On the Friction Behavior of SiO2 Tip Sliding on the Au(111) Surface: How Does an Amorphous SiO2 Tip Produce Regular Stick-Slip Friction and Friction Duality?

Friction behaviors of an amorphous SiO2 tip sliding on the Au(111) surface in atomic force microscopy (AFM) are investigated through molecular dynamics (MD) simulations. We observed a regime of extremely low, close-to-zero friction at low normal loads with clear stick-slip friction signals. The friction is almost independent of the applied normal load below a threshold value. However, above this loading threshold, friction can remain low or increase sharply. Such an unexpected friction duality is attributed to the high probability of defect formation at the sliding interface that can induce plowing friction in a high-friction state. The energy difference between the low-friction state and the high-friction state is surprisingly low, which is comparable to kT (∼25 meV) at room temperature. These findings are consistent with previous AFM friction measurements using silicon AFM tips. Further MD simulations show that one can always use an amorphous SiO2 tip to image the crystalline surface with regular stick-slip friction signals. This is largely due to the fact that there is always a small fraction of contacting Si and O atoms at the sliding interface that are sitting on the relatively stable, close-to-hollow sites of the crystalline Au(111) surface during the stick stage; thus, they are capable of sampling local energy minima. We anticipate that regular stick-slip friction can be achieved even in the intermediate loading range, so long as the low-friction state is maintained when friction duality occurs.

Will Polycrystalline Platinum Tip Sliding on a Gold(111) Surface Produce Regular Stick-Slip Friction?

Friction measurements by an atomic force microscope (AFM) frequently showed regular stick-slip friction signals with atomic-scale resolutions. Typically, for an AFM metal tip sliding on a metal crystal surface, the microstructure of the tip made from the thermally evaporated metal coating on a silicon cantilever was polycrystalline. Our detailed molecular dynamics(MD) simulations of a polycrystalline Pt tip (R = 10 nm in radius) sliding on an Au(111) surface revealed how the geometry of the polycrystalline tip took effect on the friction behavior at the contact interface. We found that the apex of the Pt tip with multiple grains near the edge of contact could induce severe plastic deformations of the gold substrate, leading to irregular stick-slip frictions upon sliding. Simulation results showed that in order to achieve a clear stick-slip friction signal with single atomic slips, the apex of the Pt tip must adopt a single crystalline protrusion without any neighboring grains involved in the metal contact. We showed that such a single crystalline protrusion, which presumably could be achieved during initial run-in or wear-out of high-energy Pt atoms in the neighboring grains, was passivated by a large number of gold atoms due to metal adhesion in the contact periphery. Using such a crystalline protrusion tip, we demonstrated that the stick-slip friction produced was very "tolerant" to the adhesion of a large number of gold atoms on the tip apex. We further showed that AFM tip mass used in MD simulations also played an important role in determining the transition between friction regimes, which could be well explained by the Prandtl-Tomlinson thermal activation model.

Nucleation of Frank Dislocation during the Squeeze-Out Process in Boundary Lubrication: A Molecular Dynamics Study.

Liquid-vapor molecular dynamics (LVMD) simulations are performed to reinvestigate the phase transition and solvation force oscillation behavior of a simple argon liquid film confined between two solid surfaces. Our simulations present a novel scenario in which the n → n - 1 layering transitions are accompanied by the formation, climb, and annihilation of Frank partial dislocations during the squeeze-out process under compression. This is indicated by the splitting of the repulsive peaks in the solvation force profile. The detailed analysis reveals that the formation-climb-annihilation mechanism of Frank dislocation occurs during approach and disappears during receding, which would result in force hysteresis. In combination with our recent works, this study provides new insights into the physical property of nanoconfined lubricant films in boundary lubrication.

Direct Measurement of Intermolecular Mechanical Force for Nonspecific Interactions between Small Molecules.

Mechanical force can evaluate intramolecular interactions in macromolecules. Because of the rapid motion of small molecules, it is extremely challenging to measure mechanical forces of nonspecific intermolecular interactions. Here, we used optical tweezers to directly examine the intermolecular mechanical force (IMMF) of nonspecific interactions between two cholesterols. We found that IMMFs of dimeric cholesterol complexes were dependent on the orientation of the interaction. The surprisingly high IMMF in cholesterol dimers (∼30 pN) is comparable to the mechanical stability of DNA secondary structures. Using Hess-like cycles, we quantified that changes in free energy of solubilizing cholesterol (ΔGsolubility) by ß-cyclodextrin (ßCD) and methylated ßCD (Me-ßCD) were as low as -16 and -27 kcal/mol, respectively. Compared to the ΔGsolubility of cholesterols in water (5.1 kcal/mol), these values indicated that cyclodextrins can easily solubilize cholesterols. Our results demonstrated that the IMMF can serve as a generic and multipurpose variable to dissect nonspecific intermolecular interactions among small molecules into orientational components.

