Quantum mechanical simulations that include the effects of the liquid environment are highly relevant for the characterization of solid-liquid interfaces, which is crucial for the design of a wide range of devices. In this work we present a rigorous and systematic study of the band alignment of semiconductors in aqueous solutions by contrasting a range of hybrid explicit/implicit models against explicit atomistic simulations based on density-functional theory. We find that consistent results are obtained provided that the first solvation shell is treated explicitly. Interestingly, the first molecular layer of explicit water is only relevant for the pristine surfaces without dissociatively adsorbed water, hinting at the importance of saturating the surface with quantum mechanical bonds. By referencing the averaged electrostatic potentials of explicit and implicit water against vacuum, we provide absolute alignments, finding maximal differences of only \(\sim\) 0.1–0.2 V. Furthermore, the implicit reference potential is shown to exhibit an intrinsic offset of −0.33 V with respect to vacuum, which is traced back to the absence of an explicit water surface in the implicit model. These results pave the way for accurate simulations of solid-liquid interfaces using minimalistic explicit/implicit models.

包括液体环境影响的量子力学模拟与固液界面的表征高度相关，这对于设计多种器件至关重要。在这项工作中，我们通过对比一系列混合显式/隐式模型与基于密度泛函理论的显式原子模拟，对水溶液中半导体的能带对准进行了严格而系统的研究。我们发现，只要第一个溶剂化壳得到明确处理，就可以获得一致的结果。有趣的是，显性水的第一分子层仅与原始表面相关，而没有离解性吸附的水，这暗示了用量子机械键使表面饱和的重要性。\（\ sim \） 0.1-0.2V。此外，隐式参考电势相对于真空表现出-0.33 V的本征偏移，这可追溯到隐式模型中不存在显式水面的情况。这些结果为使用简约显式/隐式模型进行固-液界面的精确模拟铺平了道路。