The implementation of analytical energy gradients based on a quasi‐relativistic density functional method: The application to metal carbonyls
抄録
<jats:title>Abstract</jats:title><jats:p>The capabilities of the quasi‐relativistic scheme due to J. G. Snijders at al. [Mol. Phys, <jats:bold>38</jats:bold>, 1969 (1979) <jats:italic>Ibid.</jats:italic>, J. Phys. Chem. <jats:bold>93</jats:bold>, 3050 (1989)] has been extended by deriving expressions for the energy gradients with respect to the total energy <jats:italic>E</jats:italic><jats:sup>QR</jats:sup> and implementing them into the <jats:sc>ADF</jats:sc> program system [B. to Velde and E. J. Baerends, Int. J. Quantum Chem. <jats:bold>33</jats:bold>, 87 (1988)]. This implementation enables automated geometry optimization at the relativistic level. The new scheme has been applied together with a self‐consistent nonlocal density functional scheme, <jats:sc>NL</jats:sc>–<jats:sc>SCF</jats:sc> + <jats:sc>QR</jats:sc>, to the calculation of MCO bond lengths and the first bond dissociation energy (<jats:sc>FBDE</jats:sc>) in the binary transition metal carbonyls M(CO)<jats:sub>5</jats:sub> (M = Fe, Ru, Os) and M(CO)<jats:sub>6</jats:sub> (M = Cr, Mo, W). The calculated MCO bond lengths are in good agreement with available experimental data with an error typically smaller than 0.01 Å. The calculated FBDES are 45.7 (Fe), 33.0 (Ru), 34.7 (Os), 46.2 (Cr), 39.7 (Mo), and 43.7 (W) kcal/mol, respectively. These values compare well with the available experimental estimates of 42 (Fe), 28 (Ru), 31 (Os), 37 (Cr), 41 (Mo), and 46 (W), respectively. The relativistic effects are found to contract MCO bonds by between 0.07 and 0.16 A and strengthen the FBDEs by 5‐11 kcal/mol for third‐row compounds. The relativistic stabilization of the <jats:sc>FBDES</jats:sc> among the 5<jats:italic>d</jats:italic> elements makes, in general, the MCO bond of the 4<jats:italic>d</jats:italic> element weakest within a triad. © 1995 John Wiley & Sons, Inc.</jats:p>
収録刊行物
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- International Journal of Quantum Chemistry
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International Journal of Quantum Chemistry 56 (5), 477-488, 1995-12-05
Wiley
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詳細情報 詳細情報について
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- CRID
- 1363951795328745984
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- ISSN
- 1097461X
- 00207608
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- データソース種別
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- Crossref