Department of Physics, Florida A&M University, Tallahassee, Florida 32307, USA.
J Chem Phys. 2013 Apr 28;138(16):164303. doi: 10.1063/1.4799917.
The electronic and geometrical structures of the M12 and M13 clusters where M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn along with their singly negatively and positively charged ions are studied using all-electron density functional theory within the generalized gradient approximation. The geometries corresponding to the lowest total energy states of singly and negatively charged ions of V13, Mn12, Co12, Ni13, Cu13, Zn12, and Zn13 are found to be different from the geometries of the corresponding neutral parents. The computed ionization energies of the neutrals, vertical electron detachment energies from the anions, and energies required to remove a single atom from the M13 and M13(+) clusters are in good agreement with experiment. The change in a total spin magnetic moment of the cation or anion with respect to a total spin magnetic moment of the corresponding neutral is consistent with the one-electron model in most cases, i.e., they differ by ±1.0 μ(B). Exceptions are found only for Sc12(-), Ti12(+), Mn12(-), Mn12(+), Fe12(-), Fe13(+), and Co12(+).
使用全电子密度泛函理论在广义梯度近似下，研究了 M12 和 M13 团簇（其中 M = Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Cu 和 Zn）及其单负电荷和单正电荷离子的电子和几何结构。V13、Mn12、Co12、Ni13、Cu13、Zn12 和 Zn13 的单负电荷和单正电荷离子的总能量最低状态对应的几何形状与相应中性母体的几何形状不同。中性体的计算电离能、阴离子的垂直电子离解能以及从 M13 和 M13(+)团簇中去除单个原子所需的能量与实验值吻合良好。阳离子或阴离子的总自旋磁矩相对于相应中性体的总自旋磁矩的变化在大多数情况下与单电子模型一致，即它们相差 ±1.0 μ(B)。只有 Sc12(-)、Ti12(+)、Mn12(-)、Mn12(+)、Fe12(-)、Fe13(+) 和 Co12(+) 例外。
