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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Linear Energy Relationships for the Octahedral Preference of Mg, Ca and Transition Metal Ions
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Linear Energy Relationships for the Octahedral Preference of Mg, Ca and Transition Metal Ions

机译：Mg，Ca和过渡金属离子的八面体优先级的线性能量关系

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The geometry, atomic charges, force constants, and relative energies of the symmetric and distorted M2+(H2O)4(F-)2, M3+(H2O)4(F-)2, M2+(H2O)3(F-)2, and M3+(H2O)3(F-)2 metal complexes, M ) Mg, Ca, Co, Cu, Fe, Mn, Ni, Zn, Cr, V, were calculated by using the B3LYP/TZVP density functional method in both gas phase and aqueous solution, modeled using the polarized continuum model. The deformation energy associated with moving one water ligand 12° from the initial “octahedral” arrangement, in which all O-M-O, O-M-F, and F-M-F angles are either 90° or 180°, was calculated to examine the angular ligand flexibility. For all M2+(H2O)4(F-)2 complexes, this distortion increased the energy of the complex in proportion to the electrostatic potential-derived (ESP) charge of the metal, and in proportion to D-10, where D is the distance from the distorted ligand to its closest neighbor. The octahedral stability was further examined by calculating the energies for the removal of a water ligand from the octahedral complex to form a square-pyramidal or trigonal-bipyramidal complex. The octahedral preference, defined as the negative of the corresponding binding energy of the ligand, was found to linearly correlate with the ESP charge of the metal in both the gas phase and aqueous solution. The obtained results indicate that quantum-mechanical covalent effects are of secondary importance for both the flexibility and the octahedral preference of M2+(H2O)4(F-)2 and M3+(H2O)4(F-)2 complexes. This conclusion and supporting data are important for the development of consistent molecular mechanical force fields of the studied metal ions.
机译：对称且扭曲的M2 +（H2O）4（F-）2，M3 +（H2O）4（F-）2，M2 +（H2O）3（F-）2的几何形状，原子电荷，力常数和相对能量，和M3 +（H2O）3（F-）2金属配合物M）Mg，Ca，Co，Cu，Fe，Mn，Ni，Zn，Cr，V通过B3LYP / TZVP密度泛函法在两种气体中计算得出相和水溶液，使用极化连续介质模型建模。计算了与一个水配体从初始“八面体”排列移动12°相关的变形能量，其中所有O-M-O，O-M-F和F-M-F角均为90°或180°，以检查角配体的柔性。对于所有M2 +（H2O）4（F-）2配合物，这种畸变与金属的静电势衍生（ESP）电荷成比例，与D-10成比例，从而增加了配合物的能量，其中D是从扭曲的配体到其最近邻的距离。通过计算从八面体络合物中除去水配体以形成正方形-金字塔形或三角-双锥体络合物的能量，进一步检查了八面体稳定性。发现八面体偏好定义为配体相应结合能的负值，与气相和水溶液中金属的ESP电荷线性相关。获得的结果表明，量子力学共价效应对于M2 +（H2O）4（F-）2和M3 +（H2O）4（F-）2配合物的灵活性和八面体优先性具有次要重要性。该结论和支持数据对于开发所研究金属离子的一致分子机械力场很重要。

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