Structure and Nonlinear Spectra of the Basal Face of Hexagonal Ice: A Molecular Dynamics Study

Structure and nonlinear spectra of the basal surface of ice Ih were investigated by molecular dynamics simulations. At a temperature significantly lower than the melting temperature Tm, the ice structure at the interface is only weakly perturbed by the presence of surface. The computed nonlinear spectrum of the interface well agrees with the experimental data and the results of the calculations provide the molecular-level interpretation of spectral features. In particular, the ice surface specific positive peaks in the Im[χ(2)] spectrum at ∼3180 cm−1 and at ∼3420 cm−1 were found to result from the low- and high-frequency vibrational modes of quadruply H-bonded surface molecules, respectively. The spectrum of the crystalline ice interface is significantly affected by intermolecular interactions. Upon increasing the temperature, the structural disorder extends to the second water bilayer. The thickness of the premelted water layer of 6–8 Å can be estimated at the temperature by ca. 5 K below Tm. The increase in the temperature results in a change in the intensity and shape of the nonlinear spectrum of the ice Ih interface. The changes can be explained by the interconversion between different H-bonded surface species and by an increase in disordering of water molecules that reduces strength of intermolecular interactions. Results of the present work contribute to our understanding of the structure–spectrum relationship of the ice/air interface, and shed light on the origins of features in the nonlinear spectra of the system.