A Molecular Dynamics Simulations Study of the Influence of Prestrain on the Pop-In Behavior and Indentation Size Effect in Cu Single Crystals.

The pop-in effect in nanoindentation of metals represents a major collective dislocation phenomenon that displays sensitivity in the local surface microstructure and residual stresses. To understand the deformation mechanisms behind pop-ins in metals, large scale molecular dynamics simulations are performed to investigate the pop-in behavior and indentation size effect in undeformed and deformed Cu single crystals. Tensile loading, unloading, and reloading simulations are performed to create a series of samples subjected to a broad range of tensile strains with/without pre-existing dislocations. The subsequent nanoindentation simulations are conducted to investigate the coupled effects of prestrain and the presence of resulting dislocations and surface morphology, as well as indenter size effects on the mechanical response in indentation processes. Our work provides detailed insights into the deformation mechanisms and microstructure-property relationships of nanoindentation in the presence of residual stresses and strains.

Measurement of Single-Molecule Forces in Cholesterol and Cyclodextrin Host-Guest Complexes.

Biological host molecules such as ß-cyclodextrins (ß-CDs) have been used to remove cholesterol guests from membranes and artery plaques. In this work, we calibrated the host-guest intermolecular mechanical forces (IMMFs) between cholesterol and cyclodextrin complexes by combining single-molecule force spectroscopy in optical tweezers and computational molecular simulations for the first time. Compared to native ß-CD, methylated beta cyclodextrins complexed with cholesterols demonstrated higher mechanical stabilities due to the loss of more high-energy water molecules inside the methylated ß-CD cavities. This result is consistent with the finding that methylated ß-CD is more potent at solubilizing cholesterols than ß-CD, suggesting that the IMMF can serve as a novel indicator to evaluate the solubility of small molecules such as cholesterols. Importantly, we found that the force spectroscopy measured in such biological host-guest complexes is direction-dependent: pulling from the alkyl end of the cholesterol molecule resulted in a larger IMMF than that from the hydroxyl end of the cholesterol molecule. Molecular dynamics coupled with umbrella sampling simulations further revealed that cholesterol molecules tend to enter or leave from the wide opening of cyclodextrins. Such an orientation rationalizes that cyclodextrins are rather efficient at extracting cholesterols from the phospholipid bilayer in which hydroxyl groups of cholesterols are readily exposed to the hydrophobic cavities of cyclodextrins. We anticipate that the IMMF measured by both experimental and computational force spectroscopy measurements help elucidate solubility mechanisms not only for cholesterols in different environments but also to host-guest systems in general, which have been widely exploited for their solubilization properties in drug delivery, for example.

Ultrafast photoinduced band splitting and carrier dynamics in chiral tellurium nanosheets.

Trigonal tellurium (Te) is a chiral semiconductor that lacks both mirror and inversion symmetries, resulting in complex band structures with Weyl crossings and unique spin textures. Detailed time-resolved polarized reflectance spectroscopy is used to investigate its band structure and carrier dynamics. The polarized transient spectra reveal optical transitions between the uppermost spin-split H4 and H5 and the degenerate H6 valence bands (VB) and the lowest degenerate H6 conduction band (CB) as well as a higher energy transition at the L-point. Surprisingly, the degeneracy of the H6 CB (a proposed Weyl node) is lifted and the spin-split VB gap is reduced upon photoexcitation before relaxing to equilibrium as the carriers decay. Using ab initio density functional theory (DFT) calculations, we conclude that the dynamic band structure is caused by a photoinduced shear strain in the Te film that breaks the screw symmetry of the crystal. The band-edge anisotropy is also reflected in the hot carrier decay rate, which is a factor of two slower along the c-axis than perpendicular to it. The majority of photoexcited carriers near the band-edge are seen to recombine within 30 ps while higher lying transitions observed near 1.2 eV appear to have substantially longer lifetimes, potentially due to contributions of intervalley processes in the recombination rate. These new findings shed light on the strong correlation between photoinduced carriers and electronic structure in anisotropic crystals, which opens a potential pathway for designing novel Te-based devices that take advantage of the topological structures as well as strong spin-related properties.

Molecular Understanding of Ion Effect on Polyzwitterion Conformation in an Aqueous Environment.

