Douglas Galvao, Universidade Estadual de Campinas (UNICAMP)
Xingao Gong, Fudan University
Susan Sinnott, University of Florida
Frederic Soisson, CEA Saclay
ZZ2: Functional Materials
Monday PM, November 30, 2015
Sheraton, 2nd Floor, Independence West
2:30 AM - ZZ2.01
Computationally Driven Discoveries of New MAX-Phase Materials: From Magnetic MAX-Phases to 2D-ldquo;Dirac MXenesrdquo;
Igor Abrikosov 1 2 3 Martin Dahlqvist 1 Arni Sigurdur Ingason 1 Bjorn Alling 1 Johanna Rosen 1 Hossein Fashandi 1 Viktor Ivady 1 4 Mikhail Katsnelson 5
1Linkoping Univ Linkoping Sweden2NUST "MISIS" Moscow Russian Federation3Tomsk State University Tomsk Russian Federation4Hungarian Academy of Sciences Budapest Hungary5Radboud University Nijmegen NetherlandsShow Abstract
We demonstrate the power of modern first-principles theory by presenting examples of successful knowledge-based design of novel materials belonging to a family the so-called MAX phases. The MAX phases are a comparatively new class of nanolaminated compounds with a unique combination of metallic and ceramic properties. They have a common formula Mn+1AXn (n = 1-3), where M is an early transition metal,A is an A-group element, and X is carbon or nitrogen. However, no magnetic MAX phases were known prior to our work. Using first-principles calculations, we predicted a series of thermodynamically stable magnetic MAX phases, e.g. (Cr1-xMnx)2AlC , (Cr1-xMnx)2GeC , and Mn2GaC . The materials have been synthesized [2,3] and have shown a variety of intriguing magnetic behavior. Furthermore, we have investigated theoretically a series of two-dimensional materials synthesized by selective etching of the A element from the MAX phases, known as MXenes, and have discovered MXenes with Dirac electrons . The Dirac MXenes possess twelve conical crossings in the 1st Brillouin zone with giant spin-orbit splitting. Our findings indicate that the 2D band structure of MXenes is protected against external perturbations and it is preserved even in multilayer phases. These results, together with experimental advances in MXene phases, presents a novel entire class of two-dimensional materials that may exhibit Dirac fermions with corresponding properties.
. M. Dahlqvist, B. Alling, I. A. Abrikosov, J. Rosen, Phys. Rev. B 84, 220403(R) (2011).
. A. S. Ingason, A. Mockute, M. Dahlqvist, F. Magnus, S. Olafsson, U. B. Arnalds, B. Alling, I.A. Abrikosov, B. Hjörvarsson, P. O. Å. Persson, and J. Rosen, Phys. Rev. Lett. 110, 195502 (2013).
 A. S. Ingason, A. Petruhins, M. Dahlqvist, F. Magnus, A. Mockute, B. Alling, L. Hultman, I. A. Abrikosov, P. O. Å. Persson, and J. Rosen, Mater. Res. Lett. 2, 89 (2014).
