Department of Physics, Chemistry and Pharmacy, University of Southern Denmark, DK-5230 Odense M, Denmark.
J Phys Chem B. 2023 Apr 13;127(14):3248-3256. doi: 10.1021/acs.jpcb.2c08721. Epub 2023 Apr 1.
The polarizable density embedding (PDE) model is a focused QM/QM fragment-based embedding model designed to model solvation effects on molecular properties. We extend the PDE model to include exchange and nonadditive exchange-correlation (for DFT) in the embedding potential in addition to the existing electrostatic, polarization, and nonelectrostatic effects already present. The resulting model, termed PDE-X, yields localized electronic excitation energies that accurately capture the range dependence of the solvent interaction and gives close agreement with full quantum mechanical (QM) results, even when using minimal QM regions. We show that the PDE-X embedding description consistently improves the accuracy of excitation energies for a diverse set of organic chromophores. The improved embedding description leads to systematic solvent effects that do not average out when applying configurational sampling.
极化密度嵌入（PDE）模型是一种基于QM 片段的聚焦型嵌入模型，旨在模拟溶剂对分子性质的影响。我们在嵌入势中扩展了 PDE 模型，除了现有的静电、极化和非静电效应外，还包括交换和非加性的交换相关（对于 DFT）。所得模型称为 PDE-X，可产生局域电子激发能，准确捕捉溶剂相互作用的范围依赖性，并与全量子力学（QM）结果非常吻合，即使使用最小的 QM 区域也是如此。我们表明，PDE-X 嵌入描述一致地提高了各种有机发色团激发能的准确性。改进的嵌入描述导致系统的溶剂效应，在应用构象采样时不会平均化。
