The gas-liquid interfaces distributed on a superhydrophobic (SHP) surface promote the effective slip and might result in significant drag reduction desirable in many applications. While the slippage of water past gas-liquid interfaces on structured SHP surfaces has attracted wide attention, the slip behavior at gas-liquid interfaces trapped by the wettability step still remains unclear. Using molecular dynamics simulations, we first demonstrated that the three-phase contact line can be pinned on a smooth substrate of mixed wettability. We then numerically investigated slip flows over smooth surfaces with flattened gas bubbles trapped by the wettability step. It was found that the local slip length is relatively large at the gas-liquid interface and its spatial distribution becomes asymmetric due to shear-induced deformation of the attached bubble, while the effective slip length remains nearly constant. With increasing gas areal fraction, the local and effective slip lengths become larger, especially in the case of a stripe-like continuous gas-liquid interface where the interface curvature in the flow direction is absent.
Fabrication of graphene-based surface coatings through self-assembly may provide an affordable alternative to chemical vacuum deposition. Herein, we exploited the self-assembly of graphene oxide at the oil/water interfaces to form monolayers of 2D carbons on solid surfaces with different surface energy. We showed that interfacial monolayers with controlled packing density of graphene oxide can be deposited on the hydrophilic surfaces such as silicon wafers and quartz glass as well as on the hydrophobic surface of Teflon. Graphene oxide attained flat arrangements in the monolayers on hydrophilic surfaces and yielded the films of partially scrolled particles on the surface of Teflon. The as-formed graphene oxide surface coatings underwent rapid reduction under microwave irradiation at 1000W. The efficiency of reduction was dependent on the ability of the supporting material to absorb microwaves: silicon wafer > quartz glass > Teflon. The single layers of graphene oxide reduced on the surface of silicon wafers showed extraordinary low sheet resistance 1.2 kOhm.sq-1, whereas those on Teflon exhibited low electrical properties (3.0 105 kOhm.sq-1). The results suggest that this facile and scalable soft-matter method for producing surface films of graphene oxide can be extended to other practically relevant combinations of graphene-based colloids and supporting materials.
The results of an experimental investigation of a sensor intended for detection and measurement of concentration of nanoparticles in an aqueous medium, which is based on optical-dielectric whispering-gallery- mode microcavities, are presented. Variation of the frequency and Q-factor of the eigenmodes of the microcavity upon its interaction with silver nanoparticles is studied. It is demonstrated that this type of sensor can be used for measurement of infinitesimally low concentrations of nanoparticles.
It is well recognized that excessive ice accumulation at low-temperature conditions can cause significant damage to civil infrastructure. The passive anti-icing surfaces provide a promising solution to suppress ice nucleation and enhance ice removal. However, despite extensive efforts, it remains a challenge to design anti-icing surfaces with low ice adhesion. Using all-atom molecular dynamics (MD) simulations, we show that surfaces with single-walled carbon nanotube array (CNTA) significantly reduce ice adhesion due to the extremely low solid areal fraction. It was found that the CNTA surface exhibits up to a 45% decrease in the ice adhesion strength in comparison with the atomically smooth graphene surface. The details of the ice detachment from the CNTA surface were examined for different water-carbon interaction energies and temperatures of the ice cube. Remarkably, the results of MD simulations demonstrate that the ice detaching strength depends linearly on the ratio of the ice-surface interaction energy and the ice temperature. These results open the possibility for designing novel robust surfaces with low ice adhesion for passive anti-icing applications.
We report on the quantum yield (eta) and decay time (tau) measurements at room temperature for the bright red-orange (602 nm) luminescence from new germanium-vacancy (Ge-V) centers in nano- and microcrystalline diamonds synthesized at high pressure and high temperature. The values eta = 3 +/- 1% and tau = 6.2 +/- 0.2 ns were found. The Stokes shift measured as the energy difference between the maxima of the luminescence and luminescence excitation spectra is negligible. The relative intensity of the zero-phonon line constitutes up to 70% from the total intensity of the luminescence. Results of our ab initio DFT calculations for the ground-state electronic and vibrational structure of (Ge-V)(-) in diamond are presented and discussed.
