水界面物理化学过程的研究在材料科学、能源环境科学、化学工程等领域具有重要意义。本文基于密度泛函理论、第一性原理分子动力学（AIMD）、增强采样方法等展开了一系列研究，主要分为二部分：1、固-水界面的物理化学过程：重点探讨了电化学界面上离子的尺寸、电荷对双电层结构的调控，为提高电催化效率、能源储氢等提供新的见解；2、气-水界面的物理化学过程：重点研究了N₂O₅分子在海洋气溶胶表面的反应性，揭示了不同卤素离子对反应机理的影响，为实验提供了新的研究方向。我们还讨论了基于AIMD研究的机遇与挑战，展望了机器学习在该领域研究的应用和发展。主要结论如下：

1、固-水界面：

金属界面水分子取向不仅受到界面电压调控，还与双电层中金属阳离子的尺寸和电荷密切相关。

不同阳离子与界面的相互作用对界面氢键网络具有明显的影响，Mg²⁺相较于Na⁺、Ca²⁺表现出相反趋势。

2、气-水界面：

N₂O₅与海洋气溶胶中卤素反应活性高，生成ClNO₂是其与Cl^-反应的主要反应通道，而其与Br^-/I^-反应生成BrONO/IONO几乎是无能垒过程，因此BrONO/IONO是关键反应中间体。

BrONO/IONO反应中间体能够进一步和Br^-/I^-反应产生Br₃^-/I₃^-，从而进一步蒸发形成Br₂/I₂，参与大气卤素循环。

Research on the physical and chemical processes at heterogeneous water interfaces is of significant importance in materials science, energy and environmental science, and chemical engineering. This paper presents a series of studies based on density functional theory (DFT), ab initio molecular dynamics (AIMD), enhanced sampling methods, and machine learning. The research is divided into two main parts: 1. Solid-Water Interface Physical and Chemical Processes: This section focuses on the regulation of the double layer structure by ion size and charge at electrochemical interfaces, providing new insights for improving electrocatalytic efficiency and hydrogen energy storage; 2. Gas-Water Interface Physical and Chemical Processes: This part investigates the reactivity of N₂O₅ molecules at the oceanic aerosol interface, revealing the impact of different halide ions on the reaction mechanism and offering new directions for experimental research. The opportunities and challenges of AIMD-based research are discussed, and the application and development of machine learning in this field are explored. Main conclusions are as follows:

Solid-Water Interface:

The orientation is regulated not only by interface voltage but also closely related to the size and charge of metal cations in the double layer.

The interaction significantly influences the hydrogen bond network at the interface. Mg²⁺, compared to Na⁺ and Ca²⁺, exhibits an opposite trend.

2. Air-Water Interface:

The reactivity is high, with ClNO₂ formation being the primary reaction pathway with Cl⁻. The reactions with Br⁻/I⁻, leading to BrONO/IONO, are nearly barrierless, making BrONO/IONO critical reaction intermediates.

These intermediates can further react with Br⁻/I⁻ to produce Br₃⁻/I₃⁻, which then evaporate to form Br₂/I₂, participating in the atmospheric halogen cycle.