Wang Fan, Ziegler Tom
Department of Chemistry, University of Calgary, Calgary, Alberta T2N 1N4, Canada.
J Chem Phys. 2005 Nov 15;123(19):194102. doi: 10.1063/1.2104427.
In the present work the electronic spectra of PtCl(4), PtBr(4), and Pt(CN)(4) are studied with a recently proposed relativistic time-dependent density-functional theory (TDDFT) based on the two-component zeroth-order regular approximation and a noncollinear exchange-correlation (XC) functional. The contribution to the double group excited states in terms of singlet and triplet single group excited states is estimated through the inner product of the transition density matrix obtained from two-component and scalar relativistic TDDFT calculations to better understand the double group excited states. Spin-orbital coupling effects are found to be very important in order to simulate the electronic spectra of these complexes. The results show that the two-component TDDFT formalism can afford excitation energies with high accuracy for the transition-metal systems studied here when use is made of a proper XC potential.
在本工作中，采用基于二分量零阶正则近似和非共线交换相关（XC）泛函的最近提出的相对论含时密度泛函理论（TDDFT），研究了[PtCl₄]²⁻、[PtBr₄]²⁻和[Pt(CN)₄]²⁻的电子光谱。通过从二分量和标量相对论TDDFT计算得到的跃迁密度矩阵的内积，估计单重态和三重态单群激发态对双群激发态的贡献，以便更好地理解双群激发态。发现自旋轨道耦合效应对于模拟这些配合物的电子光谱非常重要。结果表明，当使用适当的XC势时，二分量TDDFT形式体系能够为这里研究的过渡金属体系提供高精度的激发能。
