GIBBS: isothermal-isobaric thermodynamics of solids from energy curves using a quasi-harmonic Debye model

Graphene-based $s{p}^{2}$-carbon nanostructures such as carbon nanotubes and nanofibers can fail near their ideal strengths due to their exceedingly small dimensions. We have calculated the phonon spectra of graphene as a function of uniaxial tension by density functional perturbation theory to assess the first occurrence of phonon instability on the strain path, which controls the strength of a defect-free crystal at $0\phantom{\rule{0.3em}{0ex}}\mathrm{K}$. Uniaxial tensile strain is applied in the $x$ (nearest-neighbor) and $y$ (second nearest-neighbor) directions, related to tensile deformation of zigzag and armchair nanotubes, respectively. The Young's modulus $E=1050\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ and Poisson's ratio $\ensuremath{\nu}=0.186$ from our small-strain results are in good agreement with previous calculations. We find that in both $x$ and $y$ uniaxial tensions, phonon instabilities occur near the center of the Brillouin zone, at (${\ensuremath{\epsilon}}_{xx}=0.194$, ${\ensuremath{\sigma}}_{xx}=110\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$, ${\ensuremath{\epsilon}}_{yy}=\ensuremath{-}0.016$) and (${\ensuremath{\epsilon}}_{yy}=0.266$, ${\ensuremath{\sigma}}_{yy}=121\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$, ${\ensuremath{\epsilon}}_{xx}=\ensuremath{-}0.027$), respectively. Both soft phonons are longitudinal elastic waves in the pulling direction, suggesting that brittle cleavage fracture may be an inherent behavior of graphene and carbon nanotubes at low temperatures. We also predict that a phonon band gap will appear in highly stretched graphene, which could be a useful spectroscopic signature for highly stressed carbon nanotubes.

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Ab initio calculation of ideal strength and phonon instability of graphene under tension

http://myweb.clemson.edu/~daw/D_reprints/MatSciRep.v9p251y93.pdf

The embedded-atom method: a review of theory and applications

Powdered samples of the type Ce1−xRExO2−y, where RE=La, Pr, Nd, Eu, Gd, and Tb, are synthesized over the range 0≤x≤0.5 starting from nitrate solutions of the rare earths. X‐ray diffraction and Raman scattering are used to analyze the samples. These compounds, at least in the low doping regime and for strictly trivalent dopants, form solid solutions that maintain the fluorite structure of CeO2 with a change in lattice constant that is approximately proportional to the dopant ionic radius. The single allowed Raman mode, which occurs at 465 cm−1 in pure CeO2, is observed to shift to lower frequency with increasing doping level for all the rare earths. However, after correcting for the Gruneisen shift from the lattice expansion, the frequency shift is actually positive for all the strictly trivalent ions. In addition, the Raman line broadens and becomes asymmetric with a low frequency tail, and a new broad feature appears in the spectrum at ∼570 cm−1. These changes in the Raman spectrum are attributed to O va...

Raman and x‐ray studies of Ce1−xRExO2−y, where RE=La, Pr, Nd, Eu, Gd, and Tb

The structural, dynamical, and thermodynamic properties of diamond, graphite and layered derivatives (graphene, rhombohedral graphite) are computed using a combination of density-functional theory total-energy calculations and density-functional perturbation theory lattice dynamics in the generalized gradient approximation. Overall, very good agreement is found for the structural properties and phonon dispersions, with the exception of the c/a ratio in graphite and the associated elastic constants and phonon dispersions. Both the C-33 elastic constant and the F to A phonon dispersions are brought to close agreement with available data once the experimental c/a is chosen for the calculations. The vibrational free energy and the thermal expansion, the temperature dependence of the elastic moduli and the specific heat are calculated using the quasiharmonic approximation. Graphite shows a distinctive in-plane negative thermal-expansion coefficient that reaches its lowest value around room temperature, in very good agreement with experiments. Thermal contraction in graphene is found to be three times as large; in both cases, bending acoustic modes are shown to be responsible for the contraction, in a direct manifestation of the membrane effect predicted by Lifshitz over 50 years ago. Stacking directly affects the bending modes, explaining the large numerical difference between the thermal-contraction coefficients in graphite and graphene, notwithstanding their common physical origin.

I.P. Ipatova

Papers

Theory of lattice dynamics in the harmonic approximation

Electron-phonon coupling in highly doped n type silicon

The influence of surface vibrations on the equilibrium doping of a semiconductor

The influence of boron localized vibrations on the equilibrium distribution of boron between the surface and bulk of a silicon crystal