Weakly Anisotropic Dielectric Properties of Water Droplets at the Nanoscale

CC Guo and HR Qin and Y Zhu and YJ Lu, LANGMUIR, 37, 13059-13066 (2021).

DOI: 10.1021/acs.langmuir.1c02207

The slab-confined water at the nanoscale exhibits anomalous dielectric properties compared to bulk water, for example, significantly low dielectric constant. In this work, we study the dielectric properties of nanoscale water droplets at room temperature using molecular dynamics simulations. We find that the nanoscale water droplets feature weakly anisotropic dielectric constant: the radial component of dielectric constants is distinctly smaller than the tangential component although they both decrease with reducing droplet size in a similar way. Such dielectric behavior is closely related to the orientational preference of water molecules near the convex surface. The molecular dipole prefers to slightly orientate toward the interior of droplets in contrast to the out-of-plane preference for freestanding water films and slab-confined water, which suppresses the fluctuation of dipole moments in the radial direction. Meanwhile, it facilitates the formation of the open hydrogen- bond network in the surface layer and ultimately leads to the relatively weak suppression of tangential fluctuations. The differential suppression is responsible for the anisotropic dielectric constant of water droplets. This anisotropic characteristic is also found in dielectric relaxation: both the radial and the tangential relaxation are consistently slowed down upon approaching surface but the latter is universally slower.

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