大气关键活性物质的水化行为和水促反应机理的理论研究

近年来，大气污染已成为全球关注的主要环境问题之一，并引发了酸雨、臭氧层空洞和雾霾等多种污染问题。在大气污染物的生成、转化和消耗等过程中，诸如高活性氧化物、氮氧化物和卤素等物质起着关键作用。从原子尺度深入理解这些关键物质的反应活性和动力学行为，对于全面理解复杂的大气化学反应机制具有重要意义，并可以为缓解大气污染提供新思路。然而，当前对于上述关键物质的物理化学过程及其内在机制的理解尚不充分，尤其是对于水分子和水气界面在这些过程中的作用机制仍有待进一步研究。针对这些问题，本文通过采用过渡态搜索、热力学积分（Thermodynamic Integration, TI）和从头算分子动力学（Ab Initio Molecular Dynamics, AIMD）等方法，深入探究了水分子/水团簇与大气中的Criegee中间体（Criegee Intermediates, CIs）、过氧化羟基自由基（HO₂⸱）以及五氧化二氮（N₂O₅）的反应机制，同时探讨了水气界面对N₂O₅水解反应和卤素单质溶剂化过程的影响机制。

CIs与HO₂⸱间的反应对大气中二次有机气溶胶的形成起着至关重要的作用，但目前对该反应体系机制的理解仍然有限。本研究采用基于第一性原理的过渡态搜索方法和AIMD方法，研究了CIs与HO₂⸱/HO₂⸱-H₂O络合物之间的反应机制，并探究了温度效应和水分子对该反应的影响。研究结果表明，该反应遵循质子转移机制，而非此前研究所认为的氢原子转移机制。此外，通过比较不同温度下的反应自由能曲线，发现随着温度的上升反应自由能能垒显著升高，这表明熵效应在该反应具有重要作用。同时，水分子的引入会导致反应自由能能垒增大，从而阻碍反应的进行。这与水分子在其他气相反应中的起促进作用的现象显著不同。

N₂O₅作为氮循环过程中的关键物质，其在大气中的去除直接影响氮氧化物的含量。然而，基于现有理论机制计算得到的N₂O₅去除反应能垒较高，从而显著低估了其去除速率。本研究采用基于限制性AIMD的TI方法，系统性地探究了NH₃的甲基化程度以及水分子/水气界面对N₂O₅水解过程的影响，提出了一种水气界面胺催化的水解机理，其反应能垒显著低于传统水解过程。研究发现，NH₃甲基化程度的提高能有效降低N₂O₅水解反应的能垒，促进反应的进行。同时，与CIs-HO₂⸱反应类似，该反应的自由能能垒亦会随温度的升高而显著增大，进一步证明熵减效应不利于大气反应的进行。通过分析反应中心内禀坐标及周围物种相对位置的分布，证实了集合效应（非简谐熵和构型熵）是反应过程中熵效应的主要来源。此外，与CIs-HO₂⸱反应不同，水分子的引入会降低该反应的反应能垒，促进反应的进行。

大气中的卤素会显著影响平流层和对流层中的化学组分及其浓度，深入理解其溶剂化行为对揭示相关化学反应机制至关重要，但当前对于卤素单质在纳米水滴及水气界面的溶剂化行为尚不明确。本研究采用限制性AIMD和TI方法，探究了水气界面对卤素单质分子（Cl₂、Br₂和I₂）溶剂化过程的影响。研究结果表明，Cl₂和I₂的自由能在水气界面处达到最低，而Br₂的自由能最低点位于液相中。进一步分析揭示了，这种现象主要源于三种分子在卤键稳定性上的差异：Br₂在液相中能与水分子形成比界面处更稳定的卤键，因此更倾向于稳定在水滴内部；而Cl₂和I₂则在水气界面处展现出了更强的卤键稳定性。这一结果为实验中观测到的Br₂在水中溶解度更大这一反常现象提供了合理解释，并从动力学角度证明了卤键在卤素溶剂化过程中的重要性。

综上，本论文通过理论计算研究了水分子和水团簇对CIs、N₂O₅等物质的化学反应活性和反应机制的影响，以及水气界面在N₂O₅水解和卤素单质溶剂化过程中的作用，提出了不同于传统认知的新机理，阐明了大气化学反应的温度依赖性，揭示了熵效应对化学反应活性的重要性。此外，本研究还进一步发现水分子和水气界面对大气中物理化学过程起着重要作用，并且具有明显的体系依赖性。这些发现不仅有助于科研人员深入理解大气中关键物质的反应机制，也对解决当前所面临的大气污染问题具有一定的指导意义。

