Computational estimation of lanthanoid-water bond lengths by semiempirical methods

Journal of Chemical Information and Modeling

Volumn 50, Issue 2, 2010, Pages 217-220

  Seitz, Michael ^a   Alzakhem, Nicola ^a  

^a RUHR UNIVERSITY BOCHUM   (Germany)

Author keywords

[No Author keywords available]

Indexed keywords

BINARY ALLOYS; EUROPIUM ALLOYS; NORMAL DISTRIBUTION; TERBIUM ALLOYS; TERBIUM COMPOUNDS;

COMPUTATIONAL ESTIMATION; GEOMETRICAL DEVIATIONS; LANTHANOIDS; SEMI-EMPIRICAL METHODS; STATISTICAL INFERENCE; WORST CASE ERROR;

EUROPIUM COMPOUNDS;

LANTHANIDE; WATER;

ARTICLE; CHEMICAL MODEL; CHEMISTRY; COMPUTER SIMULATION; PROBABILITY; QUANTUM THEORY;

COMPUTER SIMULATION; LANTHANOID SERIES ELEMENTS; MODELS, CHEMICAL; PROBABILITY; QUANTUM THEORY; WATER;

EID: 77649199424     PISSN: 15499596     EISSN: 1549960X     Source Type: Journal    
DOI: 10.1021/ci9003442     Document Type: Article

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34. Under "real" structures, we understand the corresponding crystal structures for the purpose of this investigation. The estimated standard deviations as determined by single crystal X-ray diffraction in bond lengths between lanthanoids and N- or O-donor ligands are usually well below 0.3%. Since the errors of the computational models are much bigger than the ones associated with the crystal structure values, we assume the latter to be negligible with the acknowledgment that this is an approximation.
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41. In addition, a number of other conditions had to be fulfilled, for example, only trivalent lanthanoid centers and exclusively N- or O-donor ligands. For a full list, see Supporting Information.
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48. It should be emphasized that the errors listed are not solely the result of inadequacies of the computational models but also to a great extent a function of the statistical uncertainties due to the limited sample set sizes.
49. The statistical analysis for individual lanthanoids in cyclen-derived 2 is not meaningful because of the small sample sizes.
50. For comparison, typical errors for distances obtained from fitting of NMRD profiles for Gd-based MRI contrast agents are also about 5% (see refs 2 and 4).