Theoretical study of the structure and vibrational sum frequency generation spectroscopy of liquid–vapor interface of aqueous acetic acid

We have investigated the liquid-vapor interface of aqueous acetic acid solution through calculations of the structure and vibrational sum frequency generation (VSFG) spectra of the interfaces for varying concentrations of the acetic acid (AA). Our findings reveal the surface propensity of the AA molecules. As the concentration of AA increases, more AA molecules are found to be present in the interfacial region. The AA molecules at the interface are found to be oriented in a manner where the hydrophobic part (methyl chain) is oriented toward the vapor phase and the hydrophilic part is pointed toward the liquid phase. The total VSFG spectrum reveals that the intensity of the peak of dangling OH groups of water around 3750 cm-1 decreases when the concentration of AA increases, while the intensity of the peak around 3550 cm-1 due to OH groups having hydrogen bonds between water and AA molecules increases. Furthermore, the latter peak is redshifted as the AA concentration increases, which is due to the partial cancellation between the positive response of water OH modes and the negative response of the OH modes of AA molecules. It is also noted that the AA molecules make the interfacial water more structured by making hydrogen bonds with its otherwise dangling OH modes at the surface.