华东师范大学学报（自然科学版） ›› 2022, Vol. 2022 ›› Issue (1): 31-42.doi: 10.3969/j.issn.1000-5641.2022.01.005

• 物理学与电子学 • 上一篇    下一篇

大气气溶胶中SO3–和HSO3–的电子结构和微溶剂化作用研究

陈佳楠1, 李志鹏1, 蒋延荣1, 胡竹斌1,2, 孙海涛1,3,*(), 孙真荣1,3,*()   

  1. 1. 华东师范大学 精密光谱科学与技术国家重点实验室, 上海　200241
    2. 上海纽约大学 文理学院,上海　200122
    3. 山西大学 极端光学协同创新中心, 太原　030006
  • 收稿日期:2021-03-24 出版日期:2022-01-25 发布日期:2022-01-18
  • 通讯作者: 孙海涛,孙真荣 E-mail:htsun@phy.ecnu.edu.cn;zrsun@phy.ecnu.edu.cn

Study of electronic structures and the micro-solvation effect of SO3– and HSO3– in atmospheric aerosols

Jianan CHEN1, Zhipeng LI1, Yanrong JIANG1, Zhubin HU1,2, Haitao SUN1,3,*(), Zhenrong SUN1,3,*()   

  1. 1. State Key Laboratory of Precision Spectroscopy, East China Normal University, Shanghai　200241, China
    2. Division of Arts and Sciences, New York University Shanghai, Shanghai　200122, China
    3. Collaborative Innovation Center of Extreme Optics, Shanxi University, Taiyuan　030006, China.
  • Received:2021-03-24 Online:2022-01-25 Published:2022-01-18
  • Contact: Haitao SUN,Zhenrong SUN E-mail:htsun@phy.ecnu.edu.cn;zrsun@phy.ecnu.edu.cn

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摘要：

结合阴离子光电子能谱(Negative Ion Photoelectron Spectroscopy, NIPES)实验和量子化学计算, 研究了广泛存在于大气气溶胶中的SO3–和HSO3–的电子结构、微溶剂化作用及其稳定化机制. 首先, 基于高分辨NIPES测得了上述两种阴离子SO3–和HSO3–的垂直电离能((3.31 ± 0.02)和(3.91 ± 0.02) eV)和绝热电离能((3.02 ± 0.05)和(3.56 ± 0.05) eV). 进一步发现, 结合核系综方法和Dyson轨道计算可以很好地模拟实验测得NIPES, 而传统基于态密度方法不能很好地反映核振动效应、电离概率和电离过程中的轨道弛豫效应. 此外, 系统研究了HSO3–·(H2O)n (n = 0 ~ 5)体系的微溶剂化效应, 结果发现, 随着水分子数目的增加, 络合体系的稳定性增强, 其中静电作用占主导, 诱导作用也逐渐发挥重要作用. 相信本研究将有利于推动基于硫酸盐的大气气溶胶模型的完善, 为有效控制我国雾霾形成提供基础科学依据.

关键词: 光电子能谱, 电子结构, 密度泛函理论, 核系综, 亚硫酸盐

Abstract:

In this study, we used negative ion photoelectron spectroscopy (NIPES) combined with quantum chemical calculation to explore the electronic structures, micro-solvation effect, and stabilization mechanism of two compounds, SO3– and HSO3–, that are readily abundant in the atmosphere. Vertical detachment energies of (3.31 ± 0.02) and (3.91 ± 0.02) eV and adiabatic detachment energies of (3.02 ± 0.05) and (3.56 ± 0.05) eV were measured for SO3– and HSO3–, respectively. These results are reproduceable when using a nuclear ensemble approach and Dyson orbitals in the calculation. The typical density of states method, however, cannot demonstrate the nuclear vibration effect, ionization probability, and orbital relaxation effect during the ionization process. We studied the micro-solvation effect of HSO3–·(H2O)n (n = 0 ~ 5) and found that system stability was enhanced by an increase in the surrounding water molecules, whereby electrostatic interaction played a dominant role and the induction effect made an increasingly important contribution. We believe this work will help improve the modeling of atmospheric sulfate aerosols and provide a scientific basis for the effective control of haze formation.

Key words: photoelectron spectroscopy, electronic structure, density functional theory, nuclear ensemble approach, sulfites

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