Search

Recent experiments show that the relative dielectric constant $\epsilon$ of water confined to a film of nanometric thickness reaches a strikingly low value of 2.1, barely above the bulk's 1.8 value for the purely electronic response. We argue that $\epsilon$ is not a well-defined measure for dielectric properties at sub-nanometer scales due to the ambiguous definition of confinement width. Instead we propose the 2D polarisability $\alpha_{\perp}$ as the appropriate, well-defined response function whose magnitude can be directly obtained from both measurements and computations. Our molecular-dynamics computations based on density-functional theory and empirical force fields reproduce the previously reported low dielectric response of confined water, and importantly predict a very significant reduction, $\sim 30$\%, of the electronic response as compared with the bulk's, contrary to what is widely assumed, highlighting the importance of electronic degrees of freedom to interpret the dielectric response of polar fluids under nanoconfinement rconditions., Comment: 5 pages, 3 figures

The water/electrode interface under an applied bias potential is a challenging out-of-equilibrium phenomenon, which is difficult to accurately model at the atomic scale. In this study, we employ a combined approach of Density Functional Theory (DFT) and non-equilibrium Green's function (NEGF) methods to analyze the influence of an external bias on the properties of water adsorbed on Au(111) and Pd(111) metallic electrodes. Our results demonstrate that while both Au and Pd-electrodes induce qualitatively similar structural responses in adsorbed water molecules, the quantitative differences are substantial, driven by the distinct nature of water-metal bonding. Our findings underscore the necessity of quantum-mechanical modeling for accurately describing electrochemical interfaces.

The free energy of ion solvation can be decomposed into enthalpic and entropic contributions. This helps to understand the connection between the dielectric properties and the underlying forces. We present a simple linear-response model of screened charge interactions that provides an alternative understanding of solvation barriers. Moreover, it explains the "anti-Coulomb" interactions (attraction between like-charged ions and repulsion between opposite-charged ions) observed in both simulations and experiments. We show that this is a universal behavior associated to the non-local response function of any dielectric or metallic system., Comment: 10 + 9 pages, 8 + 14 figures

We calculate target-material responses for dark matter--electron scattering at the \textit{ab-initio} all-electron level using atom-centered gaussian basis sets. The all-electron effects enhance the material response at high momentum transfers from dark matter to electrons, $q\gtrsim \mathcal{O}\left({10\ \alpha m_e}\right)$, compared to calculations using conventional plane wave methods, including those used in QEDark; this enhances the expected event rates at energy transfers $E \gtrsim 10$~eV, especially when scattering through heavy mediators. We carefully test a range of systematic uncertainties in the theory calculation, including those arising from the choice of basis set, exchange-correlation functional, number of unit cells in the Bloch sum, $\mathbf{k}$-mesh, and neglect of scatters with very high momentum transfers. We provide state-of-the-art crystal form factors, focusing on silicon and germanium. Our code and results are made publicly available as a new tool, called Quantum Chemistry Dark (``QCDark'')., Comment: 15 pages, plus references and appendices, 12 figures

Oscura is a planned light-dark matter search experiment using Skipper-CCDs with a total active mass of 10 kg. As part of the detector development, the collaboration plans to build the Oscura Integration Test (OIT), an engineering test with 10% of the total mass. Here we discuss the early science opportunities with the OIT to search for millicharged particles (mCPs) using the NuMI beam at Fermilab. mCPs would be produced at low energies through photon-mediated processes from decays of scalar, pseudoscalar, and vector mesons, or direct Drell-Yan productions. Estimates show that the OIT would be a world-leading probe for mCPs in the MeV mass range., Comment: 13 pages, 10 figures

Oscura is a proposed multi-kg skipper-CCD experiment designed for a dark matter (DM) direct detection search that will reach unprecedented sensitivity to sub-GeV DM-electron interactions with its 10 kg detector array. Oscura is planning to operate at SNOLAB with 2070 m overburden, and aims to reach a background goal of less than one event in each electron bin in the 2-10 electron ionization-signal region for the full 30 kg-year exposure, with a radiation background rate of 0.01 dru. In order to achieve this goal, Oscura must address each potential source of background events, including instrumental backgrounds. In this work, we discuss the main instrumental background sources and the strategy to control them, establishing a set of constraints on the sensors' performance parameters. We present results from the tests of the first fabricated Oscura prototype sensors, evaluate their performance in the context of the established constraints and estimate the Oscura instrumental background based on these results.

