High and low density patches in simulated liquid water.

We present insights into the nature of structural heterogeneities in liquid water by characterizing the empty space within the hydrogen bond network. Using molecular dynamics simulations, we show that density fluctuations create regions of empty space characterized by a diverse morphology - from spherical to fractal-like voids. These voids allow for the identification of low and high density patches of the liquid, encompassing short (0.3-0.5 nm) as well as long (1-2 nm) length-scales. In addition, we show that the formation of these patches is coupled to collective fluctuations involving the topology of hydrogen-bonded rings of water molecules. In particular, water molecules in the high density patches tend to be slightly more tetrahedral - which is consistent with the predictions of the hydrophobic effect.

Density functional simulations of Sb-rich GeSbTe phase change alloys.

We generated models of the amorphous phase of Sb-rich GeSbTe phase change alloys by quenching from the melt within density functional molecular dynamics. We considered the two compositions Ge(1)Sb(1)Te(1) and Ge(2)Sb(4)Te(5). Comparison with previous results on the most studied Ge(2)Sb(2)Te(5) allowed us to draw some conclusions on the dependence of the structural properties of the amorphous phase on the alloy composition. Vibrational and electronic properties were also scrutinized. Phonons at high frequencies above 200 cm(-1) are localized in tetrahedra around Ge atoms in Sb-rich compounds as well as in Ge(2)Sb(2)Te(5). All compounds are semiconducting in the amorphous phase, with a band gap in the range 0.7-1.0 eV.

First-principles study of nitrogen doping in cubic and amorphous Ge2Sb2Te5.

We investigated the structural, electronic and vibrational properties of amorphous and cubic Ge(2)Sb(2)Te(5) doped with N at 4.2 at.% by means of large scale ab initio simulations. Nitrogen can be incorporated in molecular form in both the crystalline and amorphous phases at a moderate energy cost. In contrast, insertion of N in the atomic form is very energetically costly in the crystalline phase, though it is still possible in the amorphous phase. These results support the suggestion that N segregates at the grain boundaries during the crystallization of the amorphous phase, resulting in a reduction in size of the crystalline grains and an increased crystallization temperature.

First principles study of the optical contrast in phase change materials.

We study from first principles the optical properties of the phase change materials Ge(2)Sb(2)Te(5) (GST), GeTe and Sb(2)Te(3) in the crystalline phase and in realistic models of the amorphous phase generated by quenching from the melt in ab initio molecular dynamics simulations. The calculations reproduce the strong optical contrast between the crystalline and amorphous phases measured experimentally and exploited in optical data storage. It is demonstrated that the optical contrast is due to a change in the optical matrix elements across the phase change in all the compounds. It is concluded that the reduction of the optical matrix elements in the amorphous phases is due to angular disorder in p-bonding which dominates the amorphous network in agreement with previous proposals (Huang and Robertson 2010 Phys. Rev. B 81 081204) based on calculations on crystalline models.

Unravelling the mechanism of pressure induced amorphization of phase change materials.

Based on ab initio molecular dynamics simulations, we identify the atomistic mechanism of the pressure induced amorphization of Ge(2)Sb(2)Te(5). The simulations reveal that homopolar Ge/Sb bonds appear in cubic Ge(2)Sb(2)Te(5) under pressure, giving rise to square rings rotated by 45 degrees with respect to the crystalline axis whose formation is induced by the displacement of Te atoms filling the voids of neighboring Ge/Sb stoichiometric vacancies. The concentration of these topological defects increases with pressure up to 21 GPa at which the system is destabilized and transforms into an amorphous phase in agreement with experiments.

Vibrational properties of crystalline Sb(2)Te(3) from first principles.

Phonon dispersion relations and infrared and Raman spectra of crystalline Sb(2)Te(3) were computed within density functional perturbation theory. Overall good agreement with experiments is obtained, which allows us to assign the Raman and IR peaks to specific phonons.

First-principles study of crystalline and amorphous Ge(2)Sb(2)Te(5) and the effects of stoichiometric defects.

Based on ab initio molecular dynamics simulations, we investigated the structural, electronic and vibrational properties of cubic and amorphous Ge(2)Sb(2)Te(5) (GST) phase change material, focusing in particular on the effects of defects in stoichiometry on the electronic properties. It turned out Ge/Sb deficiencies (excess) in the cubic phase induce a shift of the Fermi level inside the valence (conduction) bands. In contrast, the amorphous network is flexible enough to accommodate defects in stoichiometry, keeping the Fermi level pinned at the center of the bandgap (at zero temperature). Changes in the structural and electronic properties induced by the use of hybrid functionals (HSE03, PBE0) instead of gradient corrected functionals (PBE) are addressed as well. Analysis of vibrational spectra and Debye-Waller factors of cubic and amorphous GST is also presented.

Vibrational properties of hexagonal Ge(2)Sb(2)Te(5) from first principles.

Phonons at the Γ point and the Raman spectrum of the hexagonal Ge(2)Sb(2)Te(5) were computed within density functional perturbation theory. The three different stackings of the Ge/Sb planes proposed in the experimental literature were considered. The theoretical Raman spectrum is similar for the three stackings with a marginally better agreement with experiments for the structure proposed by Matsunaga et al (2004 Acta Crystallogr. B 60 685) which assumes a disorder in Ge/Sb site occupation. Although the large broadening of the experimental Raman peaks prevents discriminating among the different stackings, the assignment of the Raman peaks to specific phonons is possible because the main features of the spectrum are rather insensitive to the actual distribution of atoms in the Sb/Ge sublattices. On the basis of the energetics (including configurational entropy) two stackings seem plausible candidates for GST, but only the mixed stacking by Matsunaga et al reproduces the spread of Ge/Sb-Te bond lengths measured experimentally.

Selectivity of auger decays to the local surface environment.

The line shape of the Auger decay of adatoms is studied by a joint theoretical and experimental effort, the former within a DFT framework, and the latter with synchrotron radiation measurements. We investigate the KL(2,3)V Auger deexcitation of Na on Al(111), a system with different adsorption geometries. In particular, we study the (sqrt[3]xsqrt[3])R30 degrees phase at 1/3 ML (monolayer) and the more complex (2 x 2) structure at 1/2 ML coverage. From the comparison between theory and experiment, we unambiguously determine features that allow for the determination of the adsorption environment from the adatom Auger spectrum.