标题： 通过谱矩守恒的自洽GW方法 显示英文标题

标题： Self-consistent GW via conservation of spectral moments

摘要： 我们扩展了一个最近引入的用于模拟带电激发的替代框架[$GW$] [Scott等人，J. Chem. Phys.，158，124102（2023）]，该框架基于GW自能直接计算的谱矩守恒。与其它实现相比，这一框架具有许多理想的正式属性，我们还详细介绍了效率改进和并行化策略，从而实现了一种与已建立的Hartree-Fock代码具有可证明相似缩放比例的实现，且成本仅增加一个数量级。我们还详细介绍了此框架内一系列自洽[$GW$]变体的适用性，包括所有动态变量完全自洽的方案，同时避免了Matsubara轴或解析延拓，允许在零温下形式上收敛。通过研究GW100分子测试集上的各种自洽协议，我们发现一种鲜为人知的基于简化耦合化学势和Fock矩阵优化的自洽[$GW$]方法是最准确的自洽方法。此外，我们验证了最近观察到的证据，即在[$GW$]中基于Tamm-Dancoff的屏蔽近似比这些分子测试案例中的传统随机相位近似屏蔽更准确。最后，我们考虑了叶绿素A分子，发现其结果与实验值在实验不确定性范围内一致，并描述了带电激发的全频谱。 显示英文摘要

摘要： We expand on a recently introduced alternate framework for $GW$ simulation of charged excitations [Scott et. al., J. Chem. Phys., 158, 124102 (2023)], based around the conservation of directly computed spectral moments of the GW self-energy. Featuring a number of desirable formal properties over other implementations, we also detail efficiency improvements and a parallelism strategy, resulting in an implementation with a demonstrable similar scaling to an established Hartree--Fock code, with only an order of magnitude increase in cost. We also detail the applicability of a range of self-consistent $GW$ variants within this framework, including a scheme for full self-consistency of all dynamical variables, whilst avoiding the Matsubara axis or analytic continuation, allowing formal convergence at zero temperature. By investigating a range of self-consistency protocols over the GW100 molecular test set, we find that a little-explored self-consistent variant based around a simpler coupled chemical potential and Fock matrix optimization to be the most accurate self-consistent $GW$ approach. Additionally, we validate recently observed evidence that Tamm--Dancoff based screening approximations within $GW$ lead to higher accuracy than traditional random phase approximation screening over these molecular test cases. Finally, we consider the Chlorophyll A molecule, finding agreement with experiment within the experimental uncertainty, and a description of the full-frequency spectrum of charged excitations.