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Si is an important semiconductor material in the development of modern industry. With the miniaturization trend of semiconductor devices, the size of Si has reached the cluster size. The search for stable Si clusters is an important issue. In this work, the electronic structures and stability mechanism of the W@Si12 cluster are calculated by the first-principle calculations. Different from a C2v hexacapped trigonal prism structure of Si12, the W@Si12 cluster presents an embedded hexagonal prism structure with D6h symmetry. The addition of W atom leads to a higher stability. The molecular orbitals show obvious superatomic characteristics for the W@Si12 cluster, and their energy levels are more degenerate than that of the Si12 cluster. The population analysis indicates that a total charge of 2.21e is transferred from Si atoms to the center W atom, which suggests an ionic bond for W-Si. The electron localization function further proves a covalent bond for Si–Si. The enhanced stability of the W@Si12 cluster is attributed to the combination of the ionic and covalent bonds. [ABSTRACT FROM AUTHOR]

The misfit layer compound (SnS)1.2(TiS2)2 is a promising low-cost thermoelectric material because of its low thermal conductivity derived from the superlattice-like structure. However, the strong covalent bonds within each constituent layer highly localize the electrons thereby it is highly challenging to optimize the power factor by doping or alloying. Here, we show that Bi doping at the Sn site markedly breaks the covalent bonds networks and highly delocalizes the electrons. This results in a high charge carrier concentration and enhanced power factor throughout the whole temperature range. It is highly remarkable that Bi doping also significantly reduces the thermal conductivity by suppressing the heat conduction carried by phonons, indicating that it independently modulates phonon and charge transport properties. These effects collectively give rise to a maximum ZT of 0.3 at 720 K. In addition, we apply the single Kane band model and the Debyeâ€"Callaway model to clarify the electron and phonon transport mechanisms in the misfit layer compound (SnS)1.2(TiS2)2. [ABSTRACT FROM AUTHOR]

The misfit layer compound (SnS)1.2(TiS2)2 is a promising low-cost thermoelectric material because of its low thermal conductivity derived from the superlattice-like structure. However, the strong covalent bonds within each constituent layer highly localize the electrons thereby it is highly challenging to optimize the power factor by doping or alloying. Here, we show that Bi doping at the Sn site markedly breaks the covalent bonds networks and highly delocalizes the electrons. This results in a high charge carrier concentration and enhanced power factor throughout the whole temperature range. It is highly remarkable that Bi doping also significantly reduces the thermal conductivity by suppressing the heat conduction carried by phonons, indicating that it independently modulates phonon and charge transport properties. These effects collectively give rise to a maximum ZT of 0.3 at 720 K. In addition, we apply the single Kane band model and the Debyeâ€"Callaway model to clarify the electron and phonon transport mechanisms in the misfit layer compound (SnS)1.2(TiS2)2. [ABSTRACT FROM AUTHOR]

Identification and quantification of epigoitrin (EP) in some herbs and traditional Chinese medicine (TCM) preparations are critical to pharmacokinetic study and pharmaceutical quality control due to its distinct antiviral activity. So, developing highly sensitive and selective method for detection of EP is essential for clinical treatment and drug development. In this study, a novel molecularly imprinted electrochemical sensor for detection of EP was firstly constructed. With acrylamide imprinting systems, surface imprinting on the polyaniline functionalized graphene oxide was employed to prepare molecularly imprinted polymer by electropolymerization, which follow-up constructed afford specific binding cavities, endowing the exclusive recognition ability. Furthermore, the polyacrylamide chain is anchored to the polyaniline chain by covalent bonds, which is beneficial for raising electrochemistry signal. Under the optimized condition, the sensor demonstrates a linear wide range of 4.6 × 10−7 mol l−1 ∼ 4.6 × 10−5 mol l−1 with a correlation coefficient of 0.9953 and a low LOD of 8.21 × 10−8 mol l−1 (S/N = 3). Additionally, the sensor showed good stability, repeatability (RSD 1.52%) and selectivity. The method was applied to analyze EP in the extraction from Isatidis Radix with a recovery higher than 97.8% and RSD less than 1.81%. This work provided a novel strategy for on-site, realtime and rapid detection of indicator components from TCM. [ABSTRACT FROM AUTHOR]

Using the evolutionary methodology for crystal structure prediction, we have predicted the orthorhombic Cmcm and Pnma phases for ScB4. The earlier proposed CrB4-, FeB4-, MnB4-, and ReP4-type structures for ScB4 are excluded. It is first discovered that the Cmcm phase transforms to the Pnma phase at about 18 GPa. Moreover, both phases are dynamically and mechanically stable. The large bulk modulus, shear modulus, and Young's modulus of the two phases make it an optimistic low compressible material. Moreover, the strong covalent bonding nature of ScB4 is confirmed by the ELF analysis. The strong covalent bonding contributes greatly to its stability. [ABSTRACT FROM AUTHOR]

Heterostructure with a symmetry-mismatched interface provides a promising playground for the exploration of emergent phenomena. Herein, we report a systematic investigation on La2/3Sr1/3MnO3/YBaCo2O5+δ (LSMO/YBCO) grown on SrTiO3, a heterostructure formed by perovskite oxides of different symmetry. A high-resolution lattice image shows the formation of high-quality perovskite LSMO and A-site cation-ordered oxygen-deficient double perovskite YBCO, without any signatures of atomic reconfiguration at the interface. Surprisingly, the YBCO-buffered LSMO exhibits perpendicular magnetic anisotropy (PMA), though bare LSMO film is in-plane anisotropic. The PMA is robust, appearing even when the thickness of YBCO is only one unit cell. The typical anisotropy constant is ∼4 × 106 erg cm−3. X-ray absorption spectroscopy analysis reveals a preferential occupation of the orbital compared with , which is confirmed by density functional theory calculations. This orbital reconstruction accounts for the PMA. The formation of a covalent bond between Mn and Co caged by different oxygen polyhedrons, an octahedron and a square pyramid, respectively, stabilizes the orbital reconstruction, resulting in anomalous spin orientation. [ABSTRACT FROM AUTHOR]

