中国科学院大连化学物理研究所机构知识库
Advanced  
DICP OpenIR  > 中国科学院大连化学物理研究所  > 期刊论文
题名: Cation Effects on Rotational Dynamics of Anions and Water Molecules in Alkali (Li+, Na+, K+, Cs+) Thiocyanate (SCN-) Aqueous Solutions
作者: Bian, Hongtao1;  Chen, Hailong1;  Zhang, Qiang2;  Li, Jiebo1;  Wen, Xiewen1;  Zhuang, Wei2;  Zheng, Junrong1
刊名: JOURNAL OF PHYSICAL CHEMISTRY B
发表日期: 2013-07-04
DOI: 10.1021/jp4016646
卷: 117, 期:26, 页:7972-7984
收录类别: SCI
文章类型: Article
WOS标题词: Science & Technology ;  Physical Sciences
类目[WOS]: Chemistry, Physical
研究领域[WOS]: Chemistry
英文摘要: Waiting time dependent rotational anisotropies of SCN- anions and water molecules in alkali thiocyanate (XSCN, X = Li, Na, K, Cs) aqueous solutions at various concentrations were measured with ultrafast infrared spectroscopy. It was found that cations can significantly affect the reorientational motions of both water molecules and SCN- anions. The dynamics are slower in a solution with a smaller cation. The reorientational time constants follow the order of Li+ > Na+ > K+ similar or equal to Cs+. The changes of rotational time constants of SCN- at various concentrations scale almost linearly with the changes of solution viscosity, but those of water molecules do not. In addition, the concentration-dependent amplitudes of dynamical changes are much more significant in the Li+ and Na+ solutions than those in the K+ and Cs+ solutions. Further investigations on the systems with the ultrafast vibrational energy exchange method and molecular dynamics simulations provide an explanation for the observations: the observed rotational dynamics are the balanced results of ion clustering and cation/anion/water direct interactions. In all the solutions at high concentrations (>5 M), substantial amounts of ions form clusters. The structural inhomogeneity in the solutions leads to distinct rotational dynamics of water and anions. The strong interactions of Li+ and Na+ because of their relatively large charge densities with water molecules and SCN- anions, in addition to the likely geometric confinements because of ion clustering, substantially slow down the rotations of SCN- anions and water molecules inside the ion clusters. The interactions of K+ and Cs+ with water or SCN- are much weaker. The rotations of water molecules inside ion clusters of K+ and Cs+ solutions are not significantly different from those of other water species so that the experimentally observed rotational relaxation dynamics are only slightly affected by the ion concentrations.
关键词[WOS]: VIBRATIONAL-ENERGY TRANSFER ;  HYDROGEN-BOND STRUCTURE ;  LIQUID WATER ;  MOLTEN THIOCYANATES ;  HOFMEISTER SERIES ;  PHASE-TRANSITION ;  SALT-SOLUTIONS ;  RAMAN-SPECTRA ;  IONS ;  HYDRATION
语种: 英语
WOS记录号: WOS:000321542200014
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/137611
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

Files in This Item:

There are no files associated with this item.


作者单位: 1.Rice Univ, Dept Chem, Houston, TX 77005 USA
2.Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Liaoning, Peoples R China

Recommended Citation:
Bian, Hongtao,Chen, Hailong,Zhang, Qiang,et al. Cation Effects on Rotational Dynamics of Anions and Water Molecules in Alkali (Li+, Na+, K+, Cs+) Thiocyanate (SCN-) Aqueous Solutions[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2013,117(26):7972-7984.
Service
 Recommend this item
 Sava as my favorate item
 Show this item's statistics
 Export Endnote File
Google Scholar
 Similar articles in Google Scholar
 [Bian, Hongtao]'s Articles
 [Chen, Hailong]'s Articles
 [Zhang, Qiang]'s Articles
CSDL cross search
 Similar articles in CSDL Cross Search
 [Bian, Hongtao]‘s Articles
 [Chen, Hailong]‘s Articles
 [Zhang, Qiang]‘s Articles
Related Copyright Policies
Null
Social Bookmarking
  Add to CiteULike  Add to Connotea  Add to Del.icio.us  Add to Digg  Add to Reddit 
所有评论 (0)
暂无评论
 
评注功能仅针对注册用户开放,请您登录
您对该条目有什么异议,请填写以下表单,管理员会尽快联系您。
内 容:
Email:  *
单位:
验证码:   刷新
您在IR的使用过程中有什么好的想法或者建议可以反馈给我们。
标 题:
 *
内 容:
Email:  *
验证码:   刷新

Items in IR are protected by copyright, with all rights reserved, unless otherwise indicated.

 

 

Valid XHTML 1.0!
Powered by CSpace