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Such a model is by definition oversimplified given the covalency of bonding and consequent breakdown of the ligand field approximation. It is nevertheless useful to frame the discussion of the formal valence of the manganese ion within that given in the literature
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Such a model is by definition oversimplified given the covalency of bonding and consequent breakdown of the ligand field approximation. It is nevertheless useful to frame the discussion of the formal valence of the manganese ion within that given in the literature.
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geometry optimization of complexes for which oxalate C-C bond cleavage occurs is partial, given the difficulty of locating a well-defined minimum energy structure due to flattening of the potential surface. In any event, oxalate C-C bond clearly breaks, and the linear O-C-O angles strongly suggest that the observed "cleavage" is oxidative. While recognizing that it is technically fallacious to discuss changes during a geometry optimization in terms of a chemical reaction, these changes nevertheless imply that a stable, minimum-energy structure in which the oxalate C-C bond is intact was not be found with this model chemistry, starting geometry, and gradient and Hessian update algorithms. We have therefore framed our discussion of the behavior of model complex 13 relative to that of other minimized structures obtained in these studies
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The geometry optimization of complexes for which oxalate C-C bond cleavage occurs is partial, given the difficulty of locating a well-defined minimum energy structure due to flattening of the potential surface. In any event, oxalate C-C bond clearly breaks, and the linear O-C-O angles strongly suggest that the observed "cleavage" is oxidative. While recognizing that it is technically fallacious to discuss changes during a geometry optimization in terms of a chemical reaction, these changes nevertheless imply that a stable, minimum-energy structure in which the oxalate C-C bond is intact was not be found with this model chemistry, starting geometry, and gradient and Hessian update algorithms. We have therefore framed our discussion of the behavior of model complex 13 relative to that of other minimized structures obtained in these studies.
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99
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0037044159
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This performance enhancement has been suggested to arise from a fortuitous cancellation of errors between truncated bases and the erroneous long-range behavior of the exchangecorrelation potential see ref 12
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This performance enhancement has been suggested to arise from a fortuitous cancellation of errors between truncated bases and the erroneous long-range behavior of the exchangecorrelation potential (see ref 12).
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102
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16244389024
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