Gallium arsenide (GaAs), a typical covalent semiconductor, is widely used in the electronic industry, owing to its superior electron transport properties. However, its brittle nature is a drawback that has so far significantly limited its application. An exploration of the structural deformation modes of GaAs under large strain at the atomic level, and the formulation of strategies to enhance its mechanical properties is highly desirable. The stress-strain relations and deformation modes of single-crystal and nanotwinned GaAs under various loading conditions are systematically investigated, using first-principles calculations. Our results show that the ideal strengths of nanotwinned GaAs are 14% and 15% higher than that of single-crystal GaAs under pure and indentation shear strains, respectively, without producing a significantly negative effect in terms of its electronic performance. The enhancement in strength stems from the rearrangement of directional covalent bonds at the twin boundary. Our results offer a fundamental understanding of the mechanical properties of single crystal GaAs, and provide insights into the strengthening mechanism of nanotwinned GaAs, which could prove highly beneficial in terms of developing reliable electronic devices. [ABSTRACT FROM AUTHOR]

Graphene material has a large theoretical specific surface area, excellent theoretical conductivity and mechanical flexibility, and is a promising electrode material for supercapacitors. However, two-dimensional graphene sheets are easy to stack, which affects its electrical properties. Specifically, a sponge-like composite hydrogel for high-performance supercapacitors was prepared by onestep hydrothermal method from activated carbon and graphene oxide. Benefiting from the introduced nitrogen-containing groups and the greatly increased specific surface area, the GAC-2 nitrogen-doped activated carbon/graphene hydrogel electrode showed high specific capacitance of 505.6 F g-1. In addition, the composite hydrogel presented an excellent 3D network structure with abundant internal structural pores, in which graphene and activated carbon were cross-linked by strong covalent bonds. This unique structure greatly improves the mechanical flexibility of the composite electrode (the capacitance retention rate is approximately 87.7% after 500 bending tests). And the self-assembled flexible supercapacitor shows an energy density of 26.9 Wh kg-1 at 242 W kg-1 and outstanding capacitance retention rate of about 92.1% after 5000 charge-discharge cycles, confirming its potential application in supercapacitors. [ABSTRACT FROM AUTHOR]

Grain boundaries (GBs) are significant in determining the electrical properties of polycrystalline semiconductors. However, the electronic structures and passivation mechanisms of polycrystalline semiconductors remain poorly understood. In this study, we systematically investigated the Σ3 (112) GB properties of several typical zinc-blende semiconductors via first-principles density functional calculations. We found significant differences of Σ3 (112) GB structures and properties between IV/III and V types, where dangling atoms formed new covalent bonds, and II–VI/I–VII types, where dangling atoms formed no new bonds. These different bonding configurations lead to different origins of defect states at GBs. We successfully designed a targeted doping approach to passivate such defect states for different types of semiconductors. We demonstrated the validity of the proposed approach in Σ3 (112) GB of the zinc-blende semiconductors. This work elucidates the defect states at GBs in common zinc-blende semiconductors, rationalizes diverse post-treatment approaches reported in previous experiments, and provides general guidance for defect passivation at the GBs of polycrystalline semiconductors. [ABSTRACT FROM AUTHOR]

Considering that pressure-induced formation of short, strong covalent bonds in light-element compounds can produce superhard materials, we employ structure searching and first-principles calculations to predict a new class of boron nitrides with a stoichiometry of BN2, which are stable relative to alpha-B and alpha-N2 at ambient pressure. At ambient pressure, the most stable phase has a layered structure (h-BN2) containing hexagonal BN layers between which there are intercalated N2 molecules. At 25 GPa, a three-dimensional P42/mmc structure with single N–N bonds becomes the most stable. Dynamical, thermal, and mechanical stability calculations reveal that this structure can be recovered under ambient conditions. Its calculated stress-strain relations demonstrate an intrinsic superhard nature with an estimated Vickers hardness of ∼43 GPa. This structure has a potentially high energy density of ∼4.19 kJ/g. [ABSTRACT FROM AUTHOR]

The combination of different nanomaterials through step-by-step synthesis procedures has turned into a promising alternative to fabricate high-quality nanosystems in order to satisfy the increasingly demanding requirements of the biomedical field. In this work, we report a detailed study on the synthesis and characterization of a complex nanosystem composed of nanoparticles with a single magnetic nanoparticle core and a shell of dense and mesoporous silica arranged in layers. The procedure designed to fabricate these systems lead us to the formation of a dispersion of non-agglomerated spherical nanoparticles of nearly 100 nm. The structural characterization performed over the final samples confirmed both the prevalence of single-core systems and the presence of the mesoporous silica shell in the outer layer. The performance of the nanosystem in a specific technological application was tested by sequentially loading two different fluorescents molecules by covalent and non-covalent bonding strategies. Due to the distinct loading strategies, the resulting nanosystem presented a magnetically-assisted probe & release functionality as analyzed in a magnetophoretic experiment. [ABSTRACT FROM AUTHOR]

A non-enzymatic chemical sensor for lactate (LA) detection based on an extended-gate type organic field-effect transistor (OFET) is reported. The proposed device is composed of an extended-gate electrode modified by an artificial receptor phenylboronic acid derivative as the detection part and the OFET as the drive part. The mechanism of LA detection relies on the changes in transfer characteristics of the OFET upon dynamic covalent bonding with LA. After evaluating the ability of the device to detect LA, it was applied to the selectivity study. This report proved the possibility of using the OFET-based sensor device for non-enzymatic LA detection. [ABSTRACT FROM AUTHOR]

Highly concentrated electrolytes (HCEs) are attracting interest as safer and more stable alternatives to current lithium-ion battery electrolytes, but their structure, solvation dynamics and ion transport mechanisms are arguably more complex. We here present a novel general method for analyzing both the structure and the dynamics, and ultimately the ion transport mechanism(s), of electrolytes including HCEs. This is based on automated detection of bonds, both covalent and coordination bonds, including how they dynamically change, in molecular dynamics (MD) simulation trajectories. We thereafter classify distinct local structures by their bond topology and characterize their physicochemical properties by statistical mechanics, giving both a qualitative and quantitative description of the structure, solvation and coordination dynamics, and ion transport mechanism(s). We demonstrate the method by in detail analyzing an ab initio MD simulation trajectory of an HCE consisting of the LiTFSI salt dissolved in acetonitrile at a 1:2 molar ratio. We find this electrolyte to form a flexible percolating network which limits vehicular ion transport but enables the Li+ ions to move between different TFSI coordination sites along with their first solvation shells. In contrast, the TFSI anions are immobilized in the network, but often free to rotate which further facilitates the Li+ hopping mechanism. [ABSTRACT FROM AUTHOR]

