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Excitation energies from Görling-Levy perturbation theory along the range-separated adiabatic connection

机译:沿距离分隔的绝热连接的Görling-Levy微扰理论产生的激发能

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摘要

A Görling-Levy (GL)-based perturbation theory along the range-separated adiabatic connection is assessed for the calculation of electronic excitation energies. In comparison with the Rayleigh-Schrödinger (RS)-based perturbation theory introduced in a previous work [E. Rebolini, J. Toulouse, A. M. Teale, T. Helgaker, A. Savin, Mol. Phys. 113, 1740 (2015)], this GL-based perturbation theory keeps the ground-state density constant at each order and thus gives the correct ionization energy at each order. Excitation energies up to first order in the perturbation have been calculated numerically for the helium and beryllium atoms and the hydrogen molecule without introducing any density-functional approximations. In comparison with the RS-based perturbation theory, the present GL-based perturbation theory gives much more accurate excitation energies for Rydberg states but similar excitation energies for valence states.
机译:沿距离分隔的绝热连接的基于Görling-Levy(GL)的微扰理论被评估用于电子激发能的计算。与之前的工作中介绍的基于Rayleigh-Schrödinger(RS)的摄动理论相比[E. Rebolini,J.Toulouse,A.M。Teale,T.Helgaker,A.Savin,Mol。物理113,1740(2015)],这种基于GL的微扰理论使基态密度在每个阶上保持恒定,从而在每个阶上给出正确的电离能。在不引入任何密度泛函近似的情况下,已对氦原子,铍原子和氢分子的扰动中的一级激发能进行了数值计算。与基于RS的扰动理论相比,当前基于GL的扰动理论为Rydberg态提供了更为精确的激励能量,而为化合价态提供了相似的激励能量。

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