Polyzwitterions (PZs) are promising materials for the antifouling in reverse osmosis and nanofiltration membrane technology for water treatment. Fundamental understanding of the structure and molecular interactions involving zwitterions is crucial to the optimal design of antifouling in membrane separation. Here we employ the umbrella sampling and molecular dynamics simulations to investigate molecular interactions between sulfobetaine/carboxybetaine zwitterions and different metal ions (Na+, K+, and Ca2+) in an aqueous solution. The simulation results show that these ions can form stable or metastable contact ionic/solvent-shared-ionic pairs with zwitterions. Simulations at different grafting densities of PZ brush arrays reveal complex competitive association mechanisms, which are attributed to nonbonded electrostatic and van der Waals interactions among zwitterions, water molecules, and different metal ions in an aqueous environment. While the high-grafting density of the PZ brush array leads to a strong branch association between different zwitterions in water, this association is decreased at intermediate- and low-grafting densities due to strong zwitterion-water interactions. More importantly, adding ions into water at intermediate- and low-grafting densities further breaks down the zwitterion branch association, resulting in a randomly oriented and dispersed branch configuration with significant swelling of the polymers. The degree of swelling depends on the type of ions, which further changes the surface electrostatic potential of PZ coatings.

On the shear dilation of polycrystalline lubricant films in boundary lubricated contacts.

Shearing of a solidified polycrystalline lubricant film confined between two solid surfaces has been studied by molecular dynamics simulations. In the case of a perfect commensurate contact, we observe interlayer slips within the film and shear-induced order-to-disorder transition of lubricant molecules around grain boundaries. This process is accompanied by the nucleation, propagation, and annihilation of dislocations in the solidified film, resulting in repeated dilation and collapse of the lubricant film during the stick-slip motion. In the case of an incommensurate contact, only slips at the lubricant-solid interface happen and no dilation of the lubricant film is observed during the stick-slip friction. These observations are consistent with recent surface force balance experimental measurements. In combination with our recent work [R. G. Xu and Y. S. Leng, Proc. Natl. Acad. Sci. U. S. A. 115, 6560 (2018)], this study provides a renewed picture on the physical property of nanoconfined lubricant films in boundary lubrication.

Driven Dynamics of Long-Time Bond-Breaking Events.

We present a predict-correct trajectory propagation (PCTP) method for simulating nonequilibrium driven dynamics of the long-time bond-breaking event in an atomic force microscope (AFM). Whereas the parallel replica method can extend the time scale of molecular dynamics (MD) simulations of infrequent-event systems with high parallel efficiency, the second aspect of the time scale difficulty in MD simulations for slow-driven systems, namely, the unphysically high attempt frequency of an infrequent event, cannot be resolved by this method. Here, we take a gold nanojunction under mechanical pulling as a simulation system and demonstrate that the PCTP simulation is capable of capturing key transition dynamics of bond breaking predicted by accurate MD simulations in the activationless regime, such as at cryogenic temperature with high pulling rates. The PCTP algorithm includes three steps: (i) the trajectory prediction of the AFM tip, (ii) the atomic structural relaxation of the nanojunction, and (iii) the trajectory correction of the tip motion predicted by step (i). Application of the PCTP simulation to the bond breaking at AFM experimental pulling rates reveals different rupture mechanisms, depending on temperature and single-atom nanojunction structures, which are consistent with recent AFM bond-breaking observations.

Squeezing and stick-slip friction behaviors of lubricants in boundary lubrication.

The fundamental questions of how lubricant molecules organize into a layered structure under nanometers confinement and what is the interplay between layering and friction are still not well answered in the field of nanotribology. While the phase transition of lubricants during a squeeze-out process under compression is a long-standing controversial debate (i.e., liquid-like to solid-like phase transition versus amorphous glass-like transition), recent different interpretations to the stick-slip friction of lubricants in boundary lubrication present new challenges in this field. We carry out molecular dynamics simulations of a model lubricant film (cyclohexane) confined between molecularly smooth surfaces (mica)--a prototypical model system studied in surface force apparatus or surface force balance experiments. Through fully atomistic simulations, we find that repulsive force between two solid surfaces starts at about seven lubricant layers (n = 7) and the lubricant film undergoes a sudden liquid-like to solid-like phase transition at n < 6 monolayers thickness. Shear of solidified lubricant films at three- or four-monolayer thickness results in stick-slip friction. The sliding friction simulation shows that instead of shear melting of the film during the slip of the surface, boundary slips at solid-lubricant interfaces happen, while the solidified structure of the lubricant film is well maintained during repeated stick-slip friction cycles. Moreover, no dilation of the lubricant film during the slip is observed, which is surprisingly consistent with recent surface force balance experimental measurements.

