266 nm激光光解C2H5SSC2H5产物的激光诱导荧光光谱

doi:10.3866/PKU.WHXB201509231

物理化学学报 >> 2015, Vol. 31 >> Issue (11): 2029-2035.doi: 10.3866/PKU.WHXB201509231

266 nm激光光解C₂H₅SSC₂H₅产物的激光诱导荧光光谱

郝海燕,刘振,祖莉莉*()

北京师范大学化学学院,理论与光化学教育部重点实验室,北京100875

收稿日期:2015-07-20 发布日期:2015-11-13
通讯作者: 祖莉莉 E-mail:zull@bnu.edu.cn
基金资助:
国家自然科学基金(21373033, 21173024)

Laser-Induced Fluorescence Spectra of the Photolyzed Products of C₂H₅SSC₂H₅ by 266 nm Laser

Hai-Yan. HAO,Zhen. LIU,Li-Li. ZU*()

Key Laboratory of Theoretical and Computational Photochemistry of the Ministry of Education, College of Chemistry, Beijing Normal University, Beijing 100875, P. R. China

Received:2015-07-20 Published:2015-11-13
Contact: Li-Li. ZU E-mail:zull@bnu.edu.cn
Supported by:
the National Natural Science Foundation of China(21373033, 21173024)

摘要/Abstract

摘要：

有机硫化物是大气主要污染物之一,其在大气中的光解产物还将造成二次污染,除了存在于有机硫化物中, S―S键还存在于胱氨酸等蛋白质中, S―S键的形成和断裂决定该类蛋白质的活性.本工作中,我们研究了用实验室常见的Nd:YAG激光器的四倍频266 nm激光光解C₂H₅SSC₂H₅过程,通过激光诱导荧光(LIF)光谱方法检测乙硫自由基C₂H₅S等光解产物.实验表明266 nm激光主要光解C₂H₅SSC₂H₅的S―S键产生C₂H₅S自由基.本文应用密度泛函理论的Becke3-Lee-Yang-Parr泛函(B3LYP方法)得到C₂H₅SSC₂H₅的S―S键、C―S键和C―C键的解离势能曲线,可知在266 nm光解条件下, C₂H₅SSC₂H₅在基态能够发生S―S键、C―S键解离, C―C键不发生解离.本文采用全活化空间自洽场(CASSCF)方法优化得到态和态的C₂H₅S自由基结构及其跃迁的绝热激发能,以辅助解析实验检测的C₂H₅S自由基的LIF光谱.实验结合理论计算最终得出,本实验266 nm光解条件下, C₂H₅SSC₂H₅主要发生S―S键解离,不排除少量分子发生C―S键解离的可能性.

关键词: C₂H₅S自由基, 266 nm光解, S―S键解离, 绝热激发能, LIF光谱

Abstract:

Organic sulfides are an atmospheric pollutant that photolyze in the atmosphere, causing additional pollution. The S―S bond exists not only in organic sulfides but also in some proteins such as L-cystine, and this bond is crucial to the bioactivity of this protein. In this work, we studied C₂H₅SSC₂H₅ photolysis at 266 nm, which is the quadruplicated frequency of the common Nd:YAG laser. The laser-induced fluorescence (LIF) spectra detected the photolyzed products, C₂H₅S radical. Our results show that the C₂H₅S radical was mainly created by dissociation of the S―S bond in C₂H₅SSC₂H₅. We determined the potential energy curves of the S―S, C―S, and C―C bonds in C₂H₅SSC₂H₅ at the B3LYP/6-311++G(d, p) level, finding that photolysis at 266 nm caused the S―S and C―S bonds of C₂H₅SSC₂H₅ to dissociate at the ground???2029-1??? state. Nevertheless, photolysis at 266 nm did not photolyze the C―C bond of C₂H₅SSC₂H₅. By optimizing the C_s geometry of the C₂H₅S radical at the???2029-1??? state and the???2029-2??? state, we determined the???2029-2???-???2029-1??? adiabatic transition energy at the CASSCF/6-311++G(d, p) level, and then studied the LIF spectra of the C₂H₅S radical. The main pathway is dissociation of the S―S bond of C₂H₅SSC₂H₅, though the C―S bond in a few C₂H₅SSC₂H₅ molecules did dissociate.

Key words: C₂H₅S radical, 266 nm photolysis, S―S bond dissociation, Adiabatic transition energy, LIF spectrum

MSC2000:

O644

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郝海燕,刘振,祖莉莉. 266 nm激光光解C₂H₅SSC₂H₅产物的激光诱导荧光光谱[J]. 物理化学学报, 2015, 31(11): 2029-2035.

Hai-Yan. HAO,Zhen. LIU,Li-Li. ZU. Laser-Induced Fluorescence Spectra of the Photolyzed Products of C₂H₅SSC₂H₅ by 266 nm Laser[J]. Acta Phys. -Chim. Sin., 2015, 31(11): 2029-2035.

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266 nm激光光解C₂H₅SSC₂H₅产物的激光诱导荧光光谱

Laser-Induced Fluorescence Spectra of the Photolyzed Products of C₂H₅SSC₂H₅ by 266 nm Laser

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