: An ab initio molecular orbital and a density functional theory study
Author(s) -
Csonka Gábor I.,
Hencsei Pál
Publication year - 1996
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/(sici)1096-987x(199605)17:7<767::aid-jcc2>3.0.co;2-q
Subject(s) - basis set , bond length , chemistry , molecular geometry , polarizability , ab initio , density functional theory , computational chemistry , thermodynamics , molecular physics , molecule , crystallography , physics , crystal structure , organic chemistry
The molecular geometries of the 1‐chloro‐, 1‐fluoro‐, 1‐methyl‐, and 1‐hydrogenosilatranes were fully optimized by the restricted Hartree‐Fock (HF) method supplemented with 3‐21G, 3‐21G( d ), 6‐31G( d ), and CEP‐31G( d ) basis sets; by MP2 calculations using 6‐31G( d ) and CEP‐31G( d ) basis sets; and by GGA‐DFT calculations using 6‐31G( d 5) basis set with the aim of locating the positions of the local minima on the energy hypersurface. The HF/6‐31G( d ) calculations predict long (>254 pm) and the MP2/CEP calculations predicted short (∼225 pm) equilibrium Si(SINGLE BOND)N distances. The present GGA‐DFT calculations reproduce the available gas phase experimental Si(SINGLE BOND)N distances correctly. The solid phase experimental results predict that the Si(SINGLE BOND)N distance is shorter in 1‐chlorosilatrane than in 1‐fluorosilatrane. In this respect the HF results show a strong basis set dependence, the MP2/CEP results contradict the experiment, and the GGA‐DFT results in electrolytic medium agree with the experiment. The latter calculations predict that 1‐chlorosilatrane is more polarizable than 1‐fluorosilatrane and also support a general Si(SINGLE BOND)N distance shortening trend for silatranes during the transition from gas phase to polar liquid or solid phase. The calculations predict that the ethoxy links of the silatrane skeleton are flexible. Consequently, it is difficult to measure experimentally the related bond lengths and bond and torsion angles. This is the probable origin of the surprisingly large differences for the experimental structural parameters. On the basis of experimental analogies, ab initio calculations, and density functional theory (DFT) calculations, a gas phase equilibrium ( r e ) geometry is predicted for 1‐chlorosilatrane. The semiempirical methods predict a so‐called exo minimum (at above 310 pm Si(SINGLE BOND)N distance); however, the ab initio and GGA‐DFT calculations suggest that this form is nonexistent. The GGA‐DFT geometry optima were characterized by frequency analysis. © 1996 by John Wiley & Sons, Inc.