基于绝对局域投影的激发态嵌入
Absolutely Localized Projection-Based Embedding for Excited States
摘要：
我们提出了一种量子嵌入方法，允许嵌入在Kohn-Sham密度泛函理论（DFT）环境中的局部激发态的计算。基于投影的量子嵌入方法为DFT中DFT和DFT中的波函数（WF-in-DFT）计算提供了严格的框架。绝对局域化的使用，其中每个子系统的密度仅在与该子系统的原子相关联的基函数中扩展，通过减少WF计算中的轨道数量，为WF-in-DFT计算提供了改进的计算效率。在本工作中，我们将基于绝对局域投影的量子嵌入方法推广到用EOM-CCSD-in-DFT和TDDFT-in-DFT研究局域激发态。嵌入的结果是高度准确的相应的规范EOM-CCSD和TDDFT的结果相比，在整个系统中，与TDDFT-in-DFT往往比规范TDDFT更准确。绝对定域方法可以消除电荷转移态的虚假低激发能，防止激发态的过离域。此外，我们试图恢复的环境响应所造成的电子激发在高层子系统使用不同的方案，并比较其精度。最后，我们将这种方法应用于绿色荧光蛋白的激发态能量的计算，并表明我们系统地收敛到全系统的结果。在这里，我们演示了如何这种方法可以是有用的，在理解激发态，特别是哪些化学部分的激发。这项工作表明，基于绝对局域投影的量子嵌入可以准确地处理局部电子激发，并使计算昂贵的WF方法适用于超出当前计算限制的系统。
英文摘要：
We present a quantum embedding method that allows for the calculation of local excited states embedded in a Kohn-Sham density functional theory (DFT) environment. Projection-based quantum embedding methodologies provide a rigorous framework for performing DFT-in-DFT and wave function in DFT (WF-in-DFT) calculations. The use of absolute localization, where the density of each subsystem is expanded in only the basis functions associated with the atoms of that subsystem, provide improved computationally efficiency for WF-in-DFT calculations by reducing the number of orbitals in the WF calculation. In this work, we extend absolutely localized projection-based quantum embedding to study localized excited states using EOM-CCSD-in-DFT and TDDFT-in-DFT. The embedding results are highly accurate compared to the corresponding canonical EOM-CCSD and TDDFT results on the full system, with TDDFT-in-DFT frequently more accurate than canonical TDDFT. The absolute localization method is shown to eliminate the spurious low-lying excitation energies for charge transfer states and prevent over delocalization of excited states. Additionally, we attempt to recover the environment response caused by the electronic excitations in the high-level subsystem using different schemes and compare their accuracy. Finally, we apply this method to the calculation of the excited state energy of green fluorescent protein and show that we systematically converge to the full system results. Here we demonstrate how this method can be useful in understanding excited states, specifically which chemical moieties polarize to the excitation. This work shows absolutely localized projection-based quantum embedding can treat local electronic excitations accurately, and make computationally expensive WF methods applicable to systems beyond current computational limits.
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