利用时间分辨傅里叶变换光谱法检测气态ClCS的红外吸收。

Infrared absorption of gaseous ClCS detected with time-resolved Fourier-transform spectroscopy.

作者信息

Chu Li-Kang, Han Hui-Ling, Lee Yuan-Pern

机构信息

Department of Applied Chemistry, National Chiao Tung University, 1001 Ta-Hsueh Road, Hsinchu 30010, Taiwan.

出版信息

J Chem Phys. 2007 May 7;126(17):174310. doi: 10.1063/1.2730501.

DOI:10.1063/1.2730501

PMID:17492866

Abstract

A transient infrared absorption spectrum of gaseous ClCS was detected with a step-scan Fourier-transform spectrometer coupled with a multipass absorption cell. ClCS was produced upon irradiating a flowing mixture of Cl2CS and N2 or CO2 with a KrF excimer laser at 248 nm. A transient band in the region of 1160-1220 cm-1, which diminished on prolonged reaction, is assigned to the C-S stretching (nu1) mode of ClCS. Calculations with density-functional theory (B3P86 and B3LYP/aug-cc-pVTZ) predict the geometry, vibrational wave numbers, and rotational parameters of ClCS. The rotational contour of the spectrum of ClCS simulated based on predicted rotational parameters agrees satisfactorily with experimental observation; from spectral simulation, the band origin is determined to be at 1194.4 cm-1. Reaction kinetics involving ClCS, CS, and CS2 are discussed.

摘要

利用一台与多程吸收池联用的步进扫描傅里叶变换光谱仪检测到了气态ClCS的瞬态红外吸收光谱。通过用波长为248nm的KrF准分子激光照射Cl₂CS与N₂或CO₂的流动混合气体来制备ClCS。在1160 - 1220cm⁻¹区域出现的一个瞬态谱带，随着反应时间延长而减弱，该谱带被归属于ClCS的C - S伸缩（ν₁）模式。采用密度泛函理论（B3P86和B3LYP/aug - cc - pVTZ）进行的计算预测了ClCS的几何结构、振动波数和转动参数。基于预测的转动参数模拟得到的ClCS光谱的转动轮廓与实验观测结果吻合良好；通过光谱模拟，确定谱带起源位于1194.4cm⁻¹。文中还讨论了涉及ClCS、CS和CS₂的反应动力学。