A Combined Wave Function and Density Functional Approach for K-Edge X-ray Absorption Near-Edge Spectroscopy: A Case Study of Hydrated First-Row Transition Metal Ions,The Journal of Physical Chemistry Letters

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A Combined Wave Function and Density Functional Approach for K-Edge X-ray Absorption Near-Edge Spectroscopy: A Case Study of Hydrated First-Row Transition Metal Ions
The Journal of Physical Chemistry Letters ( IF 4.8 ) Pub Date : 2023-05-31 , DOI: 10.1021/acs.jpclett.3c00611
Soumen Ghosh ₁ , Shaul Mukamel ₂ , Niranjan Govind ₁

Affiliation

The prediction of X-ray absorption spectra (XAS) of transition metal complexes has important and broad application areas in chemistry and biology. In this letter, we have investigated the predictive ability of multiconfiguration pair-density functional theory (MC-PDFT) for X-ray absorption spectra by calculating the metal K pre-edge features of aquated 3d transition metal ions in common oxidation states. MC-PDFT results were compared with experimentally measured spectra as well as analyzed against results from restricted active-space second-order perturbation theory (RASPT2) and time-dependent density functional theory (TDDFT). As expected, TDDFT performs well for excited states that can be accurately represented by singly excited configurations but fails for excited states where higher order excitations become important. On the other hand, both RASPT2 and MC-PDFT provide quantitatively accurate results for all excited states irrespective of their character. While core-level spectroscopy with RASPT2 is accurate, it is computationally expensive. Our results show that MC-PDFT performs equally well with significantly lower computational cost and is an encouraging alternate approach for X-ray spectroscopies.

中文翻译：

K 边 X 射线吸收近边光谱的组合波函数和密度泛函方法：以水合第一行过渡金属离子为例

过渡金属配合物的 X 射线吸收光谱 (XAS) 预测在化学和生物学中具有重要而广泛的应用领域。在这封信中，我们通过计算水化 3 d的金属 K 前边缘特征，研究了多构型对密度泛函理论 (MC-PDFT) 对 X 射线吸收光谱的预测能力常见氧化态的过渡金属离子。MC-PDFT 结果与实验测量的光谱进行了比较，并根据受限活动空间二阶微扰理论 (RASPT2) 和时间相关密度泛函理论 (TDDFT) 的结果进行了分析。正如预期的那样，TDDFT 对于可由单激发配置准确表示的激发态表现良好，但对于高阶激发变得重要的激发态则表现不佳。另一方面，RASPT2 和 MC-PDFT 都为所有激发态提供了定量准确的结果，而不管它们的特性如何。虽然使用 RASPT2 的核心级光谱是准确的，但计算量很大。

更新日期：2023-05-31

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