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一种用于天体化学的新仪器的设计与实现:在冷均匀超声速流中对CH + OCS反应的动力学测量及频率梳光谱学研究

Design and implementation of a new apparatus for astrochemistry: Kinetic measurements of the CH + OCS reaction and frequency comb spectroscopy in a cold uniform supersonic flow.

作者信息

Lucas Daniel I, Guillaume Théo, Heard Dwayne E, Lehman Julia H

机构信息

School of Chemistry, University of Birmingham, Edgbaston B15 2TT, United Kingdom.

School of Chemistry, University of Leeds, Leeds LS2 9JT, United Kingdom.

出版信息

J Chem Phys. 2024 Sep 7;161(9). doi: 10.1063/5.0220774.

DOI:10.1063/5.0220774
PMID:39230369
Abstract

We present the development of a new astrochemical research tool, HILTRAC, the Highly Instrumented Low Temperature ReAction Chamber. The instrument is based on a pulsed form of the CRESU (Cinétique de Réaction en Écoulement Supersonique Uniforme, meaning reaction kinetics in a uniform supersonic flow) apparatus, with the aim of collecting kinetics and spectroscopic information on gas phase chemical reactions important in interstellar space or planetary atmospheres. We discuss the apparatus design and its flexibility, the implementation of pulsed laser photolysis followed by laser induced fluorescence, and the first implementation of direct infrared frequency comb spectroscopy (DFCS) coupled to the uniform supersonic flow. Achievable flow temperatures range from 32(3) to 111(9) K, characterizing a total of five Laval nozzles for use with N2 and Ar buffer gases by impact pressure measurements. These results were further validated using LIF and direct frequency comb spectroscopy measurements of the CH radical and OCS, respectively. Spectroscopic constants and linelists for OCS are reported for the 1001 band near 2890-2940 cm-1 for both OC32S and OC34S, measured using DFCS. Additional peaks in the spectrum are tentatively assigned to the OCS-Ar complex. The first reaction rate coefficients for the CH + OCS reaction measured between 32(3) and 58(5) K are reported. The reaction rate coefficient at 32(3) K was measured to be 3.9(4) × 10-10 cm3 molecule-1 s-1 and the reaction was found to exhibit no observable temperature dependence over this low temperature range.

摘要

我们介绍了一种新的天体化学研究工具HILTRAC(高度仪器化低温反应室)的研发情况。该仪器基于CRESU(均匀超音速流反应动力学,即均匀超音速流中的反应动力学)装置的脉冲形式,旨在收集有关星际空间或行星大气中重要气相化学反应的动力学和光谱信息。我们讨论了该装置的设计及其灵活性、脉冲激光光解后接激光诱导荧光的实现方式,以及与均匀超音速流耦合的直接红外频率梳光谱(DFCS)的首次实现。通过冲击压力测量,可实现的流动温度范围为32(3)至111(9)K,共表征了五个用于N2和Ar缓冲气体的拉瓦尔喷嘴。分别使用CH自由基和OCS的激光诱导荧光(LIF)和直接频率梳光谱测量进一步验证了这些结果。使用DFCS测量了OC32S和OC34S在2890 - 2940 cm-1附近1001带的OCS光谱常数和谱线表。光谱中的其他峰暂定为OCS - Ar络合物。报告了在32(3)至58(5)K之间测量的CH + OCS反应的首个反应速率系数。在32(3)K时测量的反应速率系数为3.9(4)×10-10 cm3分子-1 s-1,并且发现在这个低温范围内该反应没有明显的温度依赖性。

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