 H. Fashandi, V. Ivády, P. Eklund, A. Lloyd. Spetz, M. I. Katsnelson, and I. A. Abrikosov, arXiv:1506.05398 [cond-mat.mtrl-sci]
3:00 AM - ZZ2.02
Local Probing of Ferroelectric and Ferroelastic Switching by Phase-Field Simulation
Ye Cao 1 5 David Edwards 2 Stephen Jesse 1 5 Long-Qing Chen 3 Amit Kumar 2 Nazanin Bassiri-Gharb 4 Sergei V. Kalinin 1 5
1Oak Ridge National Laboratory Oak Ridge United States2Queenrsquo;s University Belfast Belfast United Kingdom3The Pennsylvania State University University Park United States4Georgia Institute of Technology Atlanta United States5Oak Ridge National Laboratory Oak Ridge United StatesShow Abstract
Scanning probe induced mechanical switching has recently emerged as an alternative method for domain manipulation due to their highly localized and electrically erasable characteristics.  Therefore the fundamental understanding of the role of local strains to the large effective piezoelectric and ferroelectric response of ferroelectric thin films is imperative. Here, we developed a self-consistent phase-field model to investigate the tip pressure (600nN) induced domain reorganization in 50nm thick (001) oriented lead zirconate titanate (Pb(Zr1-xTix)O3) films of rhombohedral (R) (x=0.2), tetragonal (T) (x=0.8) and morphotropic phase boundary (MPB) compositions (x=0.47). We found that at T phase composition c(001) domains is switched into a1(100) and a2(010) lateral domains and their growths are blocked by a/c twin domain walls, while at R phase composition the initial upward r1+ (111) and r4+ (1-11) domains are vertically switched into downward r1-(11-1) and r4-(1-1-1) domains respectively. Both switchings occur in limited 10nm deep regions from the top surface where the tip is located. At MPB composition R-T switching occurs, confirming that a transition between the R and T phase is ferroelastically active and can be directly induced by externally applied pressure. The domain switching at MPB is found to penetrate the entire film thickness, highlighting that the MPB composition is indeed softer than either pure R and T compositions. Our simulation results substantiate the experimental observation of change in hysteretic piezoresponse and domain structure caused by externally applied pressure. The phase-field model, combined with strain-mediated spectroscopy approach shows capability of exploring switching behaviors in a spatially resolved manner which would be otherwise difficult to resolve.
This research was sponsored by the Division of Materials Sciences and Engineering, Basic Energy Sciences, Department of Energy (YC, SJ, SVK). Research was conducted at the Center for Nanophase Materials Sciences, which also provided support and which is a DOE Office of Science User Facility. NBG gratefully acknowledges funding from the US National Science Foundation under grant number DMR-1255379. LQC gratefully acknowledges funding from DOE under Award No. DE-FG02-07ER46417.
 H. Lu, C.-W. Bark, D. Esque de los Ojos, J. Alcala, C. B. Eom, G. Catalan and A. Gruverman, Science 336, 59 (2012)
3:15 AM - *ZZ2.03
Functional Properties of Superlattices from First-Principles Models
Karin M. Rabe 1
1Rutgers Univ Piscataway United StatesShow Abstract
The physics of perovskite superlattices is well-known to be rich and varied. A feature of particular interest is that the properties of a superlattice can be enhanced over or even distinct from those of the constituent compounds, depending furthermore on the choice of layer thicknesses, termination and epitaxial strain. In this talk I describe recent work on first-principles-based modeling of polarization, dielectric response and piezoelectric response in ferroelectric-ferroelectric BaTiO3/PbTiO3 superlattices and of a first-order coupled magnetic nonpolar-polar metal-insulator transition in epitaxially strained SrCrO3/SrTiO3. The use of the first-principles models to interpret and interpolate first-principles results forms an essential part of a guided-sampling first-principles high-throughput approach allowing the identification of superlattice materials with optimal functional behavior targeted to specific technological applications and potentially the discovery of further novel physical phenomena in these systems.
4:15 AM - ZZ2.04
First Principles Computational Screening of Earth-Abundant Nitride Semiconductors
Yoyo Hinuma 1 Taisuke Hatakeyama 3 Yu Kumagai 2 Yoshinori Muraba 3 Hikaru Sato 3 Hidenori Hiramatsu 2 3 Isao Tanaka 1 Hideo Hosono 2 3 Fumiyasu Oba 1 2 3
1Kyoto University Kyoto Japan2Tokyo Institute of Technology Yokohama Japan3Tokyo Institute of Technology Yokohama JapanShow Abstract
Semiconductors obviously cover very wide applications in electronics, optoelectronics, and photovoltaics, and suggestions for novel useful semiconducting materials are always welcome. In particular, semiconductors that consist of earth-abundant and non-toxic elements only are especially attractive; stable production is possible because short supply of key elements is less likely to happen and these materials are likely to be environmentally friendly. Nitride semiconductors are appealing because the anion is nitrogen, a very common element, but those currently commercialized are mostly limited to GaN and related alloys. This motivates us to investigate ternary nitride compounds using high-throughput first principles calculations to identify promising semiconductors. Our algorithm involves looking at thermodynamic and lattice dynamic stability as well as electronic properties. The algorithm identifies previously reported nitride ternaries. ZnSnN2 is a relatively new material that is recently gaining interest because this compound consists of earth-abundant elements only . Its theoretical direct band gap is around 1.4 eV, which makes it an excellent candidate for potential applications in thin film photovoltaics. Other examples of previously reported ternary nitrides include LiZnN , ZnSiN2  and ZnGeN2 . Unreported and promising compounds are also found through calculations.
