Notter François-Paul, Dubillard Sébastien, Bolvin Hélène
Laboratoire de Chimie Quantique, Institut de Chimie de Strasbourg, UMR 7177, 4 rue Blaise Pascal 67000 Strasbourg, France.
J Chem Phys. 2008 Apr 28;128(16):164315. doi: 10.1063/1.2889004.
The ground and excited states of the AmO(2) (+), AmO(2) (2+), and AmO(2) (3+) ions have been studied using the four-component configuration interaction singles doubles, spin-orbit complete active space self-consistent field, and spin-orbit complete active space-order perturbation theory methods. The roles of scalar relativistic effects and spin-orbit coupling are analyzed; results with different methods are carefully compared by a precise analysis of the wave functions. A molecular spinor diagram is used in relation to the four-component calculations while a ligand field model is used for the two-step method. States with the same number of electrons in the four nonbonding orbitals are in very good agreement with the two methods while ligand field and charge transfer states do not have the same excitation energies.
利用四分量组态相互作用单双激发、自旋轨道完全活性空间自洽场和自旋轨道完全活性空间微扰理论方法，对AmO(2)(+)、AmO(2)(2+)和AmO(2)(3+)离子的基态和激发态进行了研究。分析了标量相对论效应和自旋轨道耦合的作用；通过对波函数的精确分析，仔细比较了不同方法的结果。在四分量计算中使用了分子旋量图，而在两步法中使用了配体场模型。在四个非键轨道中具有相同电子数的态，两种方法的结果非常吻合，而配体场态和电荷转移态的激发能不同。