In this study, single-wall carbon nanotubes (SWCNTs) decorated by platinum-group transition metals (Pt, Pd, Rh, or Ru) were introduced as promising nanosensors for the detection of toluene, an important biomarker in the exhaled breath of the lung cancer patients. First-principle calculations based on density functional theory (DFT) was employed to scrutinize the impact of an individual toluene gas molecule on the structural, electronic, and magnetic properties of pristine and metal decorated SWCNTs. It was discovered that toluene is physisorbed on the pristine SWCNT through the interaction of the π orbitals of the carbon atoms in the toluene and the nanotube. Decoration of the SWCNT with metal atoms enhanced the adsorption energies significantly by means of strong overlapping between d orbital of the metal atoms and p orbital of C atoms in the benzene ring of toluene. Investigations showed that toluene is strongly chemisorbed on Rh- and Ru-SWCNT systems via strong covalent bonds with the superior response (−96.98% and −99.98%, respectively), and moderately chemisorbed on Pt-SWCNTs (−27.3%) and Pd-SWCNTs (61.60%). Our findings propose metal decorated SWCNT molecular sensors are attractive candidates for the detection of toluene and other lung cancer biomarkers in the exhaled breath of the lung cancer patients. [ABSTRACT FROM AUTHOR]

We focus on a Hamiltonian system with a continuous symmetry, and dynamics that takes place on a presymplectic manifold. We explain how the symmetry can become spontaneously broken by a time crystal, that we define as the minimum of the available mechanical free energy that is simultaneously a time dependent solution of Hamilton's equation. The mathematical description of such a timecrystalline spontaneous symmetry breaking builds on concepts of equivariant Morse theory in the space of Hamiltonian flows. As an example we analyze a general family of timecrystalline Hamiltonians that is designed to model polygonal, piecewise linear closed strings. The vertices correspond to the locations of pointlike interaction centers; the string is akin a chain of atoms, that are joined together by covalent bonds, modeled by the links of the string. We argue that the timecrystalline character of the string can be affected by its topology. For this we show that a knotty string is usually more timecrystalline than a string with no self-entanglement. We also reveal a relation between phase space topology and the occurrence of timecrystalline dynamics. For this we show that in the case of three point particles, the presence of a time crystal can relate to a Dirac monopole that resides in the phase space. Our results propose that physical examples of Hamiltonian time crystals can be realized in terms of closed, knotted molecular rings. [ABSTRACT FROM AUTHOR]

We review the binding and energy level alignment of π-conjugated systems on metals, a field which during the last two decades has seen tremendous progress both in terms of experimental characterization as well as in the depth of theoretical understanding. Precise measurements of vertical adsorption distances and the electronic structure together with ab initio calculations have shown that most of the molecular systems have to be considered as intermediate cases between weak physisorption and strong chemisorption. In this regime, the subtle interplay of different effects such as covalent bonding, charge transfer, electrostatic and van der Waals interactions yields a complex situation with different adsorption mechanisms. In order to establish a better understanding of the binding and the electronic level alignment of π-conjugated molecules on metals, we provide an up-to-date overview of the literature, explain the fundamental concepts as well as the experimental techniques and discuss typical case studies. Thereby, we relate the geometric with the electronic structure in a consistent picture and cover the entire range from weak to strong coupling. [ABSTRACT FROM AUTHOR]

Based on first-principles simulations, we revisit the crystal structures, electronic structures, and structural stability of the layered transition metal dichalcogenides (TMDCs) NbS2, and shed more light on the crucial roles of the van der Waals (vdW) interactions. Theoretically calculated results imply that the vdW corrections are important to reproduce the layered crystal structure, which is significant to correctly describe the electronic structure of NbS2. More interestingly, under hydrostatic pressure or tensile strain in ab plane, an isostructural phase transition from two-dimensional layered structure to three-dimensional bulk in the I4/mmm phase has been uncovered. The abnormal structural transition is closely related to the electronic structure instability and interlayer bonding effects. The interlayer Nb–S distances collapse and the interlayer vdW interactions disappear, concomitant with new covalent bond emerging and increasing coordination number. Present work highlights the significance of the vdW interactions, and provides new insights on the unconventional structural transitions in NbS2, which will attract wide audience working in the hectic field of TMDCs. [ABSTRACT FROM AUTHOR]

The formation of mono-atomic tantalum (Ta) metallic glass (MG) through ultrafast liquid cooling is investigated by ab-initio molecular dynamics (MD) simulations. It is found that there exists nearly golden ratio order (NGRO) between the nearest and second nearest atoms in Ta MG, which has been indirectly confirmed by Khmich et al. and Liang et al.. The NGRO is another universal structural feature in metallic glass besides the local five-fold symmetry (LFFS). Further analyzing of electronic structure shows that the obvious orientation of covalent bond could be attributed to the NGRO in amorphous Ta at 300 K. [ABSTRACT FROM AUTHOR]

Li+/Ni2+ disorder as an intrinsic structure defect in Ni-based layered oxides cathodes for lithium-ion batteries plays a crucial role on the overall electrochemical performances. However, the nature of Li+/Ni2+ disorder on the structure and property is still poorly understood. Herein, we design and synthesize layered LiNi1/3Co1/3Mn1/3O2 cathode materials with a different Li+/Ni2+ mixing degree, and focus on unveiling the influence mechanism of Li+/Ni2+ disorder on the surface/bulk structural evolution and the charge compensation mechanism by neutron, synchrotron radiation and electrochemical impedance techniques. High Li+/Ni2+ disorder increases the side reactions between electrolyte and electrode surface and aggravates the variation of local environment ofMn cations with (de)lithiating, which is largely responsible for the degradation of the initial capacity, rate capability and cycling performance. Interestingly, Li+/Ni2+ disorder can also relieve the electrostatic interaction between the cationic and anionic ions by enlarging the LiO6 octahedron and TMO6 octahedron, and locks the surrounding oxygen slabs by forming strong covalent bonds between antisite Ni and coordinated O ions, which alleviates the variations of the lattice parameters during charging/discharging. This study presents some new insights into designing high performance layered oxide cathodes through regulating Li+/Ni2+ disorder. [ABSTRACT FROM AUTHOR]

The study of superhard materials plays a critical role in modern industrial applications due to their widespread applications as cutting tools, abrasives, exploitation drills, and coatings. The search for new superhard materials with superior performance remains a hot topic and is mainly considered as two classes of materials: (i) the light-element compounds in the B–C–N–O(–Si) system with strong and short covalent bonds, and (ii) the transition-element light-element compounds with strong covalent bonds frameworks and high valence electron density. In this paper, we review the recent achievements in the prediction of superhard materials mostly using the advanced CALYPSO methodology. A number of novel, superhard crystals of light-element compounds and transition-metal borides, carbides, and nitrides have been theoretically identified and some of them account well for the experimentally mysterious phases. To design superhard materials via CALYPSO methodology is independent of any known structural and experimental data, resulting in many remarkable structures accelerating the development of new superhard materials. [ABSTRACT FROM AUTHOR]

