Classical equilibrium molecular dynamics simulations have been performed to investigate dynamical properties of cage radial breathing modes and intra- and inter-cage hydrogen migration in both pure hydrogen and mixed hydrogen–tetrahydrofuran sII hydrates at 0.05 kbar and up to 250 K. For the mixed H2–THF system in which there is single H2 occupation of the small cage (labelled “1SC 1LC”), we find that no H2 migration occurs, and this is also the case for pure H2 hydrate with single small-cavity occupation and quadruple occupancy for large cages (dubbed “1SC 4LC”). However, for the more densely filled H2–THF and pure-H2 systems, in which there is double H2 occupation in the small cage (dubbed “2SC 1LC” and “2SC 4LC,” respectively), there is an onset of inter-cage H2 migration events from the small cages to neighbouring cavities at around 200 K, with an approximate Arrhenius temperature-dependence for the migration rate from 200 to 250 K. It was found that these “cage hopping” events are facilitated by temporary openings of pentagonal small-cage faces with the relaxation and reformation of key stabilising hydrogen bonds during and following passage. The cages remain essentially intact up to 250 K, save for transient hydrogen bond weakening and reformation during and after inter-cage hydrogen diffusion events in the 200–250 K range. The “breathing modes,” or underlying frequencies governing the variation in the cavities’ radii, exhibit a certain overlap with THF rattling motion in the case of large cavities, while there is some overlap of small cages’ radial breathing modes with lattice acoustic modes.
Motivated by the recently observed sublattice asymmetry of substitutional nitrogen impurities in CVD grown graphene, we show, in a mathematically transparent manner, that oscillations in the local density of states driven by the presence of substitutional impurities are responsible for breaking the sublattice symmetry. While these oscillations are normally averaged out in the case of randomly dispersed impurities, in graphene they have either the same, or very nearly the same, periodicity as the lattice. As a result, the total interaction energy of randomly distributed impurities embedded in the conduction-electron-filled medium does not vanish and is lowered when their configuration is sublattice-asymmetric. We also identify the presence of a critical concentration of nitrogen above which one should expect the sublattice asymmetry to disappear. This feature is not particular to nitrogen dopants, but should be present in other impurities. * jalawlor@tcd.ie
Abstract. The indirect exchange interaction is one of the key factors in determining the overall alignment of magnetic impurities embedded in metallic host materials. In this work we examine the range of this interaction in magnetically-doped graphene systems in the presence of armchair edges using a combination of analytical and numerical Green function (GF) approaches. We consider both a semi-infinite sheet of graphene with a single armchair edge, and also quasi-one-dimensional armchair edged graphene nanoribbons (GNRs). While we find signals of the bulk decay rate in semi-infinite graphene and signals of the expected one-dimensional decay rate in GNRs, we also find an unusually rapid decay for certain instances in both, which manifests itself whenever the impurities are located at sites which are a multiple of three atoms from the edge. This decay behavior emerges from both the analytic and numerical calculations, and the result for semi-infinite graphene can be interpreted as an intermediate case between ribbon and bulk systems.Variable range of the RKKY interaction in edged graphene 2
Classical equilibrium molecular dynamics (MD) simulations have been performed to investigate the dynamical and energetic properties in hydrogen and mixed hydrogen-tetrahydrofuran sII hydrates at 30 and 200K and 0.05 kbar, and also at intermediate temperatures, using SPC/E and TIP4P-2005 water models. The potential model is found to have a large impact on overall density, with the TIP4P-2005 systems being on average 1 % more dense than their SPC/E counterparts, due to the greater guest-host interaction energy. For the lightly-filled mixed H 2 -THF system, in which there is single H 2 occupation of the small cage (1s1l), we find that the largest contribution to the interaction energy of both types of guest is the van der Waals component with the surrounding water molecules in the constituent cavities. For the more densely-filled mixed H 2 -THF system, in which there is double H 2 occupation in the small cage (2s1l), we find that there is no dominant component (i.e., van der Waals or Coulombic) in the H 2 interaction energy with the rest of the system, but for the THF molecules, the dominant contribution is again the van der Waals interaction with the surrounding cage-water molecules; again, the Coulombic component increases in importance with increasing temperature. The lightly-filled pure H 2 hydrate (1s4l) system exhibits a similar pattern vis-à-vis the H 2 interaction energy as for the lightly-filled mixed H 2 -THF system, and for the more densely-filled pure H 2 system (2s4l), there is no dominant component of interaction energy, due to the multiple occupancy of the cavities. By consideration of Kubic harmonics, there is some evidence of preferential alignment of the THF molecules, particularly at 200 K; this was found to arise at higher temperatures due to transient hydrogen bonding of the oxygen atom in THF molecules with the surrounding cage-water molecules. a ) Corresponding author.
The ease with which the physical properties of graphene can be tuned suggests a wide range of possible applications. Recently, strain engineering of these properties has been of particular interest. Possible spintronic applications of magnetically doped graphene systems have motivated recent theoretical investigations of the so-called Ruderman-Kittel-Kasuya-Yosida (RKKY) interaction between localized moments in graphene. In this work a combination of analytic and numerical techniques are used to examine the effects of uniaxial strain on such an interaction. A range of interesting features are uncovered depending on the separation and strain directions. Amplification, suppression, and oscillatory behavior are reported as a function of the strain and mathematically transparent expressions predicting these features are derived. Since a wide range of effects, including overall moment formation and magnetotransport response, are underpinned by such interactions we predict that the ability to manipulate the coupling by applying strain may lead to interesting spintronic applications.
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