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A classical force field for MgSiO 3 polymorphs is presented and tested for the perovskite, post-perovskite and enstatite phases. In this force field each ion has a fixed partial charge and a fixed polarizability and the potential energy is minimised with respect to the ions’ dipole moments at each step of molecular dynamics by iterating them to self-consistency. The potential parameters are obtained by fitting to forces, stresses and energies calculated by density functional theory. The phase transition from perovskite to post-perovskite is predicted to take place at a pressure of 60 GPa at zero temperature. The potential reproduces well structural and thermodynamic properties as well as defects formation in a wide range of pressures, and therefore will be useful for the investigation of MgSiO 3 based materials in a geophysical context.

X-ray absorption near-edge spectroscopy (XANES) spectra of solid and liquid iron at pressure and temperature obtainable at the Earth's mantle conditions have been calculated. The spectra have been obtained using the supercell with an electron core-hole approach, in an ab initio scheme based on the continued-fraction approach and norm-conserving pseudo-potentials. The atomic structures for the spectra calculations were obtained from classical molecular dynamics simulations performed using an optimized modified embedded-atom potential. Comparisons to experimental XANES data are made for both solid and liquid phases of iron. For the liquid configuration, we find excellent agreement. Calculated spectra obtained for the solid configurations are also in good agreement with the experiment, and those obtained via other theoretical methods. We discuss the electronic origin of the XANES features.

Starting from ab initio calculations and using a force matching procedure, we have developed a new force field for molecular dynamics simulations of self-assembled monolayers of methylthiolate (MT) on Au(111) surfaces. This new force field is able to reproduce several observed features of SAMs of MT on Au(111) surface, such as the formation of gold vacancy islands and the (root 3 x root 3)R30 lattice. We have studied the dynamics of Au adatoms and monatomic vacancies on the Au(111) surface for the SAM of MT at room temperature. It is observed that monatomic vacancies coarsen to form large vacancy islands while the adatoms group to form clusters. Both results are in agreement with experiments. At elevated temperatures, Au adatoms that are lifted from the surface leave an atomic vacancy on it. The liquid-like diffusion of gold adatoms on the SAM surface occurs by hopping between pairs of methylthiolate to which the adatom is temporarily bound. Our findings indicate that structural models of the c(4 x 2) unit cell including adatoms and vacancies at room temperature need to be revisited.

Annealing to several hundred Kelvin has been recently shown to induce densification in compressed SiO2 glass. By means of an ab-initio parameterised interatomic potential for SiO2 and molecular dynamic simulations, we studied the structural properties of compressed glass by cold compression at room temperature and by quenching the liquid at selected pressures. The noticeable differences found below 10 GPa between the two results are interpreted in the context of the experimentally reported temperature-induced densification and of the speculated occurrence of a first-order transition between two distinct polyamorphs. Calculated X-ray and neutron structure factors agree well with available experiments, and indicate that structural differences between annealed and cold-compressed forms take place at distances of 3.5–4 A. In contrast, short-range order (atomic coordination, bond length and angular distribution functions) is identical in the two forms of silica glass.

Clarifying the structure/dynamics relation of water hydrogen-bond network has been the aim of extensive research over many decades. By joining anvil cell high-pressure technology, femtosecond 2D infrared spectroscopy, and molecular dynamics simulations, we studied, for the first time, the spectral diffusion of the stretching frequency of an HOD impurity in liquid water as a function of pressure. Our experimental and simulation results concordantly demonstrate that the rate of spectral diffusion is almost insensitive to the applied pressure. This behavior is in contrast with the previously reported pressure-induced speed up of the orientational dynamics, which can be rationalized in terms of large angular jumps involving sudden switching between two hydrogen-bonded configurations. The different trend of the spectral diffusion can be, instead, inferred considering that the first solvation shell preserves the tetrahedral structure with pressure and the OD stretching frequency is only slight perturbed.