One of the prevailing approaches to tune properties of materials is lattice doping with metal cations. Aluminum is a common choice, and numerous studies have demonstrated the ability of Al3+ doping to stabilize different positive electrode materials, such as Li[Ni-Co-Mn]O2 (NCMs). Currently, an atomic level understanding of the stabilizing effect of Al doping in NCMs is limited. In this work, we investigate the effect of Al doping on Ni-rich-NCM-523 (LiNi0.5Co0.2Mn0.3O2). Our results suggest that Al stabilizes the structure of the cathode material via strong Al-O iono-covalent bonding due to a significant Al(s)-O(p) overlap, as well as significant charge transfer capabilities of Al. The calculated formation energies suggest that Al doping results in stabilization of partially lithiated states of NCM-523. On the other hand, calculated voltages indicate only a minor change in the voltage profiles as a function of the state-of-charge due to Al doping, and a modest increase in the Li diffusion barrier was observed. We note that high doping concentrations might mitigate the Li diffusion rates. [ABSTRACT FROM AUTHOR]

Nanoscale graphenes were used as cathode catalyst supports in proton exchange membrane fuel cells (PEMFCs). Surface-initiated polymerization that covalently bonds polybenzimidazole (PBI) polymer on the surface of graphene supports enables the uniform distribution of the Pt nanoparticles, as well as allows the sealing of the unterminated carbon bonds usually present on the edge of graphene from the chemical reduction of graphene oxide. The nanographene effectively shortens the length of channels and pores for O2 diffusion/water dissipation and significantly increases the primary pore volume. Further addition of p-phenyl sulfonic functional graphitic carbon particles as spacers, increases the specific volume of the secondary pores and greatly improves O2 mass transport within the catalyst layers. The developed composite cathode catalyst of Pt/PBI-nanographene (50 wt%) + SO3H-graphitic carbon black demonstrates a higher beginning of life (BOL) PEMFC performance as compared to both Pt/PBI-nanographene (50 wt%) and Pt/PBI-graphene (50 wt%) + SO3H-graphitic carbon black (GCB). Accelerated stress tests show excellent support durability compared to that of traditional Pt/Vulcan XC72 catalysts, when subjected to 10,000 cycles from 1.0 V to 1.5 V. This study suggests the promise of using PBI-nanographene + SO3H-GCB hybrid supports in fuel cells to achieve the 2020 DOE targets for transportation applications. [ABSTRACT FROM AUTHOR]

Simple and label-free electrochemical sensors for the detection of DNA hybridization were developed based on charge perturbation of poly(thionine)-modified glassy carbon and gold electrodes (PTH/GCE and PTH/Au). Probe DNA (pDNA) was immobilized on PTH films via covalent bonds between the amine (-NH2) group of the PTH and the phosphate (PO43-) group at the 5' end of the pDNA. The immobilized single-strand pDNA decreased the oxidation current of [Fe(CN)6]4- as a result of electrostatic repulsion by the negatively charged PO43- backbone of the pDNA. The current was further decreased subsequent to duplex formation by the hybridization of target complementary DNA (cDNA) due to increased electrostatic repulsion. Both sensors demonstrated excellent selectivity, stability, and the sensitivity of 1.27 and 58.6 µA⋅cm-2⋅pM-1 with detection limits of 0.47 and 0.20 pM, respectively, for cDNA hybridization. [ABSTRACT FROM AUTHOR]

Friction behaviour of an ultrananocrystalline diamond film deposited by the microwave plasma-enhanced chemical vapour deposition technique is studied in a controlled humid atmosphere. The value of friction coefficient consistently decreases while increasing the humidity level during the tribology test. This value is 0.13 under 10% relative humidity conditions, which is significantly decreased to 0.004 under 80% relative humidity conditions. Such a reduction in friction coefficient is ascribed to passivation of dangling covalent bonds of carbon atoms, which occurs due to the formation of chemical species of hydroxyl and carboxylic groups such as C-COO, CH3COH and CH2-O bonding states. [ABSTRACT FROM AUTHOR]

In this article, a novel hybrid fabrication technology is presented that uses both a flexible polymer (polydimethylsiloxane--PDMS) and a rigid polymer (SU-8). A covalent bond between the flexible and rigid polymer layers is achieved using an oxygen plasma treatment during a layer-by-layer direct spin-on process. Precise alignment of the features in each layer and a highly repeatable method are achieved by this new process. As a proof-of-concept, we successfully fabricated PDMS-based flexible microfluidic devices with SU-8-based rigid world-to-chip/chip-to-world interconnects. The bond strength between the PDMS and SU-8 layers is measured by three methods: (1) Instron® microtester to pull apart the layers; (2) voice coil actuator to test the bond between interconnects and the substrate; and (3) microfluidic pressurization test to evaluate the bond strength along the channels. The bond strength between the flexible PDMS layer and the rigid SU-8 features is very strong; the bond between these two polymers does not fail during these evaluations although the integrity of the PDMS layer itself fails during the microtester evaluation. Additionally, the layer-by-layer direct spin-on process resulted in a repeatable process and precise alignment of the features in each layer, which are necessary in order to achieve consistent performance from the fabricated devices. The rigid SU-8 interconnects fabricated onto a flexible PDMS device serve as a world-to-chip/chip-to-world interconnects for the direct connection with Tygon®R tubing. Three different designs of hybrid (PDMS and SU-8 based) microfluidic devices are designed, fabricated and tested. Each variation differed in the microchannel design in order to demonstrate the versatility of the process to make devices on multiple scales and patterns. These hybrid microfluidic devices are capable of functioning without leakage up to pressures of 85.85 ± 3.56 kPa. Although microfluidic channels with interconnects are shown as a proof-of-concept, the fabrication process demonstrated herein could be utilized to develop a number of more sophisticated microfluidic and biomedical devices. [ABSTRACT FROM AUTHOR]

The mechanism of contact electrification between metals was studied using the first-principles method, taking the Ag--Fe contact as an example. Charge population, charge density difference, the orbitals and densities of states (DOS) were calculated to study the electronic properties of the contacting interfacial atoms. Based on the calculation, the amount of contact charge was obtained. The investigation revealed that the electrons near Fermi levels with higher energies transfer between the outermost orbitals (s orbitals for Ag and d orbitals for Fe). Meanwhile, polarized covalent bonds form between the d electrons in the deep energy states. These two effects together lead to an increase of charge magnitude at the interface. Also, the electrons responsible for electrification can be determined by their energies and orbitals. [ABSTRACT FROM AUTHOR]

