Cebreiro-Gallardo Antonio, Casanova David
Donostia International Physics Center (DIPC), 20018 Donostia, Euskadi, Spain.
Polimero eta Material Aurreratuak: Fisika, Kimika eta Teknologia Saila, Kimika Fakultatea, Euskal Herriko Unibertsitatea (UPV/EHU), PK 1072, 20080 Donostia, Euskadi, Spain.
J Chem Theory Comput. 2025 Jul 8;21(13):6528-6544. doi: 10.1021/acs.jctc.5c00514. Epub 2025 Jun 18.
We introduce a state-interaction approach for computing -matrices within time-dependent density functional theory (TDDFT) and the Tamm-Dancoff approximation (TDA), applied here for the first time. This method provides a detailed understanding of -shifts by explicitly accounting for spin-orbit couplings (SOC) and excitation energies, enabling the analysis of different SOC orders and their contributions. To evaluate its accuracy and reliability, we compare state-interaction TDDFT and TDA with the widely used one-component coupled-perturbed Kohn-Sham approach. Applications to a diverse set of systems, including light and heavy atom molecules as well as transition-metal complexes, demonstrate that both methods yield comparable results in the absence of heavy elements, while the state-interaction approach offers improved insights into SOC effects and their impact on -shifts.
我们引入了一种态相互作用方法，用于在含时密度泛函理论（TDDFT）和塔姆 - 丹科夫近似（TDA）中计算矩阵，此方法首次在此处应用。该方法通过明确考虑自旋 - 轨道耦合（SOC）和激发能，对频移提供了详细的理解，从而能够分析不同的SOC阶次及其贡献。为了评估其准确性和可靠性，我们将态相互作用TDDFT和TDA与广泛使用的单组分耦合微扰科恩 - 沙姆方法进行了比较。对包括轻原子和重原子分子以及过渡金属配合物在内的各种体系的应用表明，在没有重元素的情况下，这两种方法都能产生可比的结果，而态相互作用方法能更深入地洞察SOC效应及其对频移的影响。