The phase diagram of ice is complex and contains many phases, but the most common (frozen water at ambient pressure, also known as Ih ice) is a non-polar material despite individual water molecules being polar. Consequently, ice is not piezoelectric and cannot generate electricity under pressure. On the other hand, the coupling between polarization and strain gradient (flexoelectricity) is universal, so ice may in theory generate electricity under bending. Here we report the experimental demonstration that ice is flexoelectric, finding a coefficient comparable to that of ceramics such as SrTiO3 or TiO2. Additionally, and unexpectedly, the sensitivity of flexoelectric measurements to surface boundary conditions has also revealed a ferroelectric phase transition around 163 confined in the near-surface region of the ice slabs. The electromechanical properties of ice may find applications for low-cost transducers made in-situ in cold and remote locations, but perhaps more important are the consequences for natural phenomena involving ice electrification. In particular, we have calculated the flexoelectric polarization generated in collisions between ice and graupel particles, which reproduces the experimentally reported results for contact electrification in such events, known to cause electrification in storm clouds.

We propose using Quantum Dots as novel targets to probe sub-GeV dark matter-electron interactions. Quantum dots are nanocrystals of semiconducting material, which are commercially available, with gram-scale quantities suspended in liter-scale volumes of solvent. Quantum dots can be efficient scintillators, with near unity single-photon quantum yields, and their band-edge electronic properties are determined by their characteristic size, which can be precisely tuned. Examples include lead sulfide (PbS) and lead selenide (PbSe) quantum dots, which can be tuned to have sub-eV optical gaps. A dark-matter interaction can generate one or more electron-hole pairs (excitons), with the multi-exciton state decaying via the emission of two photons with an efficiency of about 10% of the single-photon quantum yield. An experimental setup using commercially available quantum dots and two photo-multiplier-tubes (PMTs) for detecting the coincident two-photon signal can already improve on existing dark-matter bounds, while using photodetectors with lower dark-count rates can improve on current constraints by orders of magnitude., Comment: 12 pages, 7 figures ; Appendix 4 pages, 1 figure

The Oscura experiment will lead the search for low-mass dark matter particles using a very large array of novel silicon Charge Coupled Devices (CCDs) with a threshold of two electrons and with a total exposure of 30 kg-yr. The R&D effort, which began in FY20, is currently entering the design phase with the goal of being ready to start construction in late 2024. Oscura will have unprecedented sensitivity to sub-GeV dark matter particles that interact with electrons, probing dark matter-electron scattering for masses down to 500 keV and dark matter being absorbed by electrons for masses down to 1 eV. The Oscura R&D effort has made some significant progress on the main technical challenges of the experiment, of which the most significant are engaging new foundries for the fabrication of the CCD sensors, developing a cold readout solution, and understanding the experimental backgrounds.

SrTiO$_3$ is a highly efficient photocatalyst for the overall water splitting reaction under UV irradiation. However, an atomic-level understanding of the active surface sites responsible for the oxidation and reduction reactions is still lacking. Here we present a unified experimental and computational account of the photocatalytic activity at the SrO- and TiO$_2$- terminations of aqueous-solvated [001] SrTiO$_3$. Our experimental findings show that the overall water-splitting reaction proceeds on the SrTiO$_3$ surface only when the two terminations are simultaneously exposed to water. Our simulations explain this, showing that the photogenerated hole-driven oxidation primarily occurs at SrO surfaces in a sequence of four single hole transfer reactions, while the TiO$_2$ termination effects the crucial band alignment of the photocatalyst relative to the water oxidation potential. The present work elucidates the interdependence of the two chemical terminations of SrTiO$_3$ surfaces, and has consequent implications for maximizing sustainable solar-driven water splitting., Comment: 11 + 6 pages, 6 + 8 figures, including Supplementary Information

Using an end-to-end differentiable implementation of the Kohn-Sham self-consistent field equations, we obtain an accurate neural network-based exchange and correlation (XC) functional of the electronic density. The functional is optimized using information on both energy and density while exact constraints are enforced through an appropriate neural network architecture. We evaluate our model against different families of XC approximations and show that, for non-empirical functionals, there is a strong linear correlation between energy and density errors. We use this correlation to define a novel XC functional quality metric that includes both energy and density errors, leading to a new, improved way to rank different approximations. Judged by this metric, our machine-learned functional significantly outperforms those within the same rung of approximations.