The structural, elastic, and electronic properties of NiAl alloyed with rare earth elements Pr, Pm, Sm, and Eu are investigated by using density functional theory (DFT). The study suggests that Pr, Pm, Sm, and Eu all tend to be substituted for an Al site. Ni8Al7Pm possesses the largest ductility. Only the hardness and ductility of Ni8Al7Eu are enhanced simultaneously. The covalency strength of the Ni-Al bond in Ni8Al7Pm is higher than that in Ni8Al7Eu. The covalency strength of an Al-Al bond and that of a Ni-Ni bond in Ni8Al7Eu are higher than that in Ni8Al7Pm. The Ni-Pm bond and the Ni-Eu bond are covalent, and the covalency strength of the Ni-Pm bond is greater. The Al-Pm bond and the Al-Eu bond show great covalency strength and ionicity, respectively. [ABSTRACT FROM AUTHOR]

In order to investigate the influence of covalent bonding within the garnet framework on the conductivity of Li+ in the interstitial space, the Li+ conductivities in the family of Sn-based compounds Li6La3SnMO12 (M = Sb, Nb, Ta) have been obtained and are compared with those of Li6La3ZrMO12. Refinement of the neutron diffraction pattern of Li6La3SnNbO12 shows that the interstitial tetrahedral sites (24d) are about half-occupied and most of the Li in the interstitial bridging octahedral sites are displaced from the center position (48g). The Sb-based compound has the largest lattice parameter while the Ta-based compound has the highest Li+-ion conductivity of 0.42 x 10-4 S cm-1. [ABSTRACT FROM AUTHOR]

The electronic properties of 3C-SiC doped with different contents of Ni are investigated by using first-principles calculations. It is observed that the non-filled impurity energy levels in the band-gap region increase with increasing Ni content, which subsequently results in an enhancement of electrical conductivity of 3C-SiC. This enhancement in conductivity is verified by the conductivity spectrum in which new peaks appear in the middleinfrared region, visible region, and middle-ultraviolet region. It is further observed that the width and intensity of these newly appeared peaks increase with the increase of Ni content. The electronic density of states exhibits the peaks crossing the Fermi level, which favors the electronic transitions and proves Ni-doped 3C-SiC to be a half-metallic semiconductor. Through the analysis of electron density difference and Mulliken overlap population, it is found that the covalent bonds are formed between Ni and near-by C atoms. These features confirm that the Ni-doped 3C-SiC semiconductor is a promising material for device applications in modern day electronics. [ABSTRACT FROM AUTHOR]

The metallic carbides exhibit many novel prototypes of crystalline structure. Among these compounds Th2NiC2 was reported in 1991 as a new carbide which crystallizes in the U2IrC2 prototype structure. In this work we report a reinvestigation of the synthesis of this compound. We find that Th2NiC2 is a new superconductor. Our results suggest that this phase is stable only at high temperatures in the system Th-Ni-C. The substitution of Th by Sc stabilizes the phase and improves the superconducting properties. The highest superconducting critical temperature occurs at 11.2 K with nominal composition Th1.8C0.2NiC2 The electronic coefficient determined by specific heat measurements is close to zero. This unusual result can be explained by covalent bonding in the compound. [ABSTRACT FROM AUTHOR]

'Covalent self-assembly', i.e. the on-surface synthesis of covalent organic aggregates and networks, has received considerable attention. This review covers recent scanning tunnelling microscopy (STM) based studies on intermolecular reactions carried out on solid substrates that resulted in surface-confined covalently interlinked organic nanostructures. Experiments showed that their defect density crucially depends on the targeted dimensionality: while zero-dimensional aggregates and one-dimensional chains and ribbons can be synthesized on surfaces with utmost structural perfection, i.e. without any topological defects, realization of long-range ordered two-dimensional (2D) covalently interlinked organic networks has revealed itself as a paramount challenge for on-surface chemists. Different types of reactions, foremost condensation and addition reactions have been proven suitable as polymerization reactions for 2D cross-linked covalent networks. Yet, the emergence of topological defects during the polymerization is difficult to avoid. However, the combined experience and creativity of chemists and surface scientists has yielded encouraging first results which may open up ways for realization of extended, long-range ordered 2D polymers. This review summarizes and compares different approaches, i.e. reaction types, monomers, environments and conditions, for the on-surface synthesis of covalent organic nanostructures. The focus on STM as an analytical tool appears justified, since its unique capabilities render the STM an ideal instrument to study and even control covalent coupling reactions of organic molecules on surfaces. [ABSTRACT FROM AUTHOR]

New stable stoichiometries in K–Ga systems are firstly investigated up to 100 GPa by the unbiased structure searching techniques. Six novel compositions as K4Ga, K3Ga, K2Ga, KGa, KGa2 and KGa4 are found to be thermodynamically stable under pressure. Most of the predicted stable phases exhibit metallic character, while theKGa phase behaves as a semiconductor with a bandgap ∼1.62 eV. Notably, the gallium atoms exhibit different interesting morphologies; e.g., Ga2 units, zigzag chains, six rings and cage. We further investigate the bonding nature of K–Ga systems with help of electron localization function and Bader charge analyses. Strong covalent bonding characteristics are found between the Ga and Ga atoms, and ionic bonding patterns are observed between the K and Ga atoms. Meanwhile, we notice charge transferring from the K atom to the Ga atom in the K–Ga systems. The present results can be helpful for understanding the diverse structures and properties of K–Ga binary compounds at high pressures. [ABSTRACT FROM AUTHOR]

The formation of a self-limited metallic bilayer is reported during the growth of GaN by plasma-assisted molecular beam epitaxy on graphene on (0001) SiC. Depending on growth conditions, this layer may consist of either Ga or In, which gets intercalated between graphene and the SiC surface. Diffusion of metal atoms is eased by steps at SiC surface and N plasma induced defects in the graphene layer. Energetically favorable wetting of the (0001) SiC surface by Ga or In is tentatively assigned to the breaking of covalent bonds between (0001) SiC surface and carbon buffer layer. As a consequence, graphene doping and local strain/doping fluctuations decrease. Furthermore, the presence of a metallic layer below GaN opens the way to the development of devices with a spontaneously formed metallic electrode on their back side. [ABSTRACT FROM AUTHOR]