Molecular Simulations of the Hydration Behavior of a Zwitterion Brush Array and Its Antifouling Property in an Aqueous Environment.

We carried out umbrella sampling and molecular dynamics (MD) simulations to investigate molecular interactions between sulfobetaine zwitterions or between sulfobetaine brushes in different media. Simulation results show that it is more energetically favorable for the two sulfobetaine zwitterions or brushes to be fully hydrated in aqueous solutions than in vacuum where strong ion pairs are formed. Structural properties of the hydrated sulfobetaine brush array and its antifouling behavior against a foulant gel are subsequently studied through steered MD simulations. We find that sulfobetaine brush arrays with different grafting densities have different structures and antifouling mechanisms. At a comparably higher grafting density, the sulfobetaine brush array exhibits a more organized structure which can hold a tightly bound hydration water layer at the interface. Compression of this hydration layer results in a strong repulsive force. However, at a comparably lower grafting density, the brush array exhibits a randomly oriented structure in which the antifouling of the brush array is through the deformation of the sulfobetaine branches.

Computational simulations of solvation force and squeezing out of dodecane chain molecules in an atomic force microscope.

Understanding the squeeze out behaviors of liquid films at nanometer scale in an atomic force microscope (AFM) has been a significant interest since the 1990s. We carry out all-atom static-mode AFM simulations in a liquid-vapor molecular dynamics ensemble to investigate the solvation force oscillation and squeeze out mechanisms of a confined linear dodecane fluid between a gold AFM tip and a mica substrate. Solvation force oscillations are found to be associated with the layering transition of the liquid film and unstable jumps of the AFM tip. Detailed structural analyses and molecular animations show that the local permeation of chain molecules and the squeeze out of molecules near the edge of contact promote the layering transition under compression. The confinement-induced slow down dynamics is manifested by the decrease in diffusivity and increase in rotational relaxation times. However, the persistent diffusive behavior of dodecane chain molecules even in the single-monolayer film is attributed to the chain sliding motions in the film due to the substantial vacancy space and thermal fluctuations.

Effect of Layer Charge on CO2 and H2O Intercalations in Swelling Clays.

The effect of layer charge on the intercalation of supercritical carbon dioxide (scCO2)-H2O mixture in Na-montmorillonite clay interlayers under T = 323 K and P = 90 bar geologic sequestration conditions has been further investigated. This effect includes the charge amount and its location (within either octahedral or tetrahedral layers due to isomorphic substitutions). Two clay models with different layer charges are used in this study. Simulation results show that the increase of charge amount shifts the monolayer-to-bilayer (1W-to-2W) hydration transition toward the lower relative humidity (RH), increasing water sorption at the expense of reducing the overall sorption amount of CO2 in the clay interlayer. However, the combination of the influence of charge amount and charge location leads to insignificant changes in equilibrium basal spacings of the high- and low-charge clays. Molecular dynamics simulations show that the CO2 dimers, which are frequently seen in low-charge clay interlayers, vanish in high-charge clay interlayers even at low RH of 30%.

Contact stiffness and damping of liquid films in dynamic atomic force microscope.

The mechanical properties and dissipation behaviors of nanometers confined liquid films have been long-standing interests in surface force measurements. The correlation between the contact stiffness and damping of the nanoconfined film is still not well understood. We establish a novel computational framework through molecular dynamics (MD) simulation for the first time to study small-amplitude dynamic atomic force microscopy (dynamic AFM) in a simple nonpolar liquid. Through introducing a tip driven dynamics to mimic the mechanical oscillations of the dynamic AFM tip-cantilever assembly, we find that the contact stiffness and damping of the confined film exhibit distinct oscillations within 6-7 monolayer distances, and they are generally out-of-phase. For the solid-like film with integer monolayer thickness, further compression of the film before layering transition leads to higher stiffness and lower damping, while much lower stiffness and higher damping occur at non-integer monolayer distances. These two alternating mechanisms dominate the mechanical properties and dissipation behaviors of simple liquid films under cyclic elastic compression and inelastic squeeze-out. Our MD simulations provide a direct picture of correlations between the structural property, mechanical stiffness, and dissipation behavior of the nanoconfined film.

Molecular Dynamics Simulations of a Poly(ethylene glycol)-Grafted Polyamide Membrane and Its Interaction with a Calcium Alginate Gel.