We study ion pair dissociation in water at ambient conditions using a combination of classical and ab initio approaches. The goal of this study is to disentangle the sources of discrepancy observed in computed potentials of mean force. In particular we aim to understand why some models favor the stability of solvent-separated ion pairs versus contact ion pairs. We found that some observed differences can be explained by non-converged simulation parameters. However, we also unveil that for some models, small changes in the solution density can have significant effects on modifying the equilibrium balance between the two configurations. We conclude that the thermodynamic stability of contact and solvent-separated ion pairs is very sensitive to the dielectric properties of the underlying simulation model. In general, classical models are very robust on providing a similar estimation of the contact ion pair stability, while this is much more variable in density functional theory-based models. The barrier to transition from solvent-separated to contact ion pair is fundamentally dependent on the balance between electrostatic potential energy and entropy. This reflects the importance of water intra- and inter-molecular polarizability in obtaining an accurate description of the screened ion-ion interactions., Comment: 13 + 11 pages, 12 + 10 figures

In density functional-theoretic studies of photoionized water-based systems, the role of charge localization in proton-transfer dynamics is not well understood. This is due to the inherent complexity in extracting the contributions of coupled electron-nuclear non-adiabatic dynamics in the presence of exchange and correlation functional errors. In this work, we address this problem by simulating a model system of ionized linear H-bonded water clusters using real-time Time Dependent Density Functional Theory (rt-TDDFT)-based Ehrenfest dynamics. Our aim is to understand how self-interaction error in semilocal exchange and correlation functionals affects the probability of proton transfer. In particular, we show that for H-bonded (H$_2$O)$_n^+$ chains (with $n>3$), the proton-transfer probability attains a maximum, becoming comparable to that predicted by hybrid functionals. This is because the formation of hemibonded-type geometries is largely suppressed in extended H-bonded structures. We also show how the degree of localization of the initial photo-hole is connected to the probability of a proton-transfer reaction, as well as to the separation between electronic and nuclear charge. These results are compared to those obtained with adiabatic dynamics where the initial wavefunction is allowed to relax to the ground state of the ion cluster, explaining why different functionals and dynamical approaches lead to quantitatively different results., Comment: 14 + 7 pages; 12 + 8 figures

Tunneled metal oxides such as $\alpha-$Mn$_8$O$_{16}$ (hollandite) have proven to be compelling candidates for charge-storage materials in high-density batteries. In particular, the tunnels can support one-dimensional chains of K$^+$ ions (which act as structure-stabilizing dopants) and H$_2$O molecules, as these chains are favored by strong H-bonds and electrostatic interactions. In this work, we examine the role of water molecules in enhancing the stability of K$^+$-doped $\alpha-$Mn$_8$O$_{16}$ (cryptomelane). The combined experimental and theoretical analyses show that for high enough concentrations of water and tunnel-ions, H$_2$O displaces K$^+$ ions from their natural binding sites. This displacement becomes energetically favorable due to the formation of K$_2^+$ dimers, thereby modifying the stoichiometric charge of the system. These findings have potentially significant technological implications for the consideration of cryptomelane as a Li$^+$/Na$^+$ battery electrode. Our work establishes the functional role of water in altering the energetics and structural properties of cryptomelane, an observation that has frequently been overlooked in previous studies., Comment: 9 + 5 pages (5 + 8 figures). Published version. Open access version available from the Chemical Science website

Two-phase noble liquid detectors, with large target masses and effective background reduction, are currently leading the dark matter direct detection for WIMP masses above a few GeV. Due to their sensitivity to single ionized electron signals, these detectors were shown to also have strong constraints for sub-GeV dark matter via their scattering on electrons. In fact, the most stringent direct detection constraints for sub-GeV dark matter down to as low as ~5 MeV come from noble liquid detectors, namely XENON10, DarkSide-50, XENON100 and XENON1T, although these experiments still suffer from high background at single or a few electron level. LBECA is a planned 100-kg scale liquid xenon detector with significant reduction of the single and a few electron background. The experiment will improve the sensitivity to sub-GeV dark matter by three orders of magnitude compared to the current best constraints., Comment: to appear in the Proceedings of the TAUP 2019 Conference

We propose a new molecular simulation framework that combines the transferability, robustness and chemical flexibility of an ab initio method with the accuracy and efficiency of a machine learned force field. The key to achieve this mix is to use a standard density functional theory (DFT) simulation as a pre-processor for the atomic and molecular information, obtaining a good quality electronic density. General, symmetry preserving, atom-centered electronic descriptors are then built from this density to train a neural network to correct the baseline DFT energies and forces. These electronic descriptors encode much more information than local atomic environments, allowing a simple neural network to reach the accuracy required for the problem of study at a negligible cost. The balance between accuracy and efficiency is determined by the baseline simulation. This is shown in results where high level quantum chemical accuracy is obtained for simulations of liquid water at standard DFT cost, or where high level DFT-accuracy is achieved in simulations with a low-level baseline DFT calculation, at a significantly reduced cost.