In situ XRD and NMR experiments combined with molecular dynamics simulations using the grand canonical ensemble (GCMD) show that cation size, charge and solvation energy play critical roles in determining the interlayer expansion of smectite clay minerals when exposed to dry supercritical CO2 under conditions relevant to the earthâ€™s upper crust, petroleum reservoirs, and geological CO2 sequestration conditions (323 K and 90 bar). The GCMD results show that the smectite mineral, hectorite, containing interlayer alkali and alkaline earth cations with relatively small ionic radii and high solvation and hydration energies (e.g., Li+, Na+ Mg2+, and Ca2+) does not intercalate dry CO2 and that the fully collapsed interlayer structure is the energetically most stable configuration. With increasing cation size and decreasing cation solvation energy, the energy barrier to CO2 intercalation decreases. With K+, Rb+, Cs+, Sr2+, and Ba2+ the monolayer structure is the stable configuration, and CO2 should spontaneously enter the interlayer. With Cs+ there is not even an energy barrier for CO2 intercalation, in agreement with the experimental XRD and NMR results that show clay layer expansion and CO2 incorporation. The number of intercalated CO2 molecules decreases with increasing size of the alkali cation but does not vary with ion size for the alkaline earth cations. 13C NMR spectroscopy and the GCMD simulations show that the average orientation of the intercalated CO2 molecules is with their O-C-O axes parallel to the basal clay surface and that they undergo a combination of rapid rotation about an axis perpendicular to the main molecular axis and wobbling motion with respect to the basal surface. Incorporation of CO2 in the interlayer decreases the coordination of Cs+ by the oxygen atoms of the basal surfaces, which is compensated by CO2 molecules entering their solvation shell, as predicted based on previously published NMR results. The GCMD simulations show that the strength of the interaction between the exchangeable cation and the clay structure dominates the intercalation energetics in dry scCO2. With relatively small cations, the cation-clay interactions outcompete cation solvation by CO2 molecules. The computed residence times for coordination among of interlayer species are consistent with the computed energetics.
The intercalation of H2O, CO2, and other fluid species in expandable clay minerals (smectites) may play a significant role in controlling the behavior of these species in geological C-sequestration and enhanced petroleum production and has been the subject of intensive study in recent years. This paper reports the results of a computational study of the effects of the properties of the charge balancing, exchangeable cations on H2O and CO2 intercalation in the smectite mineral, hectorite, in equilibrium with an H2O-saturated supercritical CO2 fluid under reservoir conditions using Grand Canonical Molecular Dynamics (GCMD) methods. The results show that the intercalation behavior is greatly different with cations with relatively low hydration energies and high affinities for CO2 (here Cs+) than with cations with higher hydration energies (here Ca2+). With Cs+, CO2 intercalation occurs in a 1-layer structure and does not require H2O intercalation, whereas with Ca2+ the presence of a sub-monolayer of H2O is required for CO2 intercalation. The computational results provide detailed structural, dynamical and energetic insight into the differences in intercalation behavior and are in excellent agreement with in situ experimental XRD, IR, quartz crystal microbalance, and NMR results for smectite materials obtained under reservoir conditions.
In this study, we investigated the cytogenetic effects of single and quadruple exposureof spermatogenic cells and hepatocytesof 129 mise, which have a mutation in the gtnt that encodes DNA polymeraseiota, to ultrasmall gold nanoparticles (GNPs).The combine effects of GNPs and chemical mutagen dipin were evaluated.
Molecular dynamics simulations are carried out to study the translational and rotational diffusion of a single Janus particle immersed in a dense Lennard-Jones fluid. We consider a spherical particle with two hemispheres of different wettabilities. The analysis of the particle dynamics is based on the time-dependent orientation tensor, particle displacement, as well as the translational and angular velocity autocorrelation functions. It was found that both translational and rotational diffusion coefficients increase with decreasing surface energy at the nonwetting hemisphere, provided that the wettability of the other hemisphere remains unchanged. We also observed that in contrast to homogeneous particles, the nonwetting hemisphere of the Janus particle tends to rotate in the direction of the displacement vector during the rotational relaxation time.
We construct a distribution function of the strain-tensor components induced by point defects in an elastically anisotropic continuum, which can be used to account quantitatively for many effects observed in different branches of condensed matter physics. Parameters of the derived six-dimensional generalized Lorentz distribution are expressed through the integrals computed over the array of strains. The distribution functions for the cubic diamond and elpasolite crystals and tetragonal crystals with the zircon and scheelite structures are presented. Our theoretical approach is supported by a successful modeling of specific line shapes of singlet-doublet transitions of the Tm3+ ions doped into ABO4 (A=Y, Lu; B=P, V) crystals with zircon structure, observed in high-resolution optical spectra. The values of the defect strengths of impurity Tm3+ ions in the oxygen surroundings, obtained as a result of this modeling, can be used in future studies of random strains in different rare-earth oxides.