Molecular dynamics simulations are carried out to investigate the antifouling property of a polyethylene glycol (PEG)-grafted polyamide (PA) membrane. Our specific interest is the computational study of the interaction between a grafted PEG coating and an alginate gel foulant by a steered molecular dynamics approach. Simulation results show that the PEG coating can hold a tightly bound hydration water layer. When the alginate gel is dragged to approach the PEG coating surface, a strong repulsive hydration force is observed due to the compression of this hydration layer. Detailed calculations of the potential of mean force (PMF) show that the repulsive interaction between the alginate gel and the hydration water layer around the PEG coating has a dominant contribution to the total repulsive PMF. We have also studied the effect of the PEG coverage on the membrane-foulant interactions. We find that the alginate gel has a strong tendency to drift to the uncovered PA membrane surfaces (namely, the PEG hollows). However, direct attachment of the gel to the PA membrane surface can be avoided if the gel size is slightly larger than the PEG hollow site.

Methane aqueous fluids in montmorillonite clay interlayer under near-surface geological conditions: a grand canonical Monte Carlo and molecular dynamics simulation study.

The grand-canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations are performed to investigate the methane aqueous fluids in Na-montmorillonite clay interlayer under near-surface geological temperature and pressure conditions (T = 300 K and P = 20-50 bar). The chemical potentials of water and methane under these T/P conditions are calculated using the Widom's insertion method. These chemical potentials are used in the GCMC simulations to determine the contents of different species in the clay interlayer, especially in those that correspond to the equilibrium stable spacing distances. Simulation results show that initial clay swelling is dominated by water adsorption into the clay interlayer, followed by the intercalation of methane as the basal spacing increases. However, it is found that this methane intercalation process is strongly influenced by the relative humidity and the total gas pressure of the system. High relative humidity may facilitate water molecules entering the clay interlayer region and inhibit the intercalation of methane molecules. MD simulations show that sodium ions are fully hydrated by water molecules and clay surface oxygen atoms, while methane molecules are not fully coordinated. This situation is attributed to the less water content in clay interlayer and the subsequent formation of methane dimer or trimer clusters due to the hydrophobic nature of small hydrocarbon molecules.

Molecular dynamics simulations of polyamide membrane, calcium alginate gel, and their interactions in aqueous solution.

We perform molecular dynamics (MD) simulations to investigate the cross-linked polyamide (PA) membrane, the aggregation of alginate molecules in the presence of Ca(2+) ions, and their molecular binding mechanism in aqueous solution. We use a steered molecular dynamics (SMD) approach to simulate the unbinding process between a PA membrane and an alginate gel complex. Simulation results show that Ca(2+) ions are strongly associated with the carboxylate groups in alginate molecules, forming a web structure. The adhesion force between alginate gel and PA surface during unbinding originates from several important molecular interactions. These include the short-range hydrogen bonding and van der Waals attraction forces, and the ionic bridge binding that extends much longer pulling distances due to the significant chain deformations of alginate gel and PA membrane.

Solvation force simulations in atomic force microscopy.

Solvation force oscillation in octamethylcyclotetrasiloxane (OMCTS) versus the distance between an atomic force microscope (AFM) tip and mica substrate has been studied through molecular dynamics simulations. A driving spring model in a liquid-vapor molecular ensemble is used to explore the force oscillation mechanism. It has been found that OMCTS fluid in tip-substrate contact has a strong tendency to form a layered structure, starting from n = 8 layers. The force profile obtained from simulation is qualitatively similar to those in contact mode AFM experiments. However, the bulk-like diffusion and rotation of OMCTS molecules underneath the AFM tip suggest that, under the tip-substrate confinement geometry, the layered OMCTS film cannot form a solidified structure except under n = 2 extreme contact-layer confinement.

A comparative study by the grand canonical Monte Carlo and molecular dynamics simulations on the squeezing behavior of nanometers confined liquid films.

Grand canonical Monte Carlo (GCMC) and liquid-vapor molecular dynamics (LVMD) simulations are performed to investigate the squeezing and phase transition of a simple liquid argon film confined between two solid surfaces. Simulation results show that the LVMD simulation is capable of capturing the major thermodynamic equilibrium states of the confined film, as predicted by the GCMC simulations. Moreover, the LVMD simulations reveal the non-equilibrium squeeze out dynamics of the confined film. The study shows that the solvation force hysteresis, observed in many surface force experiments, is attributed to two major effects. The first is related to the unstable jumps during the laying transitions of the confined film, in which the gradient of force profile is larger than the driving spring constant. The second effect is related to the squeeze out dynamics of the confined film even though the first effect is absent. In general, these two dynamic processes are non-equilibrium in nature and involve significant energy dissipations, resulting in the force hysteresis.