Theoretical studies of the interaction of HCl with small water clusters have so far neglected the effect of temperature, which ranges from a few tens of kelvin in cluster experiments, up to about 250 K in typical atmospheric conditions. We study the dynamical behavior of a selected set of HCl(H2O)6 clusters, representative of undissociated and dissociated configurations, by means of DFT-based first principles molecular dynamics. We find that the thermodynamcal stability of different configurations can be affected by temperature. We also present the infrared spectra of dissociated and undissociated configurations at 200 K and discuss the origin of the spectral features.

Pressure is extremely efficient to tune intermolecular interactions, allowing the study of the mechanisms regulating, at the molecular level, the structure and dynamics of condensed phases. Among the simplest molecules, water represents in many respects a mystery despite its primary role in ruling most of the biological, physical, and chemical processes occurring in nature. Here we report a careful characterization of the dynamic regime change associated with low-density and high-density forms of liquid water by measuring the line shape of the OD stretching mode of HOD in liquid water along different isotherms as a function of pressure. Remarkably, the high-pressure studies have been here extended down to 240 K, well inside the supercooled regime. Supported by molecular dynamics simulations, a correlation among amorphous and crystalline solids and the two different liquid water forms is attempted to provide a unified picture of the metastable and thermodynamic regimes of water.

Liquid water has a primary role in ruling life on Earth in a wide temperature and pressure range as well as a plethora of chemical, physical, geological, and environmental processes. Nevertheless, a full understanding of its dynamical and structural properties is still lacking. Water molecules are associated through hydrogen bonds, with the resulting extended network characterized by a local tetrahedral arrangement. Two different local structures of the liquid, called low-density (LDW) and high-density (HDW) water, have been identified to potentially affect many different chemical, biological, and physical processes. By combining diamond anvil cell technology, ultrafast pump-probe infrared spectroscopy, and classical molecular dynamics simulations, we show that the liquid structure and orientational dynamics are intimately connected, identifying the P-T range of the LDW and HDW regimes. The latter are defined in terms of the speeding up of the orientational dynamics, caused by the increasing probability of breaking and reforming the hydrogen bonds.

Understanding the behavior of simple molecular systems under the combined effect of high pressure (P) and temperature (T) has important implications in the modeling of planetary interiors, in the chemistry of detonation, and in the synthesis of new materials. Extreme conditions of P and T can be partially accessed in the laboratory either in heated diamond-anvil cells or in shock wave experiments, where dramatic changes in the chemical and physical properties of simple molecules have been reported. Depending on the detailed situation, compression may result in the formation of intermolecular bonds, or in disproportionation, or even in full dissociation into the constituent elements. In such a context, the theoretical prediction of stable or metastable structures and of their properties is highly desirable. However, this requires an accurate quantum description, capable of discriminating the often subtle changes in the nature of chemical bonds. First-principles molecular dynamics methods with variable-cell, constant-pressure dynamics—a natural derivation of the two revolutionary methods introduced more than 20 years ago by Michele Parrinello together with Roberto Car and Anees Rahman—offer a unique tool for this kind of exploration. Molecular CO2 was independently observed [5] and predicted to transform into extended quartz-like covalent solids at moderately high pressures (about 50 GPa). The actual structure of this high-pressure phase, as well as its P–T range of thermodynamic stability, are still widely debated. High temperatures (thousands of Kelvin) were crucially required in the synthesis of an extended covalent network, both in experiments and in theoretical simulations, which indicated that large reaction barriers are overcome in the synthesis. One possible explanation is that these barriers are associated with the rehybridization of carbon atomic orbitals, from linear (sp) in the molecule, to tetrahedral (sp) in all candidates for the extended solid proposed so far. Carbon is well-known to change its hybridization state with pressure. For example, carbon’s hybridi

We present a classical interatomic force field for liquid SiO2 which has been parametrized using the forces, stresses and energies extracted from ab initio calculations. We show how inclusion of more electronic effects in a phenomenological way and parametrization at the relevant conditions of pressure and temperature allow the creation of more accurate force fields. We compare the results of simulations with this force field both to experiment and to the results of ab initio molecular dynamics simulations and show how our procedure leads to comparisons which are greatly improved with respect to the most widely used force fields for silica.