The influence of individual impurities of Fe on the electronic properties of topological insulator Bi2Se3 is studied by Scanning Tunneling Microscopy. The microscope tip is used in order to remotely charge/discharge Fe impurities. The charging process is shown to depend on the impurity location in the crystallographic unit cell, on the presence of other Fe impurities in the close vicinity, and on the overall doping level of the crystal. We present a qualitative explanation of the observed phenomena in terms of tip-induced local band bending. Our observations evidence that the specific impurity neighborhood and the position of the Fermi energy with respect to both the Dirac point and bulk bands have to be taken into account when considering the electron scattering on the disorder in topological insulators.
Here, we present a new model of adsorption-induced deformation of mesoporous solids. The model is based on a simplified version of local density functional theory in the framework of solvation free energy. Instead of density, which is treated as constant here, we used film thickness and pore radius as order parameters. This allows us to obtain a self-consistent system of equations describing simultaneously the processes of gas adsorption and adsorbent deformation, as well as conditions for capillary condensation and evaporation. In the limit of infinitely rigid pore walls, when the film becomes several monolayers thick, the model reduces to the well-known Derjaguin–Broekhoff–de Boer theory for pores with cylindrical geometry. We have investigated the effects of enhanced flexibility of the solid as well as the influence of pore size distribution on the adsorption/deformation process. The formulation of the theory allows to determine the average pore size and its width from the desorption branch of the strain isotherm only. The model reproduces the nonmonotonic behavior of the strain isotherm at low relative pressure. Furthermore, we discuss the effect of rigidity of the adsorbent on the pore size distribution, showing qualitatively different results of the adsorption isotherms for rigid and highly flexible materials, in particular, the shift of evaporation pressure to lower values and the absence of a limiting value of the loading at high relative pressure. We also discuss the results of the theory with respect to experimental data obtained from the literature.
A novel triphenylamine derivative-linked ionic liquid unit, 1-(6-((4-(bis(4-(thiophen-2-yl)phenyl)amino)- benzoyl)oxy)hexyl)-3-methyl-imidazolium tetrafluoroborate (TTPAC6IL-BF4), was designed and synthesized successfully, and its corresponding polymer PTTPAC6IL-BF4 was obtained by the electropolymerization method. The highest occupied molecular orbital energy band of TTPAC6IL-BF4 is higher and the onset oxidative potential lower compared with that of 6-bromohexyl 4-(bis(4-(thiophen-2-yl)phenyl)amino) benzoate (TTPAC6Br) without modifying the ionic liquid unit. The results imply that introducing an ionic liquid unit to the side chain is an efficient method to improve the switching time of conjugated polymers and would be inspirational for the design and preparation of novel bifunctional electrochromic polymeric electrolytes.
The formation and properties of locally tensile strained Ge microstructures (“microbridges”) based on Ge layers grown on silicon substrates are investigated. The elastic-strain distribution in suspended Ge microbridges is analyzed theoretically. This analysis indicates that, in order to attain the maximum tensile strain within a microbridge, the accumulation of strain in all corners of the fabricated microstructure has to be minimized. Measurements of the local strain using Raman scattering show significant enhancement of the tensile strain from 0.2–0.25% in the initial Ge film to ~2.4% in the Ge microbridges. A considerable increase in the luminescence intensity and significant modification of its spectrum in the regions of maximum tensile strain in Ge microbridges and in their vicinity as compared to weakly strained regions of the initial Ge film is demonstrated by microphotoluminescence spectroscopy.
The excellent electronic and mechanical properties of graphene allow it to sustain very large currents, enabling its incandescence through Joule heating in suspended devices. Although interesting scientifically and promising technologically, this process is unattainable in ambient environment, because graphene quickly oxidises at high temperatures. Here, we take the performance of graphene-based incandescent devices to the next level by encapsulating graphene with hexagonal boron nitride (hBN). Remarkably, we found that the hBN encapsulation provides an excellent protection for hot graphene filaments even at temperatures well above 2000 K. Unrivalled oxidation resistance of hBN combined with atomically clean graphene/hBN interface allows for a stable light emission from our devices in atmosphere for many hours of continuous operation. Furthermore, when confined in a simple photonic cavity.
