Photoelectron Spectroscopy and Ab Initio Calculations of CS3－ Isomers: Carbon Trisulfide and Carbon Disulfide S‐Sulfide Anions
Photoelectron Spectroscopy and Ab Initio Calculations of CS3－ Isomers: Carbon Trisulfide and Carbon Disulfide S‐Sulfide Anions
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CS3－异构体：三硫化碳和二硫化碳 S-硫化物阴离子的光电子能谱和从头算
DOI：
10.1021/acs.jpca.6b06900
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发表时间：
2016
影响因子：
2.9
通讯作者：
T. Nagata
中科院分区：
文献类型：
--
作者：
R. Nakanishi;S. Kato;Y. Matsuyama;T. Nagata
碳硫化物被称为一类二元化合物，可以以各种异构体和/或聚合物形式存在。对于组成式为CS3的富硫化合物，已经从实验上或理论上提出了两种可能的结构异构体，用于中性物种及其相应的自由基阳离子和阴离子。虽然先前的研究声称一种异构体具有三硫化碳（CS3）C-中心构型，另一种具有二硫化碳S-硫化物（SCSS）链构型，但它们尚未通过光谱方法完全鉴定。在本研究中，我们在气相中通过两种类型的反应制备了这些异构体的阴离子：解离电子附着到1，3-二硫杂环戊烯-2-酮上形成CS3-和S-+ CS2离子-分子反应形成SCSS-。光电子能谱测量结果表明，在生产的两个阴离子物种，可以很好地区分它们的垂直脱离能的反应结果。通过从头计算，将它们分别确定为二硫化碳和二硫化碳的S-硫化物阴离子。
Carbon sulfides are known as a class of binary compounds that can exist in various isomeric and/or polymeric forms. As for a sulfur-rich compound with the composition formula CS3, two possible constitutional isomers have been proposed experimentally or theoretically for the neutral species and its corresponding radical cation and anion. Although the previous studies claim that one isomer has a carbon trisulfide (CS3) C-centered configuration and the other has a carbon disulfide S-sulfide (SCSS) chain configuration, they have not yet been fully identified by a spectroscopic method. In this study, we have prepared the anions of those isomers in the gas phase by employing two types of reactions: dissociative electron attachment to 1,3-dithiole-2-thione for CS3–formation and the S–+ CS2ion–molecule reaction for SCSS–. Photoelectron spectroscopic measurements reveal that the reactions result in the production of two anionic species that can be well distinguished by their vertical detachment energy. With the aid of ab initio calculations, they are identified distinctively as the anions of carbon trisulfide and carbon disulfide S-sulfide.