We show, by electronic structure based molecular dynamics simulations, that an extra electron injected in crystalline polyethylene should fall spontaneously into a self-trapped state, a shallow donor with a large novel distortion pattern involving a pair of trans-gauche defects. Parallel calculations show instead that a hole will remain free and delocalized. We trace the difference of behavior to the intrachain nature of the hole, as opposed to the interchain one of the electron, and argue that applicability of this concept could be more general. Thus electrons (but not holes) should tend to self-trap in saturated organic insulators, but not for example in aromatic insulators, where both carriers are intrachain. © 2002 Elsevier Science B.V. All rights reserved.

The structural, dynamical, and thermal properties of crystalline polyethylene are addressed with first-principles methods based on the density functional theory. The relatively low accuracy of the local density approximation for molecular crystals is corrected with the generalized gradient approximation, supplemented with empirical van der Waals' corrections, so as to optimize the description of the static (structural and elastic) properties of crystalline polyethylene. Based on this description, we perform first-principles finite temperature molecular dynamics simulations of warm, solid polyethylene. We analyze in particular thermal disorder effects, revealing the spontaneous appearance of trans-gauche defects close to the melting temperature (430 K).

We present the K-edge X-ray absorption near edge spectra of hexagonal-closed packed iron at pressure and temperature conditions relevant to Earth's mantle conditions. The calculated spectra have been obtained using the first-principles scheme based on the continued-fraction approach and norm-conserving pseudopotentials. The atomic configurations used for the X-ray absorption near edge spectroscopy calculations were obtained from classical molecular dynamics simulations, using an optimized embedded-atom potential. We compare our calculated spectra to recently available experiment results (R. Boehler, H.G. Musshoff, R. Ditz, G. Aquilanti, and A. Trapananti, Rev. Sci. Instrum. 80 (2009), pp. 045103–045108) and identify the main features of the spectra that may indicate onset of melting in iron.

Mixed phases of titania and silica have raised interest for their high activity as photocatalysts and for their optical properties, such as a high refractive index. To rationalize their properties, it is necessary to understand their atomic structure in crystalline and amorphous phases. We have investigated Ti–Si mixed oxide phases by density functional theory and molecular dynamics. A polarizable potential has been developed for TiSiO4 and has been employed to sample the configuration space. Mixed phases are metastable with respect to separate TiO2 and SiO2, but they are only slightly higher in energy, and therefore might form under technologically relevant conditions. All Ti–Si mixed oxides considered, regardless of cation coordination, display peaks in IR and Raman spectra in the region of frequencies 880–950cm−1, while Ti-only phases do not, even if titanium is in a tetrahedral coordination. Our calculations thus confirm that these peaks are a signature of Ti–O–Si links, but they do not deliver information on the actual atomic structure of the material. Phases with titanium in a tetrahedral coordination display a higher electronic band gap than phases with titanium in octahedral coordination. This should have important consequences for the photocatalytic activity of mixed oxides of titania and silica.

We present a new method for first-principles numerical simulation of solid-solid phase transformation. The method is applied to the study of pressure induced transformations in silicon and carbon.

Melanophlogite, a low-pressure silica polymorph, has been extensively studied at different temperatures and pressures by molecular dynamics simulations. While the high-temperature form is confirmed as cubic, the low-temperature phase is found to be slightly distorted, in agreement with experiments. With increasing pressure, the crystalline character is gradually lost. At 8 GPa, the radial distribution function is consistent with an amorphous state. Like pristine glass, the topology changes, plastic behavior, and permanent densification appear above similar to 12 GPa, triggered by Si coordination number changes. We predict that a partial crystalline and amorphous sample can be obtained by recovering the sample from a pressure of similar to 12-16 GPa. (C) 2011 American Institute of Physics. [doi: 10.1063/1.3532543]

The interiors of Neptune and Uranus are believed to be primarily composed of a fluid mixture of methane and water. The mixture is subjected to pressures up to several hundred gigapascal, causing the ionization of water. Laboratory and simulation studies so far have focused on the properties of the individual components. Here we show, using first-principle molecular dynamic simulations, that the properties of the mixed fluid are qualitatively different with respect to those of its components at the same conditions. We observe a pressure-induced softening of the methane-water intermolecular repulsion that points to an enhancement of mixing under extreme conditions. Ionized water causes the progressive ionization of methane and the mixture becomes electronically conductive at milder conditions than pure water, indicating that the planetary magnetic field of Uranus and Neptune may originate at shallower depths than currently assumed.

