Liu Ling, Li Shuning, Zu Haotian, Zhang Xiuhui
Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China.
Key Laboratory of Cluster Science, Ministry of Education of China, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China; National Supercomputer Center in Tianjin, Tianjin 300451, China.
Sci Total Environ. 2023 Feb 10;859(Pt 1):159832. doi: 10.1016/j.scitotenv.2022.159832. Epub 2022 Oct 29.
Iodous acid (HIO) has been shown to play a stabilizing role in the nucleation of iodic acid (HIO) (He et al., 2021). However, the stabilization effect and specific stabilizing mechanism of HIO on HIO nucleation under different atmospheric conditions remain unclear. Therefore, we studied these two issues under different temperatures and nucleation precursor concentrations using density functional theory combined with the Atmospheric Cluster Dynamics Code. We found that HIO can form clusters with HIO via strong hydrogen bonds, halogen bonds, and proton-transfer, substantially enhancing the stability of HIO clusters and decreasing the energy barrier of HIO-based cluster formation at different temperatures and nucleation precursor concentrations. The particle formation rate and cluster concentrations of HIO-HIO nucleation were negatively correlated with temperature and positively correlated with HIO concentration. The enhancements by HIO on the particle formation rate and cluster concentration of HIO nucleation were positively correlated with temperature and HIO concentration. Interestingly, even at a low HIO concentration (1.0 × 10 molecules cm), the enhancement on the particle formation rate and cluster concentration of HIO nucleation by HIO were both unexpectedly up to 4.1 × 10-fold at 283 K. Therefore, HIO-HIO nucleation can be extremely rapid in cold regions, and the enhancement by HIO can be significant, especially in warm regions even at relatively high HIO concentrations.
已证明亚碘酸（HIO）在碘酸（HIO₃）的成核过程中起稳定作用（He等人，2021年）。然而，在不同大气条件下，HIO对HIO₃成核的稳定作用及具体稳定机制仍不清楚。因此，我们使用密度泛函理论结合大气团簇动力学代码，在不同温度和成核前驱体浓度下研究了这两个问题。我们发现，HIO可以通过强氢键、卤键和质子转移与HIO₃形成团簇，在不同温度和成核前驱体浓度下，显著提高HIO₃团簇的稳定性并降低基于HIO₃的团簇形成的能垒。HIO-HIO₃成核的粒子形成速率和团簇浓度与温度呈负相关，与HIO浓度呈正相关。HIO对HIO₃成核的粒子形成速率和团簇浓度的增强作用与温度和HIO浓度呈正相关。有趣的是，即使在低HIO浓度（1.0×10⁹分子·cm⁻³）下，在283K时HIO对HIO₃成核的粒子形成速率和团簇浓度的增强作用均意外地高达4.1×10⁴倍。因此，HIO-HIO₃成核在寒冷地区可能极其迅速，并且HIO的增强作用可能很显著，尤其是在温暖地区，即使在相对较高的HIO浓度下也是如此。
