期刊
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
卷 12, 期 7, 页码 1955-1960出版社
AMER CHEMICAL SOC
DOI: 10.1021/acs.jpclett.0c03827
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类别
资金
- RPCD, BARC
- Chemistry Group, BARC
- HBNI, BARC
Research shows that ions have a strong correlation with the structure of hydrogen bonding at the air/water interface and in bulk water. Specifically, structure-breaking anions decrease hydrogen bonding at the interface, while structure-making anions have the opposite effect. None of the electrolytes studied significantly affect the orientation of water molecules at the interface.
The prevalence of ions at the aqueous interface has been widely recognized, but their effect on the structure of interfacial water (e.g., hydrogen (H)-bonding) remains enigmatic. Using heterodyne-detected vibrational sum frequency generation (HD-VSFG) and Raman difference spectroscopy with simultaneous curve fitting (DS-SCF) analysis, we show that the ion-induced perturbations of H-bonding at the air/water interface and in the bulk water are strongly correlated. Specifically, the structure-breaking anions such as ClO3- decrease the average H-bonding of water at the air/water interface, as it does to the water in its hydration shell in the bulk. The structure-making anion of the same series (IO3-) does exactly the reverse. None of the electrolytes (NaXO3; X = Cl, Br, I) form well-defined electric double layers that significantly increase or reverse the hydrogen-down (H-down) orientation of water at the air/water interface. These results provide a unified picture of specific anion effect at the air/water interface and in the bulk water.
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