 L. Lahourcade et al., Adv. Mater. 25, 2562 (2013).  K. Kuriyama et al., Phys. Rev. B 49, 4511 (1994).  T. Endo et al., J. Mater. Sci. Lett. 11, 424 (1992).
4:30 AM - ZZ2.05
The Role of Low-Lying Optical Phonons in Lattice Thermal Conductance of Rare-Earth (RE) Pyrochlores: A First-Principle Study
Guoqiang Lan 1 Jun Song 1
1McGill Univ Montreal CanadaShow Abstract
Rare-earth pyrochlores, commonly exhibiting anomalously low lattice thermal conductivities, are considered as promising topcoat materials for thermal barrier coatings. However the structural origin underlying their low thermal conductivities remain unclear. In the present study, we investigated the phonon properties of two groups of RE pyrochlores, Ln2Zr2O7 (Ln = La, Nd, Sm, Gd) and Gd2T2O7 (T = Zr, Hf, Sn, Pb) employing density functional theory and quasi harmonic approximation. Through the relaxation time approximation (RTA) with Debye model, the thermal conductivities of those RE pyrochlores were predicted, showing good agreement with experimental measurements. The low thermal conductivities of RE pyrochlores were shown to largely come from the interference between the low-lying optical branches and acoustic branches. The structural origin underlying the low-lying optical branches was then clarified and the competition between scattering processes in transverse and longitude acoustic branches was discussed.
4:45 AM - *ZZ2.06
Ab Initio Screening of Photovoltaic Semiconductors with Benign Defect Properties
Shiyou Chen 1
1East China Normal University Shanghai ChinaShow Abstract
The number of component elements increased steadily in the 60-year development of photovoltaic semiconductors, i.e., from silicon in 1950s, to GaAs and CdTe in 1960s, CuInSe2 in 1970s, Cu(In,Ga)Se2 in 1980s, Cu2ZnSnS4 in 1990s and more recently Cu2ZnSn(S,Se)4 and CH3NH3PbI3. The increased number of elements makes the material properties more flexible, however, it also causes the dramatic increase of possible point defects in the lattice, which can significantly influence the optical and electrical properties and thus the photovoltaic performance of these multinary compound semiconductors. Whether they can work as ideal solar cell absorber material depends on the behavior of their intrinsic defects. Through ab initio calculations, we can predict the dominant defects in new semiconductors and determine whether there are high concentration of deep-level defects that may act as electron-hole recombination centers. Then the semiconductors free of detrimental defects can be identified, which will accelerate the discovery of new photovoltaic semiconductors with high energy-conversion efficiency. I will discuss such ab initio screening in four classes of semiconductor systems, including the quaternary I2-II-IV-VI4 (Cu2ZnSnS4, Cu2ZnSnSe4), the ternary I-V-VI2 (CuSbS2 and CuSbSe2), the binary Sb2Se3 as well as the halide perovskites (CsSnI3, CH3NH3SnI3 and CH3NH3PbI3), which were all proposed as the candidate photovoltaic materials with high efficiency. Based on the calculated formation energies (concentration) and transition energy levels of possible defects, I will discuss the influence of the chemical component and growth conditions on the defect formation/ionization and thus the electrical and optical properties of the samples, which will help us understand the related experiments and also judge whether the defects impose any intrinsic limit to the efficiency of these photovoltaic semiconductors.
