Division of Theoretical Chemistry, Lund University, SE-223 62 Lund, Sweden.
Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, Campusvej 55, 5230 Odense, Denmark.
J Chem Theory Comput. 2022 Jun 14;18(6):3671-3686. doi: 10.1021/acs.jctc.1c01249. Epub 2022 May 13.
Explicit embedding methods combined with the complex polarization propagator (CPP) enable the modeling of spectroscopy for increasingly complex systems with a high density of states. We present the first derivation and implementation of the CPP in four- and exact-two-component (X2C) polarizable embedding (PE) frameworks. We denote the developed methods PE-4c-CPP and PE-X2C-CPP, respectively. We illustrate the methods by estimating the solvent effect on ultraviolet-visible (UV-vis) and X-ray atomic absorption (XAS) spectra of [Rh(HO)] and [Ir(HO)] immersed in aqueous solution. We moreover estimate solvent effects on UV-vis spectra of a platinum complex that can be photochemically activated (in water) to kill cancer cells. Our results clearly show that the inclusion of the environment is required: UV-vis and (to a lesser degree) XAS spectra can become qualitatively different from vacuum calculations. Comparison of PE-4c-CPP and PE-X2C-CPP methods shows that X2C essentially reproduces the solvent effect obtained with the 4c methods.
显式嵌入方法与复杂极化传播子（CPP）相结合，可以对具有高密度状态的日益复杂的系统进行光谱建模。我们首次在四分量和精确双分量（X2C）极化嵌入（PE）框架中推导出并实现了 CPP。我们分别将开发的方法表示为 PE-4c-CPP 和 PE-X2C-CPP。我们通过估计 [Rh(HO)] 和 [Ir(HO)] 在水溶液中的紫外可见（UV-vis）和 X 射线原子吸收（XAS）光谱的溶剂效应来说明这些方法。此外，我们还估计了可以在水中被光化学激活（以杀死癌细胞）的铂配合物的紫外可见光谱的溶剂效应。我们的结果清楚地表明，必须包括环境：紫外可见（UV-vis）和（在较小程度上）XAS 光谱可以从真空计算中定性地不同。PE-4c-CPP 和 PE-X2C-CPP 方法的比较表明，X2C 本质上再现了 4c 方法获得的溶剂效应。