It is now established that nuclear quantum motion plays an important role in determining water's hydrogen bonding, structure, and dynamics. Such effects are important to include in density functional theory (DFT) based molecular dynamics simulation of water. The standard way of treating nuclear quantum effects, path integral molecular dynamics (PIMD), multiplies the number of energy/force calculations by the number of beads required. In this work we introduce a method whereby PIMD can be incorporated into a DFT simulation with little extra cost and little loss in accuracy. The method is based on the many body expansion of the energy and has the benefit of including a monomer level correction to the DFT energy. Our method calculates intramolecular forces using the highly accurate monomer potential energy surface developed by Partridge-Schwenke, which is cheap to evaluate. Intermolecular forces and energies are calculated with DFT only once per timestep using the centroid positions. We show how our method may be used in conjunction with a multiple time step algorithm for an additional speedup and how it relates to ring polymer contraction and other schemes that have been introduced recently to speed up PIMD simulations. We show that our method, which we call "monomer PIMD", correctly captures changes in the structure of water found in a full PIMD simulation but at much lower computational cost., Comment: published in PCCP

Nuclear quantum effects lead to an anomalous shift of the volume of hexagonal ice; heavy ice has a larger volume than light ice. This anomaly in ice increases with temperature and persists in liquid water up to the boiling point. We study nuclear quantum effects on the density and compressibility of several ice-like structures and crystalline ice phases. By calculating the anisotropic contributions to the stain tensor, we analyze how the compressibility changes along different directions in hexagonal ice, and find that hexagonal ice is softer along the x-y plane than the z-direction. Furthermore, by performing ab initio density functional theory calculations with a van der Waals functional and with the quasiharmonic approximation, we find an anomalous isotope effect in the bulk modulus of hexagonal ice: heavy ice has a smaller bulk modulus than light ice. In agreement with the experiments, we also obtain an anomalous isotope effect for clathrate hydrate structure I. For the rest of the ice polymorphs, the isotope effect is: i) anomalous for ice IX, Ih, Ic, clathrate, and low density liquid-like amorphous ice; ii) normal at T=0 K and becomes anomalous with increasing temperature for ice IX, II, high density liquid-like amorphous ices, and ice XV; iii) normal for ice VIII up to the melting point. There is a transition from an anomalous isotope effect to a normal isotope effect for both the volume and bulk modulus, as the density (compressibility) of the structures increases (decreases). This result can explain the anomalous isotope effect in liquid water: as the compressibility decreases from melting point to the compressibility minimum temperature, the difference between the volumes of the heavy and light water rapidly decreases, but the effect stays anomalous up to the boiling temperature as the hydrogen bond network is never completely broken by fully filling all the interstitial sites., Comment: 17 pages, 15 figures

The phases of A$_2$Mn$_8$O$_{16}$ hollandite group oxides emerge from the competition between ionic interactions, Jahn-Teller effects, charge ordering, and magnetic interactions. Their balanced treatment with feasible computational approaches can be challenging for commonly used approximations in Density Functional Theory. Three examples (A = Ag, Li and K) are studied with a sequence of different approximate exchange-correlation functionals. Starting from a generalized gradient approximation (GGA), an extension to include van der Waals interactions and a recently proposed meta-GGA are considered. Then local Coulomb interactions for the Mn $3d$ electrons are more explicitly considered with the DFT+$U$ approach. Finally selected results from a hybrid functional approach provide a reference. Results for the binding energy of the A species in the parent oxide highlight the role of van der Waals interactions. Relatively accurate results for insertion energies can be achieved with a low $U$ and a high $U$ approach. In the low $U$ case, the materials are described as band metals with a high symmetry, tetragonal crystal structure. In the high $U$ case, the electrons donated by A result in formation of local Mn$^{3+}$ centers and corresponding Jahn-Teller distortions characterized by a local order parameter. The resulting degree of monoclinic distortion depends on charge ordering and magnetic interactions in the phase formed. The reference hybrid functional results show charge localization and ordering. Comparison to low temperature experiments of related compounds suggests that charge localization is the physically correct result for the hollandite group oxides studied here. . . ., Comment: 16 pages, 8 figures