The use of improved fabrication technology, highly disordered NbN thin films, and intertwined section topology makes it possible to create high-performance photon-number-resolving superconducting single-photon detectors (PNR SSPDs) that are comparable to conventional single-element SSPDs at the telecom range. The developed four-section PNR SSPD has simultaneously an 86±3%86±3% system detection efficiency, 35 cps dark count rate, ∼2 ns∼2 ns dead time, and maximum 90 ps jitter. An investigation of the PNR SSPD’s detection efficiency for multiphoton events shows good uniformity across sections. As a result, such a PNR SSPD is a good candidate for retrieving the photon statistics for light sources and quantum key distribution systems.
We report on the first high-resolution optical spectroscopy study of LiYF4:Ho in an external magnetic field. Peculiarities in the hyperfine structure of holmium spectral lines are discussed for the cases H||c and H⊥c (H = 0.53 and 0.87 T). The spectra reveal a strong interaction between crystal-field levels, mediated by Zeeman and hyperfine terms in the Hamiltonian. A study of the magnetic-field-dependent isotope shifts in 7Li0.1 6Li0.9YF4:Ho (0.1 at.%) single crystals delivers an estimate of the difference in magnetic g factors for holmium centers with all 6Li isotopes in the nearest surrounding of Ho3+ (g(0)) and the centers having one 7Li isotope there (g(1)):g(1) − g(0) = 0.01 ± 0.005.
The effect of spherical SiO2 nanoparticles of 20 to 80 nm in diameter embedded into the PEDOT: PSS buffer layer of organic solar cells (OSC) based on star-shaped oligomers on their efficiency was studied experimentally in detail. Measurements and analysis of the current-voltage characteristics of the samples, their absorption spectra and study of the morphology of the surface of the buffer layer with embedded nanoparticles were carried out. It is shown an increase in the OSE efficiency for the case of embedded into the PEDOT:PSS layer SiO2 nanoparticles with a diameter of 20 and 50 nm, which slightly depends on the concentration of the nanoparticles in the buffer layer.
Proximity induced quantum coherence of electrons in multi-terminal voltage-driven hybrid normalsuperconducting nanostructures may result in a non-trivial interplay between topology-dependent Josephson and Aharonov-Bohm effects. We elucidate a trade-off between stimulation of the voltagedependent Josephson current due to non-equilibrium effects and quantum dephasing of quasiparticles causing reduction of both Josephson and Aharonov-Bohm currents. We also predict phase-shifted quantum coherent oscillations of the induced electrostatic potential as a function of the externally applied magnetic flux. Our results may be employed for engineering superconducting nanocircuits with controlled quantum properties.
The study of frequency-dependent intrinsic dissipation in a highly transparent Josephson junction by means of quantum-bit (qubit) spectroscopy is proposed. The spectral density of the effective dissipative bath may contain significant contributions from Andreev bound states coupled to fluctuations of the Josephson phase. Varying either the bias current applied to the junction or magnetic flux through a superconducting ring in the radiofrequency superconducting quantum interference device (rf-SQUID) setup, one can tune the level splitting value close to the bottom of the Josephson potential well. Monitoring the qubit energy relaxation time one can probe the spectral density of the effective dissipative bath and unambiguously identify the contribution emerging from Andreev levels.
Copper borate Cu3(BO3)2 is a complex compound with a layered crystallographic structure in which the Jahn-Teller active and magnetic copper Cu2+ ions occupy 16 nonequivalent positions in the unit cell displaying controversial magnetic behavior. In this paper, we report on the infrared and Raman spectroscopic studies of the lattice dynamics and the electronic structure of 3d9 copper states below the fundamental absorption band. The lattice dynamics is characterized by a large number of phonons due to a low P1 space-group symmetry and a large unit cell with Z = 10. An unusually rich set of phonons was found in the low-energy part of the infrared and Raman spectra below 100 cm−1, which we tentatively assign to interlayer vibrations activated by a crystal superstructure and/or to weak force constants for modes related to some structural groups. Several phonons show anomalous behavior in the vicinity of the magnetic phase transition at TN = 10 K, thus evidencing magnetoelastic interaction. No new phonons were found below TN, which excludes the spin-Peierls type of the magnetic transition. In the region of electronic transitions, a strong broad absorption band centered at ∼1.8 eVis observed, which we assign to overlapping of transitions between the 3d9 states of Cu2+ ions split by the crystal field in nonequivalent positions. The fundamental charge-transfer absorption band edge has a complex structure and is positioned around ∼2.8−3.0 eV.