LDF－Slater过渡态理论计算原子系统激活能

The Calculation of the Ionization Energy of Automic Systems by the LDF-Slater Transition State Theory

在ＬＤＦ理论基础上，按Ｓｌａｔｅｒ过渡态理论，利用Ｋｏｈｎ－Ｓｈａｍ－Ｄｉｒａｃ方程对原子系统的芯态和价态离化能进行第一性原理计算．以Ｃａ和Ｓ原子为例，根据ＬＤＦ本征值ξｉ、基态和激发态的ＬＤＦ自洽收敛总能差△ＳＣＦ、Ｓｌａｔｅｒ过渡态理论三种方法计算结果与实验值对比表明，△ＳＣＦ和Ｓｌａｔｅｒ过渡态理论可以明显改善原子系统激活能的计算结果，而后者更具有实用且简单的优点，可推广到更复杂的系统．

Based on the Local Density Functional (LDF) and the Slater transition-state theories, the ionization energies of the core and valence-states of atomic systems have been calculated by the first-principles method via Kohn-Sham-Dirac equation. Using Ca and S atoms as the example, the LDF eigenvalues ξi the differences of self-consistent total energy △SCF of the ground states and excited states and the results from the Slater transition state theory are compared with the experimental data. It is found that the △SCF and the Slater transition state theory greatly improve the calculational results of the ionization energies. The latter method is also of the advantage of the simplicity and able to be extended to more complicated systems.