发表机构
The Ohio State University; University of Washington; Brown University; Yale University（俄亥俄州立大学; 华盛顿大学; 布朗大学; 耶鲁大学）
机构由 AI 辅助整理，请以论文原文为准。AI 中文总结
本文提出态相互作用代数图解构造（SI-ADC）方法，系统评估其处理自旋-轨道耦合的性能，证明二阶方法在多种性质计算中兼具高效与准确，优于三阶方法。
AI 中文摘要
自旋-轨道耦合和电子关联在广泛的化学和物理现象中扮演着重要角色。在本工作中，我们系统评估了单参考代数图解构造与态相互作用相结合（SI-ADC）方法在存在自旋-轨道耦合情况下描述电子结构的性能。我们发现，二阶SI-ADC方法（SI-ADC(2)）实现的零场分裂精度可与更高水平且计算上更昂贵的方法相媲美，包括变分四分量ADC和基于自旋-轨道有效哈密顿量的二分量ADC方法。我们进一步通过评估一系列不同的自旋-轨道耦合相关性质，包括电子亲和能、电离势、中性激发能、核心电离能以及磁g张量，证明了SI-ADC的广泛适用性，所研究的体系涵盖从小分子到过渡金属配合物和f区化合物。在这些应用中，SI-ADC(2)方法提供了始终准确的结果，这可能部分得益于电子关联效应与自旋-轨道效应之间有利的误差抵消。相比之下，SI-ADC(3)方法通常准确性较低，特别是对于含有过渡金属和重元素的体系。总体而言，这些结果确立了SI-ADC作为一种高效且广泛适用的框架，用于将自旋-轨道耦合纳入ADC计算中以获得电子和光谱性质。
英文摘要
Spin-orbit coupling and electron correlation play important roles in a broad range of chemical and physical phenomena. In this work, we systematically assess the performance of single-reference algebraic diagrammatic construction combined with state interaction (SI-ADC) for describing electronic structure in the presence of spin-orbit coupling. We find that second-order SI-ADC methods (SI-ADC(2)) achieve zero-field-splitting accuracies comparable to those of higher-level and more computationally demanding approaches, including variational four-component ADC and two-component ADC methods based on spin-orbit effective Hamiltonians. We further demonstrate the broad applicability of SI-ADC by evaluating a diverse range of spin-orbit-coupled properties, including electron affinities, ionization potentials, neutral excitation energies, core-ionization energies, and magnetic g-tensors, for systems ranging from small molecules to transition-metal complexes and f-block compounds. Across these applications, SI-ADC(2) methods provide consistently accurate results, likely benefiting in part from favorable error cancellation between electron-correlation and spin-orbit effects. In contrast, SI-ADC(3) methods are generally less accurate, particularly for systems containing transition-metal and heavy elements. Overall, these results establish SI-ADC as an efficient and broadly applicable framework for incorporating spin-orbit coupling into ADC calculations of electronic and spectroscopic properties.
