采用时间分辨傅里叶变换红外吸收光谱法检测ClSO

Detection of ClSO with time-resolved Fourier-transform infrared absorption spectroscopy.

作者信息

Chu Li-Kang, Lee Yuan-Pern, Jiang Eric Y

机构信息

Department of Chemistry, National Tsing Hua University, Hsinchu 30013, Taiwan.

出版信息

J Chem Phys. 2004 Feb 15;120(7):3179-84. doi: 10.1063/1.1641007.

DOI:10.1063/1.1641007

PMID:15268470

Abstract

ClSO was produced as an intermediate upon irradiating a flowing mixture of Cl2SO and Ar with a KrF excimer laser at 248 nm. A step-scan Fourier-transform infrared spectrometer coupled with a small multipass absorption cell was employed to detect time-resolved absorption spectrum of ClSO. A transient spectrum in the region 1120-1200 cm(-1), which diminished on prolonged reaction, is assigned to the S-O stretching (nu1) mode of ClSO. A spectrum with a resolution of 0.3 cm(-1) partially reveals rotational structure with the Q-branch at 1162.9 cm(-1). Calculations with density-functional theory (B3LYP/aug-cc-pVTZ) predict the geometry, vibrational, and rotational parameters of ClSO. An IR absorption spectrum of ClSO simulated based on predicted rotational parameters agrees satisfactorily with experimental results. ClSO produced from photolysis of Cl2SO at 248 nm is internally hot.

摘要

在248纳米处用KrF准分子激光照射Cl₂SO和Ar的流动混合物时，ClSO作为中间体产生。使用一台与小型多程吸收池联用的步进扫描傅里叶变换红外光谱仪来检测ClSO的时间分辨吸收光谱。在1120 - 1200厘米⁻¹区域的一个瞬态光谱，随着反应时间延长而减弱，被归属于ClSO的S - O伸缩（ν₁）模式。分辨率为0.3厘米⁻¹的光谱部分揭示了在1162.9厘米⁻¹处有Q分支的转动结构。用密度泛函理论（B3LYP/aug - cc - pVTZ）进行的计算预测了ClSO的几何结构、振动和转动参数。基于预测转动参数模拟的ClSO红外吸收光谱与实验结果吻合良好。在248纳米处Cl₂SO光解产生的ClSO内部是热的。