The structure and dynamics of water droplets on a bilayer graphene surface are investigated using molecular dynamics simulations. The effects of solid/water and air/water interfaces on the local structure of water droplets are analyzed in terms of the hydrogen bond distribution and tetrahedral order parameter. It is found that the local structure in the core region of a water droplet is similar to that in liquid water. On the other hand, the local structure of water molecules at the solid/water and air/water interfaces, referred to as the interface and surface regions, respectively, consists mainly of three-coordinated molecules that are greatly distorted from a tetrahedral structure. This study reveals that the dynamics in different regions of the water droplets affects the intermolecular vibrational density of states: It is found that in the surface and interface regions, the intensity of vibrational density of states at ∼50 cm−1 is enhanced, whereas those at ∼200 and ∼500 cm−1 are weakened and redshifted. These changes are attributed to the increase in the number of molecules having fewer hydrogen bonds in the interface and surface regions. Both single-molecule and collective orientation relaxations are also examined. Single-molecule orientation relaxation is found to be marginally slower than that in liquid water. On the other hand, the collective orientation relaxation of water droplets is found to be significantly faster than that of liquid water because of the destructive correlation of dipole moments in the droplets. The negative correlation between distinct dipole moments also yields a blueshifted libration peak in the absorption spectrum. It is also found that the water–graphene interaction affects the structure and dynamics of the water droplets, such as the local water structure, collective orientation relaxation, and the correlation between dipole moments. This study reveals that the water/solid and water/air interfaces strongly affect the structure and intermolecular dynamics of water droplets and suggests that the intermolecular dynamics, such as energy relaxation dynamics, in other systems with interfaces are different from those in liquid water.

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