(1) S. Chen, A. Walsh, X.-G. Gong, S.-H. Wei, Adv. Mater. 25, 1522 (2013)
(2) P. Xu, S. Chen, H.-J. Xiang, X.-G. Gong, S.-H. Wei, Chem. Mater. 26, 6068 (2014)
(3) B. Yang, L. Wang, J. Han, Y. Zhou, H. Song, S. Chen, J. Zhong, L. Lv, D. Niu, J. Tang, Chem. Mater. 26, 3135 (2014)
(4) A. Walsh, D. Scanlon, S. Chen, S.-H. Wei, X.-G. Gong, Angew. Chem. Int. Ed. 54, 1791 (2015)
(5) Y. Zhou, L. Wang, S. Chen, S. Qin, X. Liu, J. Chen, D. Xue, M. Luo, Y. Cao, Y. Cheng, E. Sargent, J. Tang, Nature Photonics 9, 409 (2015)
5:15 AM - ZZ2.08
First-Principles Study of Microporous Magnets M-MOF-74 (M = Ni,Co, Fe, Mn): The Role of Metal Centers
Zhang Qiu Ju 1
1Ningbo Institute of Material technology and engineering, CAS Ningbo ChinaShow Abstract
It is anticipated that coupling the intrinsic magnetism and porosity within the same material will offer an ideal medium for applications in magnetic separation, magnetic sensing, or low-density magnets. Beyond the adsorption and separation applications, some MOFs also exhibit some unique magnetic properties. Therefore, a clear understanding of the origin of magnetism in metalminus;organic frameworks (MOFs) would provide useful insight for tuning the electromagnetic properties of MOFs and finding new applications. Motivated by the manipulation of magnetic ordering with metal-doping methods, we chose M-MOF-74 (M=Mn, Fe, Co, Ni) to systematically investigate the electromagnetic behavior in MOFs by means of a density functional theory (DFT+U) method because isostructural MOF-74 containing various paramagnetic metal centers have been successfully synthesized.
Our calculated results show that the open paramagnetic metal sites in three-dimensional porous magnets M-MOF-74 (M = Ni, Co, Fe, Mn) favor high-spin electronic arrangement. Fe- and Co-MOF-74 exhibit ferromagnetic (FM) features and significantly distinct energy gaps between spin-up and spin-down channels in metastable states. After replacement of the Co center with a Ni ion, the FM feature is exhibited for the stable state since the “extra” valence electron is filled in the spin-down 3d bands to shift the Fermi level to higher energy. In contrast, after removal of one valence electron (i.e., replacement of the Fe center with Mn atoms), the energy gap is significantly enlarged and an antiferromagnetic (AFM) feature will be discerned. Our studies may enhance the understanding of the origin of magnetism in MOFs and provide useful insight for tuning the electromagnetic properties of MOFs and designing low-magnetic materials.
ZZ1: First Principles Calculations of Electronic Materials and Alloys
Monday AM, November 30, 2015
Sheraton, 2nd Floor, Independence West
9:00 AM - *ZZ1.01
Hierarchical Structure and Mechanics of Plants
Lorna J. Gibson 1
1MIT Cambridge United StatesShow Abstract
The cell walls in plant tissues are made up of just four basic building blocks: cellulose, the main structural fiber of the plant kingdom, hemicellulose, lignin and pectin. Although the microstructure of plant cell walls varies in different types of plants, broadly speaking, cellulose fibers reinforce a matrix of hemicellulose and either pectin or lignin. The cellular structure of plants varies from the honeycomb-like cells of wood to the closed-cell, liquid-filled foam-like parenchyma cells of apples and potatoes. The arrangement of the four basic building blocks plant cell walls and the variations in cellular structure give rise to a remarkably wide range of mechanical properties: the Young&’s moduli span 4 orders of magnitude while the compressive strengths span nearly 3 orders of magnitude. Here, we review the microstructure of both the cell wall and the cellular structure in four plant materials (wood, arborescent palm stems, bamboo and parenchyma) to explain the wide range in mechanical properties in plants.
