可极化嵌入线性响应理论的量子力学观点
A quantum-mechanical perspective on linear response theory within polarizable embedding
摘要：
极化嵌入内的线性响应理论的推导进行了严格的量子力学处理的复合系统。给出了线性响应函数的两种不同的子系统分解（对称和非对称），并分析和讨论了各个项的极点结构和留数。这种理论分析澄清了哪种形式的响应函数使用在可极化嵌入，我们强调分离出子系统的分子特性的贡献的并发症。例如，基于复杂的线性响应函数的非对称分解，我们推导出守恒定律的综合吸收截面，提供了一个坚实的基础，适当计算的intersubsystem强度借贷固有的耦合子系统，以及如何可以导致负的子系统强度。最后，我们确定的步骤和近似实现从量子力学描述的复合系统的过渡到极化嵌入与经典的治疗环境，从而提供了一个彻底的理由极化嵌入模型中使用的描述。
英文摘要：
The derivation of linear response theory within polarizable embedding is carried out from a rigorous quantum-mechanical treatment of a composite system. Two different subsystem decompositions (symmetric and nonsymmetric) of the linear response function are presented, and the pole structures as well as residues of the individual terms are analyzed and discussed. This theoretical analysis clarifies which form of the response function to use in polarizable embedding, and we highlight complications in separating out subsystem contributions to molecular properties. For example, based on the nonsymmetric decomposition of the complex linear response function, we derive conservation laws for integrated absorption cross sections, providing a solid basis for proper calculations of the intersubsystem intensity borrowing inherent to coupled subsystems and how that can lead to negative subsystem intensities. We finally identify steps and approximations required to achieve the transition from a quantum-mechanical description of the composite system to polarizable embedding with a classical treatment of the environment, thus providing a thorough justification for the descriptions used in polarizable embedding models.
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