嵌入系统的垂直激发能：极化 QM/MM 中的垂直激发模型（VEM）
Vertical Excitation Energies of Embedded Systems: The Vertical Excitation Model (VEM) within Polarizable QM/MM
AI总结：
本文提出基于极化 QM/MM 的垂直激发模型（VEM）以计算溶剂化系统垂直激发能，克服了线性响应（LR）忽略溶质弛豫致溶剂重组的局限，基准测试表明针对特定系统选择合适模型可实现最佳精度。
摘要：
基于涨落电荷和偶极子的极化量子力学/分子力学（QM/FQ(F$\mu$)）方法被构建于态特定的垂直激发模型（VEM）框架内，用于计算溶剂化系统的垂直激发能。该方法克服了广泛使用的线性响应（LR）方法的局限性。虽然 LR 能够捕捉溶剂对 QM 跃迁密度的动态响应，但它忽略了电子激发后溶质弛豫所引起的溶剂重组。相比之下，VEM 框架明确地考虑了这一效应。本文报道了使用 QM/FQ(F$\mu$) 对一组代表性溶质——丙烯醛、丙酮、咖啡因、对硝基苯胺、香豆素 153、阿霉素和甜菜碱-30——进行的垂直激发能基准计算，并将 VEM 与 LR、校正 LR（cLR）以及 cLR 2 方案进行了比较。结果显示，溶剂响应因电子跃迁特性不同而存在显著差异，并表明通过为每个特定系统和激发选择最合适的模型可以实现最佳精度。
英文摘要：
Polarizable Quantum Mechanics/Molecular Mechanics (QM/MM) approaches based on fluctuating charges and dipoles (QM/FQ(F$μ$)) are formulated within the state-specific Vertical Excitation Model (VEM) to compute vertical excitation energies of solvated systems. This methodology overcomes the limitations of the widely used Linear Response (LR) approach. While LR can capture the dynamic response of the solvent to the QM transition density, it neglects the solvent reorganization that follows solute relaxation upon electronic excitation. In contrast, the VEM framework explicitly accounts for this effect. Benchmark calculations of vertical excitation energies using QM/FQ(F$μ$) are reported for a representative set of solutes - acrolein, acetone, caffeine, p-nitroaniline, coumarin 153, doxorubicin, and betaine-30 - comparing VEM with LR, corrected LR (cLR), and cLR 2 schemes. The results reveal notable variations in solvent response depending on the character of the electronic transition and demonstrate that optimal accuracy can be achieved by selecting the most appropriate model for each specific system and excitation.
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