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

Ken Ichi Inoue, Satoshi Nihonyanagi, Prashant C. Singh, Shoichi Yamaguchi, Tahei Tahara

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59 Citations (Scopus)


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.

Original languageEnglish
Article number212431
JournalJournal of Chemical Physics
Issue number21
Publication statusPublished - 2015 Jun 7
Externally publishedYes

ASJC Scopus subject areas

  • Physics and Astronomy(all)
  • Physical and Theoretical Chemistry


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