In recent years, air pollution has become one of the major environmental issues, leading to various pollution problems such as acid rain, ozone depletion, and smog. In the atmosphere, substances such as highly reactive oxidants, nitrogen oxides, and halogens play crucial roles in the formation, transformation, and consumption of pollutants. Understanding the reactivity and dynamic behavior of these key substances at the atomic scale is essential for unraveling the complex mechanisms behind atmospheric reactions, which could provide strategies for mitigating air pollution. However, our current understanding of the physicochemical processes and intrinsic mechanisms involving these key substances remains incomplete. Particularly, the role of water molecules and the air-water interface requires further investigation. Therefore, this employs theoretical simulation methods such as transition state search, thermodynamic integration (TI), and ab initio molecular dynamics (AIMD) simulation methods to thoroughly explore in detail the influence of water molecules and clusters on key atmospheric substances such as Criegee intermediates (CIs), hydroperoxyl radicals (HO₂⸱), and dinitrogen pentoxide (N₂O₅) in the gas phase. Additionally, it examines effects of interface on the hydrolysis of N₂O₅ and the solvation dynamics of the halogen elements.

The reactions between CIs and HO₂⸱ are crucial for the formation of secondary organic aerosols in the atmosphere, but the mechanisms underlying these reactions remain unclear. In this study, we used first-principles-based transition state search methods based on first principles and AIMD methods to investigate the reaction mechanisms involving CIs and HO₂⸱/HO₂⸱-H₂O complexes. The results indicate that these reactions follow a proton transfer mechanism, contradicting the previously assumed hydrogen atom transfer mechanism. Further analysis of the reaction free energy profiles at different temperatures shows that the reaction free energy barrier significantly increases with rising temperature, underscoring the entropy effect on the reaction. Additionally, the introduction of water molecules increases the reaction free energy barrier, thereby hindering the progress, which is different from their promoting effect in other gas-phase reactions.

Removal of N₂O₅, a key substance in the nitrogen cycle, directly affects the concentration of various nitrogen oxides in the atmosphere. However, existing theoretical models suggest a high energy barrier for N₂O₅ removal, potentially underestimating its actual removal rate. This study employed the TI methods based on constrained AIMD to systematically investigate the effect of NH₃ methylation and the water molecules/air-water interface on the hydrolysis of N₂O₅. An amine-catalyzed hydrolysis mechanism at the air-water interface, with an energy barrier far lower than the traditional hydrolysis process, was proposed. The study found that by increasing the methylation degree of NH₃, the reaction energy barrier for the hydrolysis of N2O5 can be significantly reduced, thereby promoting the progress of the reaction. Similarly to the CIs-HO₂⸱ reaction, the reaction free energy profiles at different temperatures indicate that the free energy barrier of the reaction also significantly increases with temperature, further proving that the entropy effect is detrimental to the progress of atmospheric reactions. It was confirmed that ensemble effects (including anharmonic and configurational entropy) are the main sources of entropy effect in the reaction by analyzing the distribution of the intrinsic coordinates of the reaction center and the relative positions of surrounding species. Additionally, unlike the CIs-HO₂⸱ reaction, the introduction of water molecules reduces the reaction energy barrier, facilitating the progress of the reaction.

Halogen elements play a pivotal role in altering the chemical components of the stratosphere and troposphere, and a thorough understanding of their solvation behavior is essential for elucidating related chemical reaction mechanisms. However, the current understanding of the solvation behavior of elemental halogens in water nanodroplets and at the air-water interface remains unclear. In this study, constrained AIMD and TI methods were applied to explore the effect of the air-water interface on the solvation process of halogen elements (Cl₂, Br₂, and I₂). The results show that the free energy of Cl₂ and I₂ minimizes at the interface, while the lowest free energy point of Br₂ is in the liquid. Further analysis indicates that this phenomenon lies in the differences in halogen bond stability among the three molecules: Br₂ can form more stable halogen bonds with water molecules in the liquid than at the interface, stabilizing inside the droplet. Whereas Cl₂ and I₂ show stronger halogen bond stability at the interface. These results provide reasonable explanations for the anomalous observation in experiments that Br₂ has a higher solubility in water and demonstrate from a dynamic perspective the importance of halogen bonding in the solvation process of halogens.

In summary, this thesis systematically studies the effects of water molecules and water clusters on the chemical reactivity and reaction mechanisms of reactive substances such as CIs and N₂O₅, as well as the influence of the air-water interface on the hydrolysis reaction of N₂O₅ and the solvation of halogen elements. These studies proposed new mechanisms different from traditional cognition and elucidated the temperature dependence of atmospheric chemical reactions. It also revealed that entropy effect is an important factor affecting chemical reactivity. Furthermore, this study has also discovered that water molecules and the air-water interface play an important role in the physicochemical processes in the atmosphere and exhibit a prominent system dependency. These findings not only aid researchers in deeply understanding the reaction mechanisms of key substances in the atmosphere but also provide some guidance for addressing the current atmospheric pollution issues.

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