Tunable Surface Wettability via Terahertz Electrowave Controlled Vicinal Subnanoscale Water Layer.

Achieving timely, reversible, and long-range remote tunability over surface wettability is highly demanded across diverse fields, including nanofluidic systems, drug delivery, and heterogeneous catalysis. Herein, using molecular dynamic simulations, we show, for the first time, a theoretical design of electrowetting to achieve remotely controllable surface wettability via using a terahertz wave. The key idea driving the design is the unique terahertz collective vibration identified in the vicinal subnanoscale water layer, which is absent in bulk water, enabling efficient energy transfer from the terahertz wave to the rotational motion of the vicinal subnanoscale water layer. Consequently, a frequency-specific alternating terahertz electric field near the critical strength can significantly affect the local hydrogen-bonding network of the contact water layer on the solid surface, thereby achieving tunable surface wettability.

Hydrogen polarity of interfacial water regulates heterogeneous ice nucleation.

Using all-atomic molecular dynamics (MD) simulations, we show that the structure of interfacial water (IW) induced by substrates characterizes the ability of a substrate to nucleate ice. We probe the shape and structure of ice nuclei and the corresponding supercooling temperatures to measure the ability of IW with various hydrogen polarities for ice nucleation, and find that the hydrogen polarization of IW even with the ice-like oxygen lattice increases the contact angle of the ice nucleus on IW, thus lifting the free energy barrier of heterogeneous ice nucleation. The results show that not only the oxygen lattice order but the hydrogen disorder of IW on substrates are required to effectively facilitate the freezing of top water.

Temperature regulation of the contact angle of water droplets on the solid surfaces.

We investigate theoretically the stability of the wetting property, i.e., the contact angle values, as a function of the temperature. We find that the estimated temperature coefficient of the contact angle for the water droplets on an ordered water monolayer on a 100 surface of face-center cubic (FCC) is about one order of magnitude larger than that on a hydrophobic hexagonal surface in the temperature range between 290 K and 350 K, using molecular dynamics simulations. As temperature rises, the number of hydrogen bonds between the ordered water monolayer and the water droplet will increase, which therefore enhances the hydrophilicity of the ordered water monolayer at the FCC model surface. Our work thus provides an easily controllable and reversible way to control the degree of hydrophobicity of various solid surfaces exhibiting a similar wetting property of water droplets on the ordered water monolayer as such particular FCC (100) surfaces.

A nonmonotonic dependence of the contact angles on the surface polarity for a model solid surface.

Based on molecular dynamics simulations, we found a nonmonotonic relationship between the contact angle of water droplets and the surface polarity on a solid surface with specific hexagonal charge patterns at room temperature. The contact angle firstly decreases and then increases as polarity (denoted as charge q) increases from 0 e to 1.0 e with a vertex value of q = 0.5 e. We observed a different wetting behavior for a water droplet on a conventional nonwetted solid surface when q ≤ 0.5 e, and a water droplet on an ordered water monolayer adsorbed on a highly polar solid surface when q > 0.5 e. The solid-water interaction, density of water, hydrogen bonds, and water structures were analyzed. Remarkably, there was up to six times difference in the solid-water interactions despite the same value of the apparent contact angle values.

Room temperature bilayer water structures on a rutile TiO2(110) surface: hydrophobic or hydrophilic?

The lack of understanding of the molecular-scale water adsorbed on TiO2 surfaces under ambient conditions has become a major obstacle for solving the long-time scientific and applications issues, such as the photo-induced wetting phenomenon and designing novel advanced TiO2-based materials. Here, with the molecular dynamics simulation, we identified an ordered water bilayer structure with a two-dimensional hydrogen bonding network on a rutile TiO2(110) surface at ambient temperature, corroborated by vibrational sum-frequency generation spectroscopy. The reduced number of hydrogen bonds between the water bilayer and water droplet results in a notable water contact angle (25 ± 5°) of the pristine TiO2 surface. This surface hydrophobicity can be enhanced by the adsorption of the formate/acetate molecules, and diminishes with dissociated H2O molecules. Our new physical framework well explained the long-time controversy on the origin of the hydrophobicity/hydrophilicity of the TiO2 surface, thus help understanding the efficiency of TiO2 devices in producing electrical energy of solar cells and the photo-oxidation of organic pollutants.

Anomalously Low Dielectric Constant of Ordered Interfacial Water.

Despite considerable effort, the dielectric constant of interfacial water at solid surfaces is still not fully understood, thus hindering our understanding of the ubiquitous physical interactions in many materials and biological surfaces. In this study, we used molecular dynamics simulations to show that the parallel dielectric constant at the solid/water interface depends on solid-water interactions as well as the interfacial water structure on various solid crystal faces. In particular, ordered water structures can lead to a significant reduction (∼44%) in the parallel dielectric constant at the solid/water interface compared with that of bulk water. This sharp decrease in the parallel dielectric constant can be attributed to the specific antiferroelectric ordered structure of interfacial water molecules, which significantly suppresses the amplitude of the dipolar fluctuation associated with both the number of hydrogen bonds and the degree of order of interfacial water.

Terahertz Wave Accelerates DNA Unwinding: A Molecular Dynamics Simulation Study.

Unwinding the double helix of the DNA molecule is the basis of gene duplication and gene editing, and the acceleration of this unwinding process is crucial to the rapid detection of genetic information. Based on the unwinding of six-base-pair DNA duplexes, we demonstrate that a terahertz stimulus at a characteristic frequency (44.0 THz) can serve as an efficient, nonthermal, and long-range method to accelerate the unwinding process of DNA duplexes. The average speed of the unwinding process increased by 20 times at least, and its temperature was significantly reduced. The mechanism was revealed to be the resonance between the terahertz stimulus and the vibration of purine connected by the weak hydrogen bond and the consequent break in hydrogen bond connections between these base pairs. Our findings potentially provide a promising application of terahertz technology for the rapid detection of nucleic acids, biomedicine, and therapy.

Unexpected large impact of small charges on surface frictions with similar wetting properties.

Generally, the interface friction on solid surfaces is regarded as consistent with wetting behaviors, characterized by the contact angles. Here using molecular dynamics simulations, we find that even a small charge difference (≤0.36 e) causes a change in the friction coefficient of over an order of magnitude on two-dimensional material and lipid surfaces, despite similar contact angles. This large difference is confirmed by experimentally measuring interfacial friction of graphite and MoS2 contacting on water, using atomic force microscopy. The large variation in the friction coefficient is attributed to the different fluctuations of localized potential energy under inhomogeneous charge distribution. Our results help to understand the dynamics of two-dimensional materials and biomolecules, generally formed by atoms with small charge, including nanomaterials, such as nitrogen-doped graphene, hydrogen-terminated graphene, or MoS2, and molecular transport through cell membranes.