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Mechanical properties of layered silicates on the nanometer scale have been associated with large uncertainty. We attempt to clarify the linear elastic properties including tensile moduli, shear moduli, and potential failure mechanisms for the minerals pyrophyllite, montmorillonite, and mica in the order of increasing cation exchange capacity (CEC) under a broad range of stress using electronic structure calculations, semiempirical classical molecular dynamics simulation, and the comparison to available macroscopic experimental data. In-plane tensile moduli (xx and yy) are ∼160 GPa independent of CEC and stress, whereas perpendicular tensile moduli (zz) range from 5 to 60 GPa as a function of CEC at low stress (0.01 to 1 GPa) and approach in-plane values at high stress. In-plane shear moduli (xy) are ∼70 GPa independent of CEC and the shear strength increases from ∼1 to ∼3 GPa with increasing cation density. Shear moduli parallel to the layers (xz and yz) are between 2 and 20 GPa as a function of CEC, with a shear strength of 0.2 to 1 GPa beyond which the layers exhibit lateral shear flow. Tensile zz moduli, shear moduli, and shear strength in the xz and yz direction reach a local minimum at a cation density of 0.3 relative to mica. The simulation suggests sliding of the layers, in-plane kinks, and cation intrusion into the layers as potential failure mechanisms equal to amorphization on the macroscale. The anisotropy and stress-dependence of the mechanical properties is determined by the presence of rigid layers and flexible interlayer spaces of variable cation density. Current classical simulation models tend to overestimate in-plane moduli (xx, yy, xy) in a systematic way relative to electronic structure (DFT) and experimental results.

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In this work, to explain doping behavior of single-layer graphene upon HSSYWYAFNNKT (P1) and HSSAAAAFNNKT (P1-3A) adsorption in field-effect transistors (GFETs), we applied a combined computational approach, whereby peptide adsorption was modeled by molecular dynamics simulations, and the lowest energy configuration was confirmed by density functional theory calculations. On the basis of the resulting structures of the hybrid materials, electronic structure and transport calculations were investigated. We demonstrate that π-π stacking of the aromatic residues and proximate peptide backbone to the graphene surface in P1 have a role in the p-doping. These results are consistent with our experimental observation of the GFET's p-doping even after a 24-h annealing procedure. Upon substitution of three of the aromatic residues to Ala in (P1-3A), a considerable decrease from p-doping is observed experimentally, demonstrating n-doping as compared to the nonadsorbed device, yet not explained based on the atomistic MD simulation structures. To gain a qualitative understanding of P1-3A's adsorption over a longer simulation time, which may differ from aromatic amino acid residues' swift anchoring on the surface, we analyzed equilibrated coarse-grain simulations performed for 500 ns. Desorption of the Ala residues from the surface was shown computationally, which could in turn affect charge transfer, yet a full explanation of the mechanism of n-doping will require elucidation of differences between various aromatic residues as dependent on peptide composition, and inclusion of effects of the substrate and environment, to be considered in future work.

In this letter, we report on the evaluation of diphenylalanine (FF), dityrosine (YY), and phenylalanine-tryptophan (FW) self-assembled peptide nanotube structures for electronics and photonics applications. Realistic bulk peptide nanotube material models were used in density functional theory calculations to mimic the well-ordered tubular nanostructures. Importantly, validated functionals were applied, specifically by using a London dispersion correction to model intertube interactions and a range-separated hybrid functional for accurate bandgap calculations. Bandgaps were found consistent with available experimental data for FF, and also corroborate the higher conductance reported for FW in comparison to FF peptide nanotubes. Interestingly, the predicted bandgap for the YY tubular nanostructure was found to be slightly higher than that of FW, suggesting higher conductance as well. In addition, the band structure calculations along the high symmetry line of nanotube axis revealed a direct bandgap for FF. The results enhance our understanding of the electronic properties of these material systems and will pave the way into their application in devices.

Recently, several experiments demonstrated the stability of chain-like carbon nanowires bridged between graphene nanoribbons, paving the way for potential applications in nanodevices. On the basis of density functional tight-binding calculations, we demonstrated switching for chains terminated with a five-membered ring under an applied strain, serving as a model for morphological changes in realistic materials. Electron transport calculations showed an increase of up to 100% in the output current, achieved at a reverse bias voltage of -2 V and an applied strain of just 1.5%. Structural analysis suggested that the switching is driven by conformational changes, where in our case is triggered by the formation and annihilation of a five-membered ring at the interface of the chain-graphene edge. In addition, we showed that a five-membered ring can easily be formed at the interface under a source-drain bias or through a gate voltage. This mechanism can serve as an explanation of experimentally observed conductance for the materials.

We report a first-principles theoretical investigation on the electronic structure and electron transport of defective single-layer (SL) MoS2, as well as of corresponding structures adsorbed with benzyl viologen (BV), which was shown to provide improved performance of a field effect transistor. O2 adsorption was included to gain an understanding of the response upon air-exposure. Following analysis of the structure and stability of sulfur single vacancy and line defects in SL MoS2, we investigated the local transport at the adsorbed sites via a transport model that mimics a scanning tunneling spectroscopy experiment. Distinct current-voltage characteristics were indicated for adsorbed oxygen species at a sulfur vacancy. The electronic structures of defective MoS2 indicated the emergence of impurity states in the bandgap due to sulfur defects and oxygen adsorption. Electron transport calculations for the MoS2 surface with an extended defect in a device setting demonstrated that physisorption of BV enhances the output current, while facile chemisorption by O2 upon air-exposure causes degradation of electron transport.

In this paper, we explored computationally the feasibility of modulating the bandgap in a single-wall BN nanotube (BNNT) upon noncovalent adsorption of organic molecules, combined with the application of a transverse electric field. Effects of analytes' physisorption on the surface of BNNTs regarding structural and electronic properties were delineated. Relatively large binding energies were calculated, however, with minimal perturbation of the structural framework. Electronic structure calculations indicated that the bandgap of BNNTs can be modified by weak adsorption due to the presence of adsorbate states in the gap of the host system. Furthermore, we have shown that the application of a transverse electric field can tune the bandgap by shifting adsorbate states, consistent with calculated current-voltage characteristics.