Dissociation of chlorofluorocarbons in the atmosphere is a heterogeneous process that takes place mainly on the surface of ice particles. Recently an enhancement of the dissociation rate due to excess electrons has been shown theoretically and correspondingly measured experimentally. Our density functional theory calculations show that CCl(4) dissociates due to an excess electron with an energy gain of 0.8 eV on the ice surface as opposed to in the gas phase. Through the use of ab initio molecular dynamics, an atomistic pathway for this dissociation has been elucidated, this pathway shows the capture of Cl(-) by the ice surface through a partial solvation mechanism, in agreement with recent experimental findings.

I will review some fundamental aspects of atomistic simulations in high-pressure research, including the construction of the interatomic potentials and the basic methods to sample the constant-pressure and constant-temperature statistical ensemble. I will also present a couple of examples where such methods have been used to describe materials of planetary interest.

We combine density functional theory (DFT) with molecular dynamics simulations based on an accurate atomistic force field to calculate the pressure derivative of the melting temperature of magnesium oxide at ambient pressure - a quantity for which a serious disagreement between theory and experiment has existed for almost 15 years. We find reasonable agreement with previous DFT results and with a very recent experimental determination of the slope. We pay particular attention to areas of possible weakness in theoretical calculations and conclude that the long-standing discrepancy with experiment could only be explained by a dramatic failure of existing density functionals or by flaws in the original experiment.

We calculate by molecular dynamics the optical functions of MgO in the far infrared region 100-1000 cm(-1), for pressures up to 40 GPa and temperatures up to 4000 K. An ab initio parametrized many-body force field is used to generate the trajectories. Infrared spectra are obtained from the time correlation of the polarization, and from Kramers-Kronig relations. The calculated spectra agree well with experimental data at ambient pressure. We find that the infrared absorption of MgO at CO(2) laser frequencies increases substantially with both pressure and temperature and we argue that this may explain the underestimation, with respect to theoretical calculations, of the high-pressure melting temperature of MgO determined in CO(2) laser-heated diamond-anvil cell experiments.

A combination of ab initio molecular dynamic simulations and fully relaxed total energy calculations is used to predict that molecular CO2should transform to nonmolecular carbonate phases based on CO4tetrahedra at pressures in the range of 35 to 60 gigapascals. The simulation suggests a variety of competing phases, with a more facile transformation of the molecular phase at high temperatures. Thermodynamically, the most stable carbonate phase at high pressure is predicted to be isostructural to SiO2α-quartz (low quartz). A class of carbonates, involving special arrangements of CO4tetrahedra, is found to be more stable than all the other silica-like polymorphs.

Based on first-principle molecular dynamic simulations, we calculate the far-infrared spectra of small water clusters (H2O)(n) (n=2,4,6) at frequencies below 1000 cm(-1) and at 80 K and at atmospheric temperature (T > 200 K). We find that cluster size and temperature affect the spectra significantly. The effect of the cluster size is similar to the one reported for confined water. Temperature changes not only the shape of the spectra but also the total strength of the absorption, a consequence of the complete anharmonic nature of the classical dynamics at high temperature. In particular, we find that in the frequency region up to 320 cm(-1), the absorption strength per molecule of the water dimer at 220 K is significantly larger than that of bulk liquid water, while tetramer and hexamer show bulklike strengths. However, the absorption strength of the dimer throughout the far-infrared region is too small to explain the measured vapor absorption continuum, which must therefore be dominated by other mechanisms. (c) 2008 American Institute of Physics.

