No Arabic abstract
We present a study of resonant vibrational coupling between adsorbates and an elastic substrate at low macroscopic coverages. In the first part of the paper we consider the situation when adsorbates form aggregates with high local coverage. Based upon our previously published theory, we derive formulas describing the damping rate of adsorbate vibrations for two cases of such aggregation: (i) adsorbates attached to step edges and (ii) adsorbates forming two-dimensional islands. We have shown that damping is governed by local coverage. Particularly, for a wide range of resonant frequencies, the damping rate of adsorbates forming well separated islands is described by the damping rate formula for a periodic overlayer with the coverage equal to the local coverage in the island. The second part of the paper is devoted to facilitating the evaluation of damping rates for a disordered overlayer. The formula describing the damping rate involves the parameter $beta$ which is related to the local density of phonon states at the substrate surface and does not allow a closed-form representation. For substrates of isotropic and cubic symmetries, we have developed a good analytical approximation to this parameter. For a vast majority of cubic substrates the difference between the analytical approximation and numerical calculation does not exceed 4%.
We formulate the theory of the perturbation caused by an adsorbate upon the substrate lattice in terms of a local modification of the interatomic potential energy around the adsorption site, which leads to the relaxation of substrate atoms. We apply the approach to CO chemisorption on close-packed metal surfaces, and show that the adsorbate-adsorbate interaction and a variety of other properties can be well described by a simple model.
We conduct experiments on two-dimensional packings of colloidal thermosensitive hydrogel particles whose packing fraction can be tuned above the jamming transition by varying the temperature. By measuring displacement correlations between particles, we extract the vibrational properties of a corresponding shadow system with the same configuration and interactions, but for which the dynamics of the particles are undamped. The vibrational spectrum and the nature of the modes are very similar to those predicted for zero-temperature idealized sphere models and found in atomic and molecular glasses; there is a boson peak at low frequency that shifts to higher frequency as the system is compressed above the jamming transition.
We show clear experimental evidence of co-operative terahertz (THz) dynamics observed below 3 THz (~100 cm-1), for a low-symmetry Zr-based metal-organic framework (MOF) structure, termed MIL-140A [ZrO(O2C-C6H4-CO2)]. Utilizing a combination of high-resolution inelastic neutron scattering and synchrotron radiation far-infrared spectroscopy, we measured low-energy vibrations originating from the hindered rotations of organic linkers, whose energy barriers and detailed dynamics have been elucidated via ab initio density functional theory (DFT) calculations. For completeness, we obtained Raman spectra and characterized the alterations to the complex pore architecture caused by the THz rotations. We discovered an array of soft modes with trampoline-like motions, which could potentially be the source of anomalous mechanical phenomena, such as negative linear compressibility and negative thermal expansion. Our results also demonstrate coordinated shear dynamics (~2.5 THz), a mechanism which we have shown to destabilize MOF crystals, in the exact crystallographic direction of the minimum shear modulus (Gmin).
We show that the low-frequency regime of the density of states of structural glass formers is crucially sensitive to the stress-ensemble from which the configurations are sampled. Specifically, in two dimensions, an exactly isotropic ensemble with zero shear stress fluctuations, displays a $D(omega_{min}) sim omega^{5}_{min}$ regime, as opposed to the $omega^{4}_{min}$ regime observed under unstrained conditions. We also study an ensemble of strained amorphous solids near a plastic event. We show that the minimum eigenvalue distribution at a strain $gamma$ near the plastic event occurring at $gamma_{P}$, displays a collapse when scaled by $sqrt{gamma_P - gamma}$, and with the number of particles as $N^{-0.22}$. Notably, at low-frequencies, this scaled distribution displays a robust $D(omega_{min}) sim omega^{6}_{min}$ power-law regime, which survives in the large $N$ limit. Finally, we probe the universal properties of this ensemble through a characterization of the second and third eigenvalues of the Hessian matrix near a plastic event.
The structural and electronic properties of twisted bilayer graphene are investigated from first principles and tight binding approach as a function of the twist angle (ranging from the first magic angle $theta=1.08^circ$ to $theta=3.89^circ$, with the former corresponding to the largest unit cell, comprising 11164 carbon atoms). By properly taking into account the long-range van der Waals interaction, we provide the patterns for the atomic displacements (with respect to the ideal twisted bilayer). The out-of-plane relaxation shows an oscillating (buckling) behavior, very evident for the smallest angles, with the atoms around the AA stacking regions interested by the largest displacements. The out-of-plane displacements are accompanied by a significant in-plane relaxation, showing a vortex-like pattern, where the vorticity (intended as curl of the displacement field) is reverted when moving from the top to the bottom plane and viceversa. Overall, the atomic relaxation results in the shrinking of the AA stacking regions in favor of the more energetically favorable AB/BA stacking domains. The measured flat bands emerging at the first magic angle can be accurately described only if the atomic relaxations are taken into account. Quite importantly, the experimental gaps separating the flat band manifold from the higher and lower energy bands cannot be reproduced if only in-plane or only out-of-plane relaxations are considered. The stability of the relaxed bilayer at the first magic angle is estimated to be of the order of 0.5-0.9 meV per atom (or 7-10 K). Our calculations shed light on the importance of an accurate description of the vdW interaction and of the resulting atomic relaxation to envisage the electronic structure of this really peculiar kind of vdW bilayers.