2D heterodyne-detected sum frequency generation study on the ultrafast vibrational dynamics of H2O and HOD water at charged interfaces.

Two-dimensional heterodyne-detected vibrational sum-frequency generation (2D HD-VSFG) spectroscopy is applied to study the ultrafast vibrational dynamics of water at positively charged aqueous interfaces, and 2D HD-VSFG spectra of cetyltrimethylammonium bromide (CTAB)/water interfaces in the whole hydrogen-bonded OH stretch region (3000 cm(-1) ≤ ωpump ≤ 3600 cm(-1)) are measured. 2D HD-VSFG spectrum of the CTAB/isotopically diluted water (HOD-D2O) interface exhibits a diagonally elongated bleaching lobe immediately after excitation, which becomes round with a time constant of ∼0.3 ps due to spectral diffusion. In contrast, 2D HD-VSFG spectrum of the CTAB/H2O interface at 0.0 ps clearly shows two diagonal peaks and their cross peaks in the bleaching region, corresponding to the double peaks observed at 3230 cm(-1) and 3420 cm(-1) in the steady-state HD-VSFG spectrum. Horizontal slices of the 2D spectrum show that the relative intensity of the two peaks of the bleaching at the CTAB/H2O interface gradually change with the change of the pump frequency. We simulate the pump-frequency dependence of the bleaching feature using a model that takes account of the Fermi resonance and inhomogeneity of the OH stretch vibration, and the simulated spectra reproduce the essential features of the 2D HD-VSFG spectra of the CTAB/H2O interface. The present study demonstrates that heterodyne detection of the time-resolved VSFG is critically important for studying the ultrafast dynamics of water interfaces and for unveiling the underlying mechanism.