Hidden Isolated OH at the Charged Hydrophobic Interface Revealed by Two-Dimensional Heterodyne-Detected VSFG Spectroscopy.

ABSTRACT

Water around hydrophobic groups mediates hydrophobic interactions that play key roles in many chemical and biological processes. Thus, the molecular-level elucidation of the properties of water in the vicinity of hydrophobic groups is important. We report on the structure and dynamics of water at two oppositely charged hydrophobic ion/water interfaces, that is, the tetraphenylborate-ion (TPB- )/water and tetraphenylarsonium-ion (TPA+ )/water interfaces, which are clarified by two-dimensional heterodyne-detected vibrational sum-frequency generation (2D HD-VSFG) spectroscopy. The obtained 2D HD-VSFG spectra of the anionic TPB- interface reveal the existence of distinct π-hydrogen bonded OH groups in addition to the usual hydrogen-bonded OH groups, which are hidden in the steady-state spectrum. In contrast, 2D HD-VSFG spectra of the cationic TPA+ interface only show the presence of usual hydrogen-bonded OH groups. The present study demonstrates that the sign of the interfacial charge governs the structure and dynamics of water molecules that face the hydrophobic region.