The structure of self-assembled monolayers (SAMs) of long-chain alkyl sulfides on gold(111) has been resolved by density functional theory–based molecular dynamics simulations and grazing incidence x-ray diffraction for hexanethiol and methylthiol. The analysis of molecular dynamics trajectories and the relative energies of possible SAM structures suggest a competition between SAM ordering, driven by the lateral van der Waals interaction between alkyl chains, and disordering of interfacial Au atoms, driven by the sulfur-gold interaction. We found that the sulfur atoms of the molecules bind at two distinct surface sites, and that the first gold surface layer contains gold atom vacancies (which are partially redistributed over different sites) as well as gold adatoms that are laterally bound to two sulfur atoms.

[1] Constant-pressure constant-temperature ab initio molecular dynamics simulations at high temperatures have been used to study MgSiO3, the major constituent of the Earth's lower mantle to conditions of the Earth's core-mantle boundary. The calculated equilibrium volumes and densities are compared with simulations using an orthorhombic perovskite configuration under the same conditions. For molten MgSiO3, we have determined the diffusion coefficients and shear viscosities at different thermodynamic conditions. Our results provide new constraints on the properties of molten MgSiO3 at conditions near the core-mantle boundary. The volume of the liquid is greater than that of the solid throughout the pressure-temperature conditions examined, and the volume change on fusion ranges from 5% at 88 GPa and 3500 K to 2.9% at 120 GPa and 5000 K. Existing experimental constraints on solid-liquid partition coefficients for Fe suggest that Fe is preferentially partitioned into the liquid. Such enrichment of Fe increases the density of the liquid, thus allowing the possibility of negatively buoyant melts from (Mg,Fe)SiO3 perovskite compositions at deep lower mantle conditions for plausible values of solid-liquid partition coefficients for Fe. At 120 GPa and 4500–5000 K, the diffusion coefficient of liquid MgSiO3 is 2–3 × 10−5 cm 2/s and the diffusion rates of the different chemical species are similar. The shear viscosity is estimated using Zwanzig's formula to be 19–31 cP under these conditions. On the basis of our calculated diffusivities, MgSiO3 is above the glass transition temperature at 120 GPa and 4500 K.

Contrary to ordinary solids, which are normally known to harden by compression, the compressibility of $\mathrm{Si}{\mathrm{O}}_{2}$ (silica) glass has a maximum at about $2--4\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ and its mechanical strength shows a minimum around $10\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$. At this pressure, the compression of silica glass undergoes a change from purely elastic to plastic, and samples recovered from above $10\phantom{\rule{0.3em}{0ex}}\mathrm{GPa}$ are found to be permanently densified. Using an improved, ab initio parametrized interatomic potential for $\mathrm{Si}{\mathrm{O}}_{2}$ we provide here a unified picture of the compression mechanisms based on the pressure-induced appearance of unquenchable fivefold defects. By means of molecular-dynamic simulations we find them to be responsible for the reduction of the mechanical strength and for permanent densification. We also find that the compressibility maximum does not require changes of the tetrahedral network topology.

The general aim of this study is to test the reliability of polarizable model potentials for the prediction of vibrational infrared and Raman spectra in highly anharmonic systems such as high temperature crystalline phases. By using an ab initio parametrized interatomic potential for SiO2 and molecular dynamics simulations, we calculate the infrared and Raman spectra for quartz, cristobalite, and stishovite at various thermodynamic conditions. The model is found to perform very well in the prediction of infrared spectra. Raman peak positions are also reproduced very well by the model; however, Raman intensities calculated by explicitly taking the derivative of the polarizability with respect to the atomic displacements are found to be in poorer agreement than intensities calculated using a parametrized “bond polarizability” model. Calculated spectra for the high temperature phases, where the role of dynamical disorder and anharmonicities is predominant, are found to be in excellent agreement with experiments. For the octahedral phases, our simulations are able to reproduce changes in the Raman spectra across the rutile-to-CaCl2 transition around 50 GPa, including the observed phonon softening. © 2006 American Institute of Physics. DOI: 10.1063/1.2390709

Constant-pressure, first-principles molecular dynamic simulations were used to investigate the behavior of methane at high pressure and temperature. Contrary to the current interpretation of shock-wave experiments, the simulations suggest that, below 100 gigapascals, methane dissociates into a mixture of hydrocarbons, and it separates into hydrogen and carbon only above 300 gigapascals. The simulation conditions (100 to 300 gigapascals; 4000 to 5000 kelvin) were chosen to follow the isentrope in the middle ice layers of Neptune and Uranus. Implications on the physics of these planets are discussed.

