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题名: Hydration Dynamics of Cyanoferrate Anions Examined by Ultrafast Infrared Spectroscopy
作者: Yu, Pengyun1, 2;  Yang, Fan1;  Zhao, Juan1;  Wang, Jianping1
刊名: JOURNAL OF PHYSICAL CHEMISTRY B
发表日期: 2014-03-20
DOI: 10.1021/jp410614f
卷: 118, 期:11, 页:3104-3114
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: In this work, we carried out steady-state IR absorption, transient IR pump-probe, and waiting-time-dependent two-dimensional (2D) IR measurements on ferrocyanide and ferricyanide ions solvated in water and deuterated water. These two anions are highly symmetric and have distributed cyano groups with IR-active stretching modes in the 5 mu m wavelength region. The line width of their linear IR spectra and the initial value of the vibrational frequency-frequency correlation function extracted from their 2D IR spectra indicate water molecules in the hydration shell of the ferro-species are more inhomogeneously distributed but more tightly bound to the cyano groups than those of the fern-species. Different charges and their distributions in the two anions cause different hydrogen bonding strengths with solvent. The frequency correlation relaxes somewhat slower in ferrocyanide, agreeing with stronger solute-solvent hydrogen-bonding interaction in this case. Mechanisms of the solvent isotope effect on the vibrational relaxation dynamics of the cyano stretching mode are discussed. These results also suggest that in the hydration shell the ferro-species breaks more water structure than the fern-species, which is opposite to the situation of the bulk water region (beyond the hydration shell) reported previously. This work demonstrated that combined IR methods can be very useful for understanding the molecular. details of the structure and dynamics of the hydrated ions.
关键词[WOS]: VIBRATIONAL-ENERGY RELAXATION ;  AQUEOUS SOLVATION SHELLS ;  HYDROGEN-BOND STRUCTURE ;  2D IR SPECTROSCOPY ;  POPULATION RELAXATION ;  LIQUID WATER ;  DEPHASING DYNAMICS ;  IONS ;  SOLVENTS ;  COMPLEXES
语种: 英语
WOS记录号: WOS:000333381800033
Citation statistics: 
内容类型: 期刊论文
URI标识: http://cas-ir.dicp.ac.cn/handle/321008/145918
Appears in Collections:中国科学院大连化学物理研究所_期刊论文

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作者单位: 1.Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
2.Univ Chinese Acad Sci, Beijing 100049, Peoples R China

Recommended Citation:
Yu, Pengyun,Yang, Fan,Zhao, Juan,et al. Hydration Dynamics of Cyanoferrate Anions Examined by Ultrafast Infrared Spectroscopy[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2014,118(11):3104-3114.
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