硫氰酸钠在水中的微溶剂化作用：气相阴离子光电子能谱及理论计算
Microsolvation of Sodium Thiocyanate in Water: Gas Phase Anion Photoelectron Spectroscopy and Theoretical Calculations.
作者信息
Gong Shiyan, Wang Peng, Wei Zhiyou, Yang Bin, Xu Xiling, Xu Hongguang, Zheng Weijun
机构信息
Beijing National Laboratory for Molecular Sciences, State Key Laboratory of Molecular Reaction Dynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
出版信息
J Phys Chem A. 2020 Sep 24;124(38):7816-7826. doi: 10.1021/acs.jpca.0c07071. Epub 2020 Sep 10.
We studied NaSCN(HO) clusters in the gas phase using size-selected anion photoelectron spectroscopy. Vertical detachment energies (VDEs) of NaSCN(HO) ( = 0-6) clusters were obtained in the experiment. Structures of NaSCN(HO) ( = 0-6) clusters and their corresponding neutral counterparts were investigated by theoretical calculations. Our studies show that the Na-NCS type of structures rather than the Na-SCN type of structures are dominant in the gas phase for both anionic and neutral NaSCN(HO) clusters. For NaSCN(HO) anions, the contact ion pair (CIP) and solvent-separated ion pair (SSIP) type of structures coexist at = 2 and 3, the SSIP type of structures become dominant at ≥ 4. For neutral NaSCN(HO), the CIP type of structures are dominant from = 1 to 6 and the SSIP type of structures start to appear at = 6. The gas phase structures in this work support the existence of ion clustering in concentrated NaSCN aqueous solutions.
我们使用尺寸选择阴离子光电子能谱研究了气相中的NaSCN(HO)团簇。实验中获得了NaSCN(HO)（n = 0 - 6）团簇的垂直脱附能（VDEs）。通过理论计算研究了NaSCN(HO)（n = 0 - 6）团簇及其相应中性对应物的结构。我们的研究表明，对于阴离子和中性的NaSCN(HO)团簇，气相中占主导地位的是Na - NCS型结构而非Na - SCN型结构。对于NaSCN(HO)阴离子，接触离子对（CIP）和溶剂分离离子对（SSIP）型结构在n = 2和3时共存，在n≥4时SSIP型结构占主导。对于中性NaSCN(HO)，CIP型结构在n = 1到6时占主导，SSIP型结构在n = 6时开始出现。这项工作中的气相结构支持了浓NaSCN水溶液中离子簇的存在。
Zotero 插件