Vibrational sum frequency generation spectra of water are calculated for air-water interfaces covered by alcohol molecules for different surface coverages. Two different alcohols of varying hydrophobic parts are considered and the spectral features are connected to the interfacial structure and interactions. The effects of coupling between vibrational modes of interest are also presented.
The present study deals with the effects of varying coverage of water surface by alcohols on the vibrational sum frequency generation (VSFG) spectrum of interfacial water. We have considered two different alcohols: Tertiary butyl alcohol (TBA) whose alkyl part is fully branched and stearyl alcohol (STA) which has a long linear alkyl chain with larger hydrophobic surface area than that of TBA. With increase of the alcohol concentration, the hydrogen bonded OH stretch region of the VSFG spectrum is found to change following a regular trend for the STA-water system, whereas non-monotonic variation of the VSFG spectrum is observed for the TBA-water system which can be correlated with the presence of very different interactions of TBA molecules at different concentrations. On increasing the concentration of TBA, the hydrophobic groups get more tilted towards the water phase and significant hydrophobic interactions are introduced at higher concentrations. Whereas, for STA, there is a gradual increase in the hydrophilic interaction. Because of stacking interactions between the long chain alkyl groups, the hydrophobic parts stay outward from the water phase at higher concentrations and a regular change in the VSFG spectrum is observed. We have also presented a computationally efficient scheme to calculate the VSFG spectrum of interfacial systems for coupled oscillators which is expected to be beneficial for the treatment of coupling where the interfacial system size is inherently large.Zum Volltext