论文标题
激发态的自洽Møller-plesset扰动理论
Self-consistent Møller-Plesset Perturbation Theory For Excited States
论文作者
论文摘要
在量子化学中，获得系统的平均场溶液，并以后孔（HF）方式纳入电子相关性，这是基本计算的标准方案之一。原则上，该方案还可以描述激发态，但目前尚未广泛使用，这主要是由于难以定位平均场激发态。随着激发状态轨道放松的最新发展，现在可以定期将自洽的兴奋状态解决方案位于各种理论上。在这项工作中，我们探讨了使用Møller-plesset摄动理论纠正HF激发态的可能性。在各种PT2变体中，我们发现受限制的开壳MP2（ROMP2）给出了与最佳密度功能理论结果相当的激发能，从而提供$ \ sim 0.2 $ eV的平均无符号误差，这在广泛的单个单调状态函数激励上，仅在非文字$ o（n^5）$（n^5）$计算量表上。
In quantum chemistry, obtaining a system's mean-field solution and incorporating electron correlation in a post Hartree-Fock (HF) manner comprise one of the standard protocols for ground-state calculations. In principle, this scheme can also describe excited states but is not widely used at present, primarily due to the difficulty of locating the mean-field excited states. With recent developments in excited-state orbital relaxation, self-consistent excited-state solutions can now be located routinely at various levels of theory. In this work, we explore the possibility of correcting HF excited states using Møller-Plesset perturbation theory to the second order. Among various PT2 variants, we find that the restricted open-shell MP2 (ROMP2) gives excitation energies comparable to the best density functional theory results, delivering $\sim 0.2$ eV mean unsigned error over a wide range of single-configuration state function excitations, at only non-iterative $O(N^5)$ computational scaling.