Machine learning methods are being explored in many areas of science, with the aim of finding solution to problems that evade traditional scientific approaches due to their complexity. In general, an order parameter capable of identifying two different phases of matter separated by a correspond- ing phase transition is constructed based on symmetry arguments. This parameter measures the degree of order as the phase transition proceeds. However, when the two distinct phases are highly disordered it is not trivial to identify broken symmetries with which to find an order parameter. This poses an excellent problem to be addressed using machine learning procedures. Room tem- perature liquid water is hypothesized to be a supercritical liquid, with fluctuations of two different molecular orders associated to two parent liquid phases, one with high density and another one with low density. The validity of this hypothesis is linked to the existence of an order parameter capable of identifying the two distinct liquid phases and their fluctuations. In this work we show how two different machine learning procedures are capable of recognizing local order in liquid water. We argue that when in order to learn relevant features from this complexity, an initial, physically motivated preparation of the available data is as important as the quality of the data set, and that machine learning can become a successful analysis tool only when coupled to high level physical information., Comment: 14 pages, 12 figures, 2 appendices

Understanding the local structure of water at the interfaces of metallic electrodes is a key problem in aqueous-based electrochemistry. Nevertheless, a realistic simulation of such setup is challenging, particularly when the electrodes are maintained at different potentials. To correctly compute the effect of an external bias potential applied to truly semi-infinite surfaces, we combine Density Functional Theory (DFT) and Non-Equilibrium Green's Functions (NEGF) methods. This framework allows for the out-of-equilibrium calculation of forces and dynamics, and directly correlates to the chemical potential of the electrodes, which is the one introduced experimentally. In this work, we apply this methodology to study the electronic properties and atomic forces of one water molecule at the interface of gold surface. We find that the water molecule tends to align its dipole moment with the electric field, and it is either repelled or attracted to the metal depending on the sign and magnitude of the applied bias, in an asymmetric fashion.

We describe a method, that we call data projection onto parameter space (DPPS), to optimize an energy functional of the electron density, so that it reproduces a dataset of experimental magnitudes. Our scheme, based on Bayes theorem, constrains the optimized functional not to depart unphysically from existing ab initio functionals. The resulting functional maximizes the probability of being the \correct" parametrization of a given functional form, in the sense of Bayes theory. The application of DPPS to water sheds new light on why density functional theory has performed rather poorly for liquid water, on what improvements are needed, and on the intrinsic limitations of the generalized gradient approximation to electron exchange and correlation. Finally, we present tests of our water-optimized functional, that we call vdW-DF-w, showing that it performs very well for a variety of condensed water systems., Comment: 10 pages, 10 figures

First-principles calculations are made for the primary pyroelectric coefficients of wurtzite GaN and ZnO. The pyroelectricity is attributed to the quasiharmonic thermal shifts of internal strains (internal displacements of cations and anions carrying their Born effective charges). The primary (zero-external-strain) pyroelectricity dominates at low temperatures, while the secondary pyroelectricity (the correction from external thermal strains) becomes comparable with the primary pyroelectricity at high temperatures. Contributions from the acoustic and the optical phonon modes to the primary pyroelectric coefficient are only moderately well described by the corresponding Debye function and Einstein function respectively.

Liquid water is not only of obvious importance but also extremely intriguing, displaying many anomalies that still challenge our understanding of such an a priori simple system. The same is true when looking at nanoconfined water: The liquid between constituents in a cell is confined to such dimensions, and there is already evidence that such water can behave very differently from its bulk counterpart. A striking finding has been reported from computer simulations for two-dimensionally confined water: The liquid displays continuous or discontinuous melting depending on its density. In order to understand this behavior, we have analyzed the melting exhibited by a bilayer of nanoconfined water by means of molecular dynamics simulations. At high density we observe the continuous melting to be related to the phase change of the oxygens only, with the hydrogens remaining liquid-like throughout. Moreover, we find an intermediate hexatic phase for the oxygens between the liquid and a triangular solid ice phase, following the Kosterlitz-Thouless-Halperin-Nelson-Young theory for two-dimensional melting. The liquid itself tends to maintain the local structure of the triangular ice, with its two layers being strongly correlated, yet with very slow exchange of matter. The decoupling in the behavior of the oxygens and hydrogens gives rise to a regime in which the complexity of water seems to disappear, resulting in what resembles a simple monoatomic liquid. This intrinsic tendency of our simulated water may be useful for understanding novel behaviors in other confined and interfacial water systems.

