提升XPS计算的准确性：探索用于CVS-EOMIP-CCSD计算的混合基组方案
Enhancing the Accuracy of XPS Calculations: Exploring Hybrid Basis Set Schemes for CVS-EOMIP-CCSD Calculations
AI总结：
本研究针对X射线光谱计算中基组规模带来的精度与成本权衡问题，结合CVS-EOMIP-CCSD方法构建分段混合基组，分析其对第一周期p区元素K边电离能计算的影响，建立了可靠低成本的小分子电离能估算方案。
摘要：
可靠的计算方法与基组对于X射线光谱建模至关重要，是从实验X射线光谱中提取并解读电子与结构信息的基础。尤其值得注意的是，基组规模带来的数值精度与计算成本之间的权衡是一大核心挑战，因为分子轨道在芯空穴态下会发生剧烈弛豫。此前研究已证实，为清晰理解芯空穴形成引发的电子结构变化，必须使用具备足够灵活性的基组来展开轨道，尤其是芯区轨道。本研究聚焦于芯空穴电离态计算的优化，采用运动方程耦合簇（EOM-CC）方法族，对“混合”基组与混搭基组的有效性开展了系统性分析。研究中我们结合使用CVS-EOMIP-CCSD方法，利用现成的Dunning相关一致基组分段构建混合基组，对一组气相小分子的X射线电离能进行了计算。我们的结果揭示了基组对第一周期p区元素K边电离能的CVS-EOMIP-CCSD计算的影响规律。这些发现帮助我们更深入地理解所计算的芯电离能的基组依赖性，同时为建立一套可靠且高性价比的理论估算流程提供了依据，可用于计算含此类元素的小分子的电离能。
英文摘要：
Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between numerical accuracy and computational cost due to the size of the basis set is a major challenge, since molecular orbitals undergo extreme relaxation in the core-hole state. To gain clarity on changes in electronic structure induced by the formation of a core-hole, the use of sufficiently flexible basis for expanding the orbitals, particularly for the core region, has been shown to be essential. This work focuses on the refinement of core-hole ionized state calculations using the equation-of-motion coupled cluster (EOM-CC) family of methods through an extensive analysis on the effectiveness of "hybrid" and mixed basis sets. In this investigation, we utilize the CVS-EOMIP-CCSD method in combination and construct hybrid basis sets piece-wise from readily available Dunning's correlation consistent basis sets in order to calculate x-ray ionization energies for a set of small gas phase molecules. Our results provide insights into the impact of basis sets on CVS-EOMIP-CCSD calculations of K-edge ionization energies of first-row p-block elements. These insights enable us to understand more about the basis set dependence of the core IEs computed and allow us to establish a protocol for deriving reliable and cost-effective theoretical estimates for computing IEs of small molecules containing such elements.
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