9:30 AM - ZZ1.02
Electronic Structure of Si Nano Sheets under the Strain Induced by the Surface Oxidation
Mina Park 1 Seungchul Kim 1 Kwang-Ryeol Lee 1
1KIST Seoul Korea (the Republic of)Show Abstract
Nano structure of Si has drawn much attention owing to their unique electronic and optical properties. Recently, two dimensional silicon nano sheets (Si-NSs) were successfully synthesized [1,2] and extensively investigated on the possible applications to novel devices. It is common for the nanostructured materials to be under high level of stressed state due to the significant surface or interfacial effect. In the present work, we focused on the effect of lattice strain induced by surface oxidation of Si-NSs on their electronic band structures. We employed the density functional theory for the electronic structure calculation of the oxidized Si-NSs simulated by reactive molecular dynamics simulation. Si-NSs exhibit either direct or indirect band gap depending on the growth orientation while the bulk Si shows only indirect band gap. Moreover, applying bilateral strain to the Si-NSs induces the change in the conduction band minimum of the electronic band structure and leads to the band gap transition. For the (111) surface orientation, Si-NSs undergoes the indirect-to-direct transition by tensile strain. Meanwhile, (001)/(110) orientation Si-NSs undergoes the direct-to-indirect transition by compression. We suppose that the structural deformation due to the strain leads to the adjustment of the conduction band minimum energy according to its bonding or antibonding character. The present work revealed a general tendency that increasing the bond length along the lateral dimension enhanced the Si-NSs to possess the direct band gap characteristics. This finding would be very important for the strain engineering of the Si-NSs, because a slight change in the surface state such as surface oxidation can affect significantly the physical properties of the materials.
 U. Kim et al, “Synthesis of Si Nanosheets by a Chemical Vapor Deposition Process and Their Blue Emissions”, ACS Nano, 5, 2176 (2011).
 S. Kim et al, “Two-dimensionally Grown Single-Crystal Silicon Nanosheets with Tunable Visible-Light Emissions”, ACS Nano, 8, 6556-6562 (2014).
9:45 AM - ZZ1.03
Electronic Transport in VO2: A DFT - Boltzmann Transport Approach
Alper Kinaci 1 Motohisa Kado 2 Daniel Rosenmann 1 Chen Ling 2 Gaohua Zhu 2 Debasish Banerjee 2 Maria K Chan 1
1Argonne National Laboratory Lemont United States2Toyota Motor Eng amp; Mfg NA Ann Arbor United StatesShow Abstract
Materials that undergo metal-insulator transitions (MITs) are under intense study because the transition is scientifically fascinating and technologically promising for various applications. Among these materials, VO2 has served as a prototype due to its favorable transition temperature. While the physical underpinnings of the transition have been heavily investigated experimentally and computationally, quantitative modeling of electronic transport in the two phases has yet to be undertaken. In this work, we establish a density-functional-theory-based (DFT) approach to model electronic transport properties in VO2 in the semiconducting and metallic regimes, focusing on band transport using Boltzmann transport equation. Free parameters in the model are calibrated using experimentally measured transport quantities. We find that the approach can efficiently model the metallic and semiconducting phases. Using this methodology, we performed high throughput DFT calculations to investigate effects of doping on VO2 from mechanical, thermodynamic and electronic transport aspects.
10:00 AM - *ZZ1.04
Electronic Structure and Charge Transport in Nanosystems with Ab Initio Calculations
Lin-Wang Wang 1
1Lawrence Berkeley National Lab Berkeley United StatesShow Abstract
In this talk, I will present our recent simulations of nanostructure systems using linear scaling three dimensional fragment method (LS3DF) and nonadiabatic molecular dynamics (NMD). The LS3DF method is used to study the effects of Moire's pattern of a double layer MoS2 and MoSe2, and it is found that the structural Moire's pattern will localize the electronic states in such systems. The LS3DF method is also used to study the effect of electrostatic potential fluctuations in hybrid perovskite (CH3NH3)PbI3, and found that the random orientation of the organic molecule will cause carrier localization in the system, which will have significant impact on the carrