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Specific Na+ and K+ cation effects on the interfacial water molecules at the air/aqueous salt solution interfaces probed with nonresonant second harmonic generation
Bian, Hong-tao1; Feng, Ran-ran1; Guo, Yuan1; Wang, Hong-fei1
2009-04-07
Source PublicationJOURNAL OF CHEMICAL PHYSICS
ISSN0021-9606
Volume130Issue:13
AbstractHere we report on the polarization dependent nonresonant second harmonic generation (SHG) measurement of the interfacial water molecules at the aqueous solution of the following salts: NaF, NaCl, NaBr, KF, KCl, and KBr. Through quantitative polarization analysis of the SHG data, the orientational parameter D (D=< cos theta >/< cos(3) theta >) value and the relative surface density of the interfacial water molecules at these aqueous solution surfaces were determined. From these results, we found that addition of each of the six salts caused an increase in the thickness of the interfacial water layer at the surfaces to a certain extent. Noticeably, both the cations and the anions contributed to the changes, and the abilities to increase the thickness of the interfacial water layer were in the following order: KBr>NaBr>KCl>NaCl similar to NaF>KF. Since these changes cannot be factorized into individual anion and cation contributions, there are possible ion pairing or association effects, especially for the NaF case. We also found that the orientational parameter D values of the interfacial water molecules changed to opposite directions for the aqueous solutions of the three sodium salts versus the aqueous solutions of the three potassium salts. These findings clearly indicated unexpected specific Na+ and K+ cation effects at the aqueous solution surface. These effects were not anticipated from the recent molecular dynamics simulation results, which concluded that the Na+ and K+ cations can be treated as small nonpolarizable hard ions and they are repelled from the aqueous interfaces. These results suggest that the electrolyte aqueous solution surfaces are more complex than the currently prevalent theoretical and experimental understandings.
KeywordAssociation Electrolytes Optical Harmonic Generation Photochemistry Positive Ions Potassium Sodium Water
DOI10.1063/1.3104609
Indexed BySCI
Language英语
WOS IDWOS:000265053200057
PublisherAMER INST PHYSICS
Citation statistics
Cited Times:28[WOS]   [WOS Record]     [Related Records in WOS]
Document Type期刊论文
Identifierhttp://ir.iccas.ac.cn/handle/121111/67132
Collection中国科学院化学研究所
Corresponding AuthorWang, Hong-fei
Affiliation1.Chinese Acad Sci, Inst Chem, State Key Lab Mol React Dynam, Beijing Natl Lab Mol Sci, Beijing 100190, Peoples R China
2.Chinese Acad Sci, Grad Univ, Beijing 100190, Peoples R China
Recommended Citation
GB/T 7714
Bian, Hong-tao,Feng, Ran-ran,Guo, Yuan,et al. Specific Na+ and K+ cation effects on the interfacial water molecules at the air/aqueous salt solution interfaces probed with nonresonant second harmonic generation[J]. JOURNAL OF CHEMICAL PHYSICS,2009,130(13).
APA Bian, Hong-tao,Feng, Ran-ran,Guo, Yuan,&Wang, Hong-fei.(2009).Specific Na+ and K+ cation effects on the interfacial water molecules at the air/aqueous salt solution interfaces probed with nonresonant second harmonic generation.JOURNAL OF CHEMICAL PHYSICS,130(13).
MLA Bian, Hong-tao,et al."Specific Na+ and K+ cation effects on the interfacial water molecules at the air/aqueous salt solution interfaces probed with nonresonant second harmonic generation".JOURNAL OF CHEMICAL PHYSICS 130.13(2009).
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