开壳层参考波函数的相对论运动方程耦合团簇方法
Relativistic equation-of-motion coupled-cluster method using open-shell reference wavefunction
摘要：
在考虑单激发和双激发近似的情况下，成功地实现了开壳层参考相对论运动方程耦合团簇方法的四分量描述。关联计算所需的单体和两体矩阵元使用狄拉克-库仑哈密顿量生成。作为第一次尝试，实施的方法被用来计算一些低的重原子（Ag，Cs，Au，Fr，Lr）和分子（HgH，PbF）系统的价电离能的电离态，相对论的影响确实很重要，以获得高精度的结果。在这些重原子和分子系统中，不仅相对论效应，而且电子关联效应也是至关重要的。为了证明这一事实，我们在四分量相对论运动方程的框架下进一步进行了两次近似，以量化电子关联效应在不同近似水平下的计算值中所起的作用。所有这些计算结果与现有的实验数据以及与其他理论计算值进行比较，以判断在我们的计算中获得的准确度的程度。对所考虑的所有系统的计算结果都取得了很好的一致性，验证了开壳层参考相对论运动方程耦合团簇方法的性能。
英文摘要：
The open-shell reference relativistic equation-of-motion coupled-cluster method within its four-component description is successfully implemented with the consideration of single- and double- excitation approximation. The one-body and two-body matrix elements required for the correlation calculation are generated using Dirac-Coulomb Hamiltonian. As a first attempt, the implemented method is employed to calculate a few of the low-lying ionized states of heavy atomic (Ag, Cs, Au, Fr, Lr) and valence ionization potential of molecular (HgH, PbF) systems, where the effect of relativity does really matter to obtain highly accurate results. Not only the relativistic effect, but also the effect of electron correlation is crucial in these heavy atomic and molecular systems. To justify the fact, we have taken two further approximations in the four-component relativistic equation-of-motion framework to quantify how the effect of electron correlation plays a role in the calculated values at different level of the approximation. All these calculated results are compared with the available experimental data as well as with other theoretically calculated values to judge the extent of accuracy obtained in our calculations. A nice agreement is achieved for all the considered systems which validates the performance of the open-shell reference relativistic equation-of-motion coupled-cluster method.
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