First-principles evolutionary calculation was performed to search for all probable stable Ga–Te compounds at extreme pressure. In addition to the well-known structures of P63/mmc and Fm-3m GaTe and I4/m Ga2Te5, several new structures were uncovered at high pressure, namely, orthorhombic I4/mmm GaTe2 and monoclinic C2/m GaTe3, and all the Ga–Te structures stabilize up to a maximum pressure of 80 GPa. The calculation of the electronic energy band indicated that the high-pressure phases of the Ga–Te system are metallic, whereas the low-pressure phases are semiconductors. The electronic localization functions (ELFs) of the Ga–Te system were also calculated to explore the bond characteristics. The results showed that a covalent bond is formed at low pressure, however, this bond disappears at high pressure, and an ionic bond is formed at extreme pressure. [ABSTRACT FROM AUTHOR]

Several unidentified infrared emission bands (UIBs) have been assigned to neutral C60 molecules present in circumstellar and interstellar environments. However, due to the similarity of the infrared (IR) spectra of C60 in the solid state and in the gas phase, as of yet there is no consensus on the aggregation state of C60. In this article, we show that even strong covalent chemical bonding might have very little influence on the IR spectrum of C60, and that therefore such chemically bonded C60 could be the carrier of the same UIBs. It would best explain observations like the missing emission from C60 ions and a large variation of relative band intensities between different sources. We demonstrate that such a chemically bonded C60 can be produced by the co-condensation of C atoms together with C60 molecules, which leads to the formation of a three-dimensional C60 polymer film. Such polymerized C60 molecules cannot easily desorb, while their spectral properties in the visible and IR spectral ranges are almost undisturbed by polymerization. [ABSTRACT FROM AUTHOR]

The fullerene C60, one of the largest molecules identified in the interstellar medium (ISM), has been proposed to form top-down through the photochemical processing of large (more than 60 C atoms) polycyclic aromatic hydrocarbon (PAH) molecules. In this article, we focus on the opposite process, investigating the possibility that fullerenes form from small PAHs, in which bowl-forming plays a central role. We combine laboratory experiments and quantum chemical calculations to study the formation of larger PAHs from charged fluorene clusters. The experiments show that with visible laser irradiation, the fluorene dimer cation—[C13H9−C13H9]+—and the fluorene trimer cation—[C13H9−C13H8−C13H9]+—undergo photodehydrogenation and photoisomerization, resulting in bowl-structured aromatic cluster ions, C26H12+ and C39H20+, respectively. To study the details of this chemical process, we employ quantum chemistry that allows us to determine the structures of the newly formed cluster ions, to calculate the dissociation energies for hydrogen loss, and to derive the underlying reaction pathways. These results demonstrate that smaller PAH clusters (with less than 60 C atoms) can convert to larger bowled geometries that might act as building blocks for fullerenes, because the bowl-forming mechanism greatly facilitates the conversion from dehydrogenated PAHs to cages. Moreover, the bowl-forming induces a permanent dipole moment that—in principle—allows one to search for such species using radio astronomy. [ABSTRACT FROM AUTHOR]

The use of sulfur as a cathode material for lithium−sulfur (Li−S) batteries has attracted significant attention due to its high theoretical specific capacity (1675 mA h g−1); however, practicality is hindered by a number of obstacles, including the shuttling effect of polysulfides and the low electrical conductivity of sulfur. Herein, ball milling sulfur with unzipped multiwalled carbon nanotubes (UMWNTs) was found to covalently immobilize sulfur nanoparticles to the UMWNTs and resulted in composites (designated as S@UMWNTs) with high electrical conductivity. The unzipping degree of MWNTs was first controlled to optimize the immobilization of sulfur nanoparticles to UMWNTs and the electrochemical performance of the resulting Li−S batteries. The presence of C−S covalent bonds between the UMWNTs and sulfur nanoparticles was verified using x-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy, and the formation of C−S bonds was ascribed to the reactions between the mechanically-induced sulfur radicals and the functional groups of UMWNTs. As a result, when used as a cathode material for Li−S batteries, the S@UMWNTs exhibited excellent electrochemical performance, including a good long-term cycling stability and low capacity decay (e.g., ca. 0.09% per cycle over 500 charge/discharge cycles at 1 C) due to the suppression of the shuttling effect by the C−S covalent bonds. [ABSTRACT FROM AUTHOR]

Two-dimensional (2D) graphene-like layered semiconductors provide a new platform for materials research because of their unique mechanical, electronic and optical attributes. Their in-plane covalent bonding and dangling-bond-free surface allow them to assemble various van der Waals heterostructures (vdWHSs) with sharply atomic interfaces that are not limited by lattice matching and material compatibility. Interlayer coupling, as a ubiquitous phenomenon residing among 2D materials (2DMs) systems, controls a thin layer exfoliation process and the assembly of vdWHSs and behaves with a unique degree of freedom for engineering the properties of 2DMs. Interlayer coupling provides an opportunity to observe new physics and provides a novel strategy to modulate the electronic and optoelectronic properties of materials for practical device applications. We herein review recent progress in the exploration of interlayer coupling in 2D semiconducting vdWHSs for potential applications in electronics and optoelectronics. [ABSTRACT FROM AUTHOR]

The ability of gold nanoparticles to bind different substances has resulted in the high interest of researchers determining their usage as a promising carrier of various biological substances including nucleic acids (NAs) for therapeutic applications. Most publications report covalent binding (conjugation) of an NA to spherical AuNPs via the Au–S bond. In this work, we obtained non-covalent associates of different ssDNA, ssRNA and siRNAs with spherical gold nanoparticles (AuNPs) and examined their physico-chemical properties and stability in media mimicking intracellular space (bacterial ‘cytosol’) and cell culture media (10% FBS in DMEM). The ‘cytosol’ was obtained from E. coli and possessed nuclease activity. For the first time, we used the phosphoryl guanidine (dimethylimidazolidin-2-imine, Dmi) group for modification of 3′-ends to enhance the stability of ssRNAs and siRNAs against nuclease destruction. Trying to evaluate the material balance, we analyzed the whole nucleotide species obtained after incubation of NA-AuNPs associates in ‘cytosol’ and FBS and evaluated the degree of NAs destruction, a share of full-size NAs remained on the surface of the AuNPs and in the solution. Native ss- and siRNAs, both free and in composition of non-covalent associates with AuNPs, were less resistant to degrading factors than ssDNA. The introduction of two Dmi-groups into the ssDNA increased its stability in ‘cytosol’ three times within 2.5 h. Dmi-modified siRNAs in non-covalent associates with AuNPs were two times more stable than unmodified siRNA within 4 h. We showed that non-covalent siRNA-AuNPs associates serve as a kind of storage for full-size NAs and thereby prolong their presence in nuclease-active media. Our study showed that non-covalent binding of siRNAs with a surface of AuNPs provides desorption of both strands, which is necessary for siRNA functioning in living cells, and could be considered as an important way to construct siRNA and ssDNA delivery systems based on AuNPs. [ABSTRACT FROM AUTHOR]