Dark matter in the sub-GeV mass range is a theoretically motivated but largely unexplored paradigm. Such light masses are out of reach for conventional nuclear recoil direct detection experiments, but may be detected through the small ionization signals caused by dark matter-electron scattering. Semiconductors are well-studied and are particularly promising target materials because their ${\cal O}(1~\rm{eV})$ band gaps allow for ionization signals from dark matter as light as a few hundred keV. Current direct detection technologies are being adapted for dark matter-electron scattering. In this paper, we provide the theoretical calculations for dark matter-electron scattering rate in semiconductors, overcoming several complications that stem from the many-body nature of the problem. We use density functional theory to numerically calculate the rates for dark matter-electron scattering in silicon and germanium, and estimate the sensitivity for upcoming experiments such as DAMIC and SuperCDMS. We find that the reach for these upcoming experiments has the potential to be orders of magnitude beyond current direct detection constraints and that sub-GeV dark matter has a sizable modulation signal. We also give the first direct detection limits on sub-GeV dark matter from its scattering off electrons in a semiconductor target (silicon) based on published results from DAMIC. We make available publicly our code, QEdark, with which we calculate our results. Our results can be used by experimental collaborations to calculate their own sensitivities based on their specific setup. The searches we propose will probe vast new regions of unexplored dark matter model and parameter space., Comment: 30 pages + 22 pages appendices/references, 17 figures, website at http://ddldm.physics.sunysb.edu/, v2 added references, minor edits to text and Figs. 2 and 14, version to appear in JHEP

The local structure of liquid water as a function of temperature is a source of intense research. This structure is intimately linked to the dynamics of water molecules, which can be measured using Raman and infrared spectroscopies. The assignment of spectral peaks depends on whether they are collective modes or single molecule motions. Vibrational modes in liquids are usually considered to be associated to the motions of single molecules or small clusters. Using molecular dynamics simulations we find dispersive optical phonon-like modes in the librational and OH stretching bands. We argue that on subpicosecond time scales these modes propagate through water's hydrogen bond network over distances of up to two nanometers. In the long wavelength limit these optical modes exhibit longitudinal-transverse splitting, indicating the presence of coherent long range dipole-dipole interactions, as in ice. Our results indicate the dynamics of liquid water have more similarities to ice than previously thought., Comment: accepted into Nat. Comm

We study the isotope effect on the temperature of the proton order/disorder phase transition between ice XI and ice Ih, using the quasiharmonic approximation combined with \textit{ab initio} density functional theory calculations. We show that this method is accurate enough to obtain a phase transition temperature difference between light ice (H$_2$O) and heavy ice (D$_2$O) of 6 K as compared to the experimental value of 4 K. More importantly, we are able to explain the origin of the isotope effect on the much debated large temperature difference observed in the phase transition. The source of the difference is directly linked to the physics behind the anomalous isotope effect on the volume of hexagonal ice that was recently explained in [Phys. Rev. Lett. 108, 193003 (2012)]. These results indicate that the same physics might be behind the isotope effects in transition temperatures between other ice phases., Comment: 8 pages, 6 figures

This paper studies short-range order (SRO) in the semiconductor alloy (GaN)$_{1-x}$(ZnO)$_x$. Monte Carlo simulations performed on a density functional theory (DFT)-based cluster expansion model show that the heterovalent alloys exhibit strong SRO because of the energetic preference for the valence-matched nearest-neighbor Ga-N and Zn-O pairs. To represent the SRO-related structural correlations, we introduce the concept of Special Quasi-ordered Structure (SQoS). Subsequent DFT calculations reveal dramatic influence of SRO on the atomic, electronic and vibrational properties of the (GaN)$_{1-x}$(ZnO)$_x$ alloy. Due to the enhanced statistical presence of the energetically unfavored Zn-N bonds with the strong Zn3$d$-N2$p$ repulsion, the disordered alloys exhibit much larger lattice bowing and band-gap reduction than those of the short-range ordered alloys. Inclusion of lattice vibrations stabilizes the disordered alloy.

