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Cation Effects on Rotational Dynamics of Anions and Water Molecules in Alkali (Li+, Na+, K+, Cs+) Thiocyanate (SCN-) Aqueous Solutions
Bian, Hongtao1; Chen, Hailong1; Zhang, Qiang2; Li, Jiebo1; Wen, Xiewen1; Zhuang, Wei2; Zheng, Junrong1
刊名JOURNAL OF PHYSICAL CHEMISTRY B
2013-07-04
DOI10.1021/jp4016646
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
关键词[WOS]VIBRATIONAL-ENERGY TRANSFER ; HYDROGEN-BOND STRUCTURE ; LIQUID WATER ; MOLTEN THIOCYANATES ; HOFMEISTER SERIES ; PHASE-TRANSITION ; SALT-SOLUTIONS ; RAMAN-SPECTRA ; IONS ; HYDRATION
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.
语种英语
WOS记录号WOS:000321542200014
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文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/137611
专题中国科学院大连化学物理研究所
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
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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.
APA Bian, Hongtao.,Chen, Hailong.,Zhang, Qiang.,Li, Jiebo.,Wen, Xiewen.,...&Zheng, Junrong.(2013).Cation Effects on Rotational Dynamics of Anions and Water Molecules in Alkali (Li+, Na+, K+, Cs+) Thiocyanate (SCN-) Aqueous Solutions.JOURNAL OF PHYSICAL CHEMISTRY B,117(26),7972-7984.
MLA Bian, Hongtao,et al."Cation Effects on Rotational Dynamics of Anions and Water Molecules in Alkali (Li+, Na+, K+, Cs+) Thiocyanate (SCN-) Aqueous Solutions".JOURNAL OF PHYSICAL CHEMISTRY B 117.26(2013):7972-7984.
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