The relative performance of the local density approximation and gradient-corrected density functional theory for computing metal–ligand distances in Werner-type and organometallic complexes
✍ Scribed by Mark R. Bray; Robert J. Deeth; Veronica J. Paget; Paul D. Sheen
- Publisher
- John Wiley and Sons
- Year
- 1997
- Tongue
- English
- Weight
- 157 KB
- Volume
- 61
- Category
- Article
- ISSN
- 0020-7608
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✦ Synopsis
Optimized metal᎐ligand M᎐L bond lengths for 17 classical Werner-type transition-metal Ž . complexes were calculated using the local density approximation LDA and a gradient-Ž .
corrected
GC extension. GCs lengthen the bonds by between 0.02 and 0.09 A relative to ˚the LDA results. The latter range from 0.02 A shorter than observed to 0.05 A longer, ẘhile the GC data range from exact agreement with experiment to some 0.12 A too long.
˚The LDA rms deviation is 0.025 A compared to the GC error of 0.070 A. In contrast, data from the literature for organometallic species show that the LDA gives systematically too short M᎐L distances and GCs lead to a better agreement with experiment. The relative performance of LDA and GC functionals reflects the qualitatively different chemistries of organometallic and Werner-type complexes. The magnitude of the GC bond-length expansion for the latter correlates with the ionicity of the M᎐L interaction.