We studied theoretically the behavior of an injected electron-hole pair in crystalline polyethylene. Time-dependent adiabatic evolution by ab-initio molecular dynamics simulations show that the pair will become self-trapped in the perfect crystal, with a trapping energy of about 0.38 eV, with formation of a pair of trans-gauche conformational defects, three C$_2$H$_4$ units apart on the same chain. The electron is confined in the inter-chain pocket created by a local, 120$^\circ$ rotation of the chain between the two defects, while the hole resides on the chain and is much less bound. Despite the large energy stored in the trapped excitation, there does not appear to be a direct non-radiative channel for electron-hole recombination. This suggests that intrinsic self-trapping of electron-hole pairs inside the ideal quasi-crystalline fraction of PE might not be directly relevant for electrical damage in high-voltage cables., Comment: 9 pages, 3 figs; using iopart.cls

The thermal conductivity of solid argon in the classical limit has been calculated by equilibrium molecular dynamic simulations using the Green–Kubo formalism and a Lennard-Jones interatomic potential. Contrary to previous theoretical reports, we find that the computed thermal conductivities are in good agreement with experimental data. The computed values are also in agreement with the high-temperature limit of the three-phonon scattering contribution to the thermal conductivity. We find that finite-size effects are negligible and that phonon lifetimes have two characteristic time scales, so that agreement with kinetic theory is obtained only after appropriate averaging of the calculated phonon lifetimes.

The properties of compressed liquid hydrogen, the most abundant fluid in the universe, have been investigated by means of first-principles molecular dynamics at pressures between 75 and 175 GPa and temperatures closer to the freezing line than so far reported in shock-wave experiments. Evidence for a liquid–liquid transition between a molecular and a dissociated phase is provided. The transition is accompanied by a 6% increase in density and by metallization. This finding has important implications for our understanding of the interiors of giant planets and supports predictions of a quantum fluid state at low temperatures.

First-principles molecular dynamics simulations at constant pressure have been used to investigate the mechanisms of compression of liquid SiO2. Liquid SiO2 is found to become denser than quartz at a pressure of about 6 GPa, in agreement with extrapolations of lower pressure experimental data. The high compressibility of the liquid is traced to medium-range changes in the topology of the atomic network. These changes consist in an increase of network connectivity caused by the pressure-induced appearance of coordination defects.

By performing constant pressure ab initio molecular dynamics simulations we analyse the high pressure phases of molecular solid hydrogen. We use a gradient corrected LDA, and a freshly implemented efficient technique for Brillouin zone sampling. An extremely good k-point sampling turns out to be crucial for obtaining the correct ground state. Our constant pressure approach allows us to optimize simultaneously the ori-entational degrees of freedom, the lattice constants, and the space group. This can be done either by a local optimization tehcnique, or by running molecular dynamics (MD) trajectories. The MD allows for the system to undergo structural transformations spontaneously. In the lower pressure, namely for the broken symmetry phase (BSP or phase II), we find a quadrupolar orthorhombic structure, of Pca21 symmetry. By means of an MD investigation, we find, at higher pressures, a slightly distorted orthorhombic structure of Cmc21 symmetry. This structure cannot be straightforwardly identified with the H-A phase (or phase III) because: 1) it is metallic, and 2) the Raman vibron discontinuity would be far too large compared to experiment. In fact, we argue that this phase is the first metallic molecular phase of hydrogen. Metallization would happen then, not via a band-overlap mechanism, but due to a structural transformation. By comparing total enthalpies, we also give suggestions for the structure of phase III.