We study the structure and dynamics of liquid water in contact with Pd and Au (111) surfaces using \emph{ab initio} molecular dynamics simulations with and without van der Waals interactions. Our results show that the structure of water at the interface of these two metals is very different. For Pd, we observe the formation of two different domains of preferred orientations, with opposite net interfacial dipoles. One of these two domains has a large degree of in-plane hexagonal order. For Au a single domain exists with no in-plane order. For both metals, the structure of liquid water at the interface is strongly dependent on the use of dispersion forces. The origin of the structural domains observed in Pd is associated to the interplay between water/water and water/metal interactions. This effect is strongly dependent on the charge transfer that occurs at the interface, and which is not modeled by current state of the art semi-empirical force fields.

We present a critical comparison of the dielectric properties of three models of water - TIP4P/2005, TIP4P/2005f and TTM3F. Dipole spatial correlation is measured using the distance dependent Kirkwood function along with one dimensional and two dimensional dipole correlation functions. We find that the introduction of flexibility alone does not significantly affect dipole correlation and only affects $\varepsilon(\omega)$ at high frequencies. By contrast the introduction of polarizability increases dipole correlation and yields a more accurate $\varepsilon(\omega)$. Additionally the introduction of polarizability creates temperature dependence in the dipole moment even at fixed density, yielding a more accurate value for $d \varepsilon / d T$ compared to non-polarizable models. To better understand the physical origin of the dielectric properties of water we make analogies to the physics of polar nanoregions in relaxor ferroelectric materials. We show that $\varepsilon(\omega,T)$ and $\tau_D(T)$ for water have striking similarities with relaxor ferroelectrics, a class of materials characterized by large frequency dispersion in $\varepsilon(\omega,T)$, Vogel-Fulcher-Tamann behaviour in $\tau_D(T)$, and the existence of polar nanoregions., Comment: 13 pages, 16 figures. Accepted in JCP. Updated figs 1, 3, & 4, added acknowledgement

We present total energy and force calculations on the (GaN)$_{1-x}$(ZnO)$_{x}$ alloy. Site-occupancy configurations are generated by Monte Carlo (MC) simulations, based on a cluster expansion (CE) model proposed in a previous study. Surprisingly large local atomic coordinate relaxations are found by density-functional calculations using a 432-atom periodic supercell, for three representative configurations at $x=0.5$. These are used to generate bond length distributions. The configurationally averaged composition- and temperature-dependent short-range order (SRO) parameters of the alloys are discussed. Entropy is approximated in terms of pair distribution statistics and thus related to SRO parameters. This approximate entropy is compared with accurate numerical values from MC. An empirical model for the dependence of bond length on local chemical environments is proposed.

Finite-range numerical atomic orbitals are the basis functions of choice for several first principles methods, due to their flexibility and scalability. Generating and testing such basis sets, however, remains a significant challenge for the end user. We discuss these issues and present a new scheme for generating improved polarization orbitals of finite range. We then develop a series of high-accuracy basis sets for the water molecule, and report on their performance in describing the monomer and dimer, two phases of ice, and liquid water at ambient and high density. The tests are performed by comparison with plane-wave calculations, and show the atomic orbital basis sets to exhibit an excellent level of transferability and consistency. The highest-order bases (quadruple-zeta) are shown to give accuracies comparable to a plane-wave kinetic energy cutoff of at least ~1000 eV for quantities such as energy differences and ionic forces, as well as achieving significantly greater accuracies for total energies and absolute pressures., Comment: 17 pages, 14 figures

The isothermal compressibility of water is essential to understand its anomalous properties. We compute it by ab initio molecular dynamics simulations of 200 molecules at five densities, using two different van der Waals density functionals. While both functionals predict compressibilities within ~30% of experiment, only one of them accurately reproduces, within the uncertainty of the simulation, the density dependence of the self-diffusion coefficient in the anomalous region. The discrepancies between the two functionals are explained in terms of the low- and high-density structures of the liquid., Comment: 12 pages, 16 figures

Several thermodynamic properties of ice Ih, II, and III are studied by a quasi-harmonic approximation and compared to results of quantum path integral and classical simulations. This approximation allows to obtain thermodynamic information at a fraction of the computational cost of standard simulation methods, and at the same time permits studying quantum effects related to zero point vibrations of the atoms. Specifically we have studied the crystal volume, bulk modulus, kinetic energy, enthalpy and heat capacity of the three ice phases as a function of temperature and pressure. The flexible q-TIP4P/F model of water was employed for this study, although the results concerning the capability of the quasi-harmonic approximation are expected to be valid independently of the employed water model. The quasi-harmonic approximation reproduces with reasonable accuracy the results of quantum and classical simulations showing an improved agreement at low temperatures (T < 100 K). This agreement does not deteriorate as a function of pressure as long as it is not too close to the limit of mechanical stability of the ice phases., Comment: 13 pages, 15 figures

