We investigate the accuracy of the Outer-Valence Green’s Function (OVGF) electron propagator approach for the computation of vertical ionization energies (IEs) of several hydrogen-bonded dimers. The vertical IEs were computed with 10 different basis sets (i.e. Pople, correlation-consistent and augmented correlation-consistent) and compared with references obtained at the extrapolated equation-of-motion coupled-cluster singles and doubles level. Our study shows that the OVGF method predicts accurately the IEs of hydrogen-bonded clusters. Furthermore, the choice of an optimal basis set is analyzed: our results suggest that the aug-cc-pVDZ basis set provides the best compromise between accuracy and computational costs. The benchmark study provided in this work represents an essential step to investigate molecular ionization, and thus molecular reduction–oxidation properties, in the liquid phase.

我们调查外价格林函数（OVGF）电子传播方法的准确性，以计算几个氢键二聚体的垂直电离能（IEs）。垂直IE是用10个不同的基础集（即Pople，相关性一致和增强的相关性一致），并与外推运动方程耦合群集单双打水平获得的参考值进行比较。我们的研究表明，OVGF方法可以准确预测氢键团簇的IE。此外，分析了最佳基础集的选择：我们的结果表明aug-cc-pVDZ基础集在准确性和计算成本之间提供了最佳折衷方案。这项工作中提供的基准研究代表了研究液相中分子电离以及分子还原-氧化性质的重要步骤。