Combining spin-adapted open-shell TD-DFT with spin-orbit coupling
Combining spin-adapted open-shell TD-DFT with spin-orbit coupling
复制标题
将自旋适应开壳层 TD-DFT 与自旋轨道耦合相结合
DOI：
10.1080/00268976.2013.785611
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发表时间：
2013-12-01
影响因子：
1.7
通讯作者：
Liu, Wenjian
中科院分区：
文献类型：
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作者：
Li, Zhendong;Suo, Bingbing;Liu, Wenjian
将最近提出的自旋自适应含时密度泛函理论(S-TD-DFT)推广到相对论领域，用于开壳系统激发态的精细结构分裂。标量相对论效应通过精确的双分量(X2C)哈密顿量的无自旋(SF)部分被处理到无穷级，而标量激发态之间的自旋轨道耦合(SOC)则通过由相同的X2C哈密顿量导出的有效的单电子自旋轨道算符来微扰处理。对含有重元素的典型开壳系统的计算结果表明，SF-X2C-S-TD-DFT-SOC组合方法是非常有前途的。空间简并基态的精细结构分裂也可以用非简并激发态作为参考来描述。
The recently proposed spin-adapted time-dependent density functional theory (S-TD-DFT) is extended to the relativistic domain for fine-structure splittings of excited states of open-shell systems. Scalar-relativistic effects are treated to infinite order via the spin-free (sf) part of the exact two-component (X2C) Hamiltonian, whereas the spin-orbit couplings (SOC) between the scalar-excited states are treated perturbatively via an effective one-electron spin-orbit operator derived from the same X2C Hamiltonian. The calculated results for prototypical open-shell systems containing heavy elements reveal that the composite approach sf-X2C-S-TD-DFT-SOC is very promising. The fine-structure splitting of a spatially degenerate ground state can also be described properly by taking a non-degenerate excited state as the reference.