Molecules like water have vibrational modes with a zero-point energy well above room temperature. As a consequence, classical molecular dynamics simulations of their liquids largely underestimate the energy of modes with a higher zero-point temperature, which translates into an underestimation of covalent interatomic distances due to anharmonic effects. Zero-point effects can be recovered using path integral molecular dynamics simulations, but these are computationally expensive, making their combination with ab initio molecular dynamics simulations a challenge. As an alternative to path integral methods, from a computationally simple perspective, one would envision the design of a thermostat capable of equilibrating and maintaining the different vibrational modes at their corresponding zero-point temperatures. Recently, Ceriotti et al. (Phys. Rev. Lett. 102 020601 (2009)) introduced a framework to use a custom-tailored Langevin equation with correlated noise that can be used to include quantum fluctuations in classical molecular dynamics simulations. Here we show that it is possible to use the generalized Langevin equation with suppressed noise in combination with Nose-Hoover thermostats to efficiently impose a zero-point temperature on independent modes in liquid water. Using our simple and inexpensive method, we achieve excellent agreement for all atomic pair correlation functions compared to the path integral molecular dynamics simulation., Comment: 27 pages, 12 figs, Published version

We have fabricated PbTiO$_{3}$/SrRuO$_{3}$ superlattices with ultra-thin SrRuO$_{3}$ layers. Due to the superlattice geometry, the samples show a large anisotropy in their electrical resistivity, which can be controlled by changing the thickness of the PbTiO$_{3}$ layers. Therefore, along the ferroelectric direction, SrRuO$_{3}$ layers can act as dielectric, rather than metallic, elements. We show that, by reducing the concentration of PbTiO$_{3}$, an increasingly important effect of polarization asymmetry due to compositional inversion symmetry breaking occurs. The results are significant as they represent a new class of ferroelectric superlattices, with a rich and complex phase diagram. By expanding our set of materials we are able to introduce new behaviors that can only occur when one of the materials is not a perovskite titanate. Here, compositional inversion symmetry breaking in bi-color superlattices, due to the combined variation of A and B site ions within the superlattice, is demonstrated using a combination of experimental measurements and first principles density functional theory., Comment: To be published in Physical Review Letters

One striking anomaly of water ice has been largely neglected and never explained. Replacing hydrogen ($^1$H) by deuterium ($^2$H) causes ice to expand, whereas the "normal" isotope effect is volume contraction with increased mass. Furthermore, the anomaly increases with temperature $T$, even though a normal isotope shift should decrease with $T$ and vanish when $T$ is high enough to use classical nuclear motions. In this study, we show that these effects are very well described by {\it ab initio} density functional theory. Our theoretical modeling explains these anomalies, and allows us to predict and to experimentally confirm a counter effect, namely that replacement of $^{16}$O by $^{18}$O causes a normal lattice contraction., Comment: 5 pages, 3 figures

We study the interplay between charge doping and intermolecular distance in the polymerization of C60 fullerene chains by means of density functional theory (DFT)-based first principle calculations. The potential energy surface analysis shows that both the equilibrium intermolecular distance of the unpolymerized system and the polymerization energy barrier are inversely proportional to the electron doping of the system. We analyze the origin of this charge-induced polymerization effect by studying the behavior of the system's wavefunctions around the Fermi level and the structural modifications of the molecules as a function of two variables: the distance between the centers of the molecules and the number of electrons added to the system.

Density Functional Theory calculations are used to investigate the role of substrate-induced cooperative effects on the adsorption of water on a partially oxidized transition metal surface, O(2x2)/Ru(0001). Focussing particularly on the dimer configuration, we analyze the different contributions to its binding energy. A significant reinforcement of the intermolecular hydrogen-bond (H-bond), also supported by the observed frequency shifts of the vibration modes, is attributed to the polarization of the donor molecule when bonded to the Ru atoms in the substrate. This result is further confirmed by our calculations for a water dimer interacting with a small Ru cluster, which clearly show that the observed effect does not depend critically on fine structural details and/or the presence of co-adsorbates. Interestingly, the cooperative reinforcement of the H-bond is suppressed when the acceptor molecule, instead of the donor, is bonded to the surface. This simple observation can be used to rationalize the relative stability of different condensed structures of water on metallic substrates., Comment: Phys.Rev.B, 2010 (Accepted)