All-carbon heterostructures consisting of carbon allotropes have attracted considerable attention because of their intriguing properties. However, understanding is still lacking of the interactions at the interface, as well as the connection between such interactions and their performance. Herein, we systematically explore the interfacial interaction in all-carbon penta-graphene (PG)/C20 (C60) heterostructures, and its effect on structural and electronic properties. Based on first-principles calculations, we report that the all-carbon PG/C20 (C60) heterostructures show two types of interfacial interactions: dispersive and covalent. The PG/C20 van der Waals (vdWs) heterostructure is less stable than its covalent one. By contrast, the PG/C60 vdWs heterostructure is the more stable. In the covalent heterostructures, either two or four C–C bonds can be formed between PG and C20, whereas only two can be formed between PG and C60. The near-gap electronic structures depend on the interfacial interactions, and the levels near the Fermi level are mainly composed of C20 (C60) states, giving rise to a small band gap of heterostructure, making them promising for visible light absorption. All the differences in these PG/C20 (C60) heterostructures can be well understood in terms of the different topology of fullerene. This finding indicates that all-carbon PG/fullerene heterostructures are promising candidates for photocatalysis, photodetectors, and solar energy harvesting and conversion. [ABSTRACT FROM AUTHOR]

The structural, electronic and magnetic properties of Cr, Mn, Fe, Co and Ni-doped bilayer WSe2 are predicted by using first principles calculations. The doped transition-metal (TM) atoms show a covalent-binding with the nearest Se atoms. The calculated electronic structures reveal that the TM Cr, Mn, Fe and Co-doped bilayer WSe2 exhibits a half-metallic character with a 100% spin polarization at the Fermi level, and the reason is ascribed to the strong hybridization peak between the transition metals and the parent W and Se atoms. The Ni-doped bilayer WSe2 is still a semiconductor with nonmagnetism. The Fe-doped system has a robust stability of half-metallicity because there are three connected states peak spanning the Fermi level. The doping of Cr, Mn, Fe and Co atoms leads to a prominent total magnetism (0.93–3.65 moment per unit cell), and an induced ∼0.3 moment in parent W atoms is found in addition to the main contribution of TM atomic magnetism (0.71–3.33 moment per atom). The predicted Cr, Mn, Fe and Co-doped bilayer WSe2 should be the candidate materials for spintronic devices due to their magnetic and half-metallic nature. [ABSTRACT FROM AUTHOR]

The presence of carbon atoms in silicon carbide and diamond makes these materials ideal candidates for direct fast neutron detectors. Furthermore the low atomic number, strong covalent bonds, high displacement energies, wide bandgap and low intrinsic carrier concentrations make these semiconductor detectors potentially suitable for applications where rugged, high-temperature, low-gamma-sensitivity detectors are required, such as active interrogation, electronic personal neutron dosimetry and harsh environment detectors. A thorough direct performance comparison of the detection capabilities of semi-insulating silicon carbide (SiC–SI), single crystal diamond (D–SC), polycrystalline diamond (D–PC) and a self-biased epitaxial silicon carbide (SiC–EP) detector has been conducted and benchmarked against a commercial silicon PIN (Si–PIN) diode, in a wide range of alpha (Am-241), beta (Sr/Y-90), ionizing photon (65 keV to 1332 keV) and neutron radiation fields (including 1.2 MeV to 16.5 MeV mono-energetic neutrons, as well as neutrons from AmBe and Cf-252 sources). All detectors were shown to be able to directly detect and distinguish both the different radiation types and energies by using a simple energy threshold discrimination method. The SiC devices demonstrated the best neutron energy discrimination ratio (( MeV)/( MeV)  ≈5), whereas a superior neutron/photon cross-sensitivity ratio was observed in the D–PC detector ((AmBe)/(Co-60)  ≈16). Further work also demonstrated that the cross-sensitivity ratios can be improved through use of a simple proton-recoil conversion layer. Stability issues were also observed in the D–SC, D–PC and SiC–SI detectors while under irradiation, namely a change of energy peak position and/or count rate with time (often referred to as the polarization effect). This phenomenon within the detectors was non-debilitating over the time period tested (5 h) and, as such, stable operation was possible. Furthermore, the D–SC, self-biased SiC–EP and semi-insulating SiC detectors were shown to operate over the temperature range °C to °C. [ABSTRACT FROM AUTHOR]

In bond-order potentials (BOPs) for transition metals only the bonding mediated by the d electrons is included explicitly and the covalent part of the cohesive energy is evaluated using Slater–Koster dd bond integrals. However, the effect of s electrons with orbitals centered on atoms neighboring the corresponding dd bond is not necessarily negligible. As shown in Nguyen-Manh et al (2000 Phys. Rev. Lett. 85 4136) this can be taken into account via screening of the dd bond integrals. In a recent paper (Lin et al 2014 Model. Simul. Mater. Sci. Eng. 22 034002) the dd bond integrals were determined using a projection scheme utilizing atomic orbitals that give the best representation of the electronic wave functions in the calculations based on the density functional theory (DFT) (Madsen et al 2011 Phys. Rev. B 83 4119) and it was inferred that in this case the effect of s electrons was already included. In this paper we analyze this hypothesis by comparing studies employing BOPs with both unscreened and screened dd bond integrals. In all cases results are compared with calculations based on DFT and/or experiments. Studies of structures alternate to the bcc lattice, transformation paths that connect the bcc structure with fcc, simple cubic (sc), body centered tetragonal (bct) and hcp structures via continuously distorted configurations and calculations of γ-surfaces were all found to be insensitive to the screening of bond integrals. On the other hand, when the bond integrals are screened, formation energies of vacancies are improved and calculated phonon dispersion spectra reproduce the experimentally observed ones much better. Most importantly, dislocation core structure and dislocation glide are significantly different without and with screening of dd bond integrals. The latter lead to a much better agreement with available experiments. These findings suggest that the effect of s electrons on dd bonds, emulated by the screening of corresponding bond integrals, is the least significant when the lattice is distorted away from the ideal bcc structure homogeneously even if such distortion is large. On the other hand, when the distortion is local and inhomogeneous the impact of screening of the dd bond integrals is significant. In the studies presented in this paper such local inhomogeneities occur when phonons propagate through the lattice, at point defects and in the cores of dislocations. [ABSTRACT FROM AUTHOR]

The increasing power density and the decreasing dimensions of transistors present severe thermal challenges to the design of modern microprocessors. Furthermore, new technologies such as three-dimensional chip-stack architectures require novel cooling solutions for their thermal management. Here, we demonstrate, through transient heat-dissipation simulations, that a covalently bonded graphene-carbon nanotube (G-CNT) hybrid immersed in water is a promising solution for the ultrafast cooling of such high-temperature and high heat-flux surfaces. The G-CNT hybrid offers a unique platform to integrate the superior axial heat transfer capability of individual CNTs via their parallel arrangement. The immersion of the G-CNT in water enables an additional heat dissipation path via the solid–liquid interaction, allowing for the sustainable cooling of the hot surface under a constant power input of up to 10 000 W cm−2. [ABSTRACT FROM AUTHOR]

It is still a huge challenge to find a new strategy for rationally designing covalent drugs because most of them are discovered by serendipity. Considering that the effect of covalent drugs is closely associated with the kinetics of the reaction between drug molecule and its target protein, here we first demonstrate an example of the kinetic effect of pi-stacking of drug molecules on covalent antimicrobial drug design. When PEGylated 7-aminocephalosporanic acid (PEG-ACA) is used as a substrate drug, pi-stacking of the ACA group via the self-assembly of PEG-ACA on the surface of gold nanoparticles (i.e. Au@ACA) exhibits antibacterial activity against E. coli fourfold higher than a PEG-ACA monomer does. The reason can be reasonably attributed to the kinetic rate enhancement for the covalent reaction between Au@ACA and penicillin binding proteins. We believe that the self-assembly of functional groups onto the surface of gold nanoparticles represents a new strategy for covalent drug design. [ABSTRACT FROM AUTHOR]

The EPR parameters of trivalent Er3+ ions doped in hexagonal GaN crystal have been studied by diagonalizing the 364×364 complete energy matrices. The results indicate that the resonance ground states may be derived from the Kramers doublet Γ6. The EPR g-factors may be ascribed to the stronger covalent bonding and nephelauxetic effects compared with other rare-earth doped complexes, as a result of the mismatch of ionic radii of the impurity Er3+ ion and the replaced Ga3+ ion apart from the intrinsic covalency of host GaN. Furthermore, the J–J mixing effects on the EPR parameters from the high-lying manifolds have been evaluated. It is found that the dominant J–J mixing contribution is from the manifold 2K15/2, which accounts for about 2.5%. The next important J–J contribution arises from the crystal–field mixture between the ground state 4I15/2 and the first excited state 4I13/2, and is usually less than 0.2%. The contributions from the rest states may be ignored. [ABSTRACT FROM AUTHOR]

The magnetisms of RCo5 (R = rare earth) intermetallics are systematically studied with the empirical electron theory of solids and molecules (EET). The theoretical moments and Curie temperatures agree well with experimental ones. The calculated results show strong correlations between the valence electronic structure and the magnetic properties in RCo5 intermetallic compounds. The moments of RCo5 intermetallics originate mainly from the 3d electrons of Co atoms and 4f electrons of rare earth, and the s electrons also affect the magnetic moments by the hybridization of d and s electrons. It is found that moment of Co atom at 2c site is higher than that at 3g site due to the fact that the bonding effect between R and Co is associated with an electron transformation from 3d electrons into covalence electrons. In the heavy rare-earth-based RCo5 intermetallics, the contribution to magnetic moment originates from the 3d and 4f electrons. The covalence electrons and lattice electrons also affect the Curie temperature, which is proportional to the average moment along the various bonds. [ABSTRACT FROM AUTHOR]

Natural cotton was dissolved in a room-temperature ionic liquid 1-ethyl-3-methyl acetate and wet-jet electrospun to obtain nanoscale cotton fibers with a substantially reduced diameter—and therefore an increased surface area—relative to natural cotton fibers. The resulting nano-cotton fibers were esterified with trityl-3-mercaptopropionic acid, which after selective de-tritylation afforded nano-cotton fibers containing reactive thiol functionality. Silver nanoparticles that were covalently attached to these sulfhydryl groups were assembled next. The microstructure of the resulting nanocomposite was characterized, and the antibacterial activity of the resulting nano-cotton Ag-nanoparticle composite was also studied. This nanocomposite showed significant activity against both Gram-negative and Gram-positive bacteria. [ABSTRACT FROM AUTHOR]

The bond-order potentials are derived from density functional theory by a systematic coarse graining of the electronic structure. Within their functional form the bond-order potentials comprise covalent bond formation, charge transfer and magnetism. We review the derivation of the bond-order potentials from density functional theory and discuss their application to the simulation of refractory transition metals. We show that the derived functional form of the bond-order potentials ensures the transferability of the potentials to atomic environments that have not been taken into account in the parameterization. [ABSTRACT FROM AUTHOR]

Bond-order potentials (BOPs) have been used successfully in simulations of a wide range of processes. A brief overview of bond-order potentials is provided which focuses on the reactive empirical bond-order (REBO) potential for hydrocarbons (Brenner et al 2002 J. Phys.: Condens. Matter14 783) and the large number of useful potentials it has spawned. Two specific extensions of the REBO potential that make use of its formalism are discussed. First, the 2B-SiCH potential (Schall and Harrison 2013 J. Phys. Chem. C 117 1323) makes the appropriate changes to the hydrocarbon REBO potential so that three atom types, Si, C, and H, can be modeled. Second, we recently added the electronegative element O, along with the associated charge terms, to the adaptive intermolecular REBO (AIREBO) potential (Stuart et al 2000 J. Chem. Phys. 112 6472). The resulting qAIREBO potential (Knippenberg et al 2012 J. Chem. Phys. 136 164701) makes use of the bond-order potential/split-charge (BOP/SQE) equilibration method (Mikulski et al 2009 J. Chem. Phys. 131 241105) and the Lagrangian approach to charge dynamics (Rick et al 1994 J. Chem. Phys. 101 6141). The integration of these two techniques allows for atomic charges to evolve with time during MD simulations: as a result, chemical reactions can be modeled in C-, O-, and H-containing systems. The usefulness of the 2B-SiCH potential for tribological investigations is demonstrated in molecular dynamics (MD) simulations of axisymmetric tips composed of Si and SiC placed in sliding contact with diamond(1 1 1) surfaces with varying amounts of hydrogen termination. The qAIREBO potential is used to investigate confinement of sub-monolayer coverages of water between nanostructured surfaces. [ABSTRACT FROM AUTHOR]