论文标题
运动方程式耦合群集阻尼 - 响应框架,并具有说明性应用程序,用于共鸣X射线散射
New Implementation of an Equation-of-Motion Coupled-Cluster Damped-Response Framework with Illustrative Applications to Resonant Inelastic X-ray Scattering
论文作者
论文摘要
我们介绍了一个阻尼响应框架的实现,用于在运动方程耦合群集群单打和双打(CCSD)(CCSD)和二阶近似耦合群集群单打(CC2)(CC2)的理论中,以开放式耦合的群集群和双打(CCSD)计算谐振非弹性X射线散射(RIX)。该框架为将来扩展到更高的激发方法(值得注意的是,耦合的群集单打和双扰动三元组,CC3)和多级方法奠定了基础。 我们的实施采用了完全放松的基础状态,以及核心价分离投影技术的不同变体来解决融合问题。将说明性的结果与在QCHEM以及实验中可用的冷冻核心核价分离方法中获得的结果进行了比较。 与CCSD相比,评估了CC2方法的性能。已经发现,尽管CC2方法明显低于X射线吸收光谱的CCSD,但当对相同的价值激发态进行探测时,CC2 RIXS光谱的质量通常与CCSD理论水平的质量相当。最后,我们提出了水溶液中溶剂分子的初步RIXS结果。
We present an implementation of a damped response framework for calculating resonant inelastic X-ray scattering (RIXS) at the equation-of-motion coupled cluster singles and doubles (CCSD) and second-order approximate coupled cluster singles and doubles (CC2) levels of theory in the open-source program $e^T$. This framework lays the foundation for future extension to higher excitation methods (notably, the coupled cluster singles and doubles with perturbative triples, CC3) and to multilevel approaches. Our implementation adopts a fully relaxed ground state, and different variants of the core-valence separation projection technique to address convergence issues. Illustrative results are compared with those obtained within the frozen-core core-valence separated approach, available in Q-Chem, as well as with experiment. The performance of the CC2 method is evaluated in comparison with that of CCSD. It is found that, while the CC2 method is noticeably inferior to CCSD for X-ray absorption spectra, the quality of the CC2 RIXS spectra is often comparable to that of the CCSD level of theory, when the same valence excited states are probed. Finally, we present preliminary RIXS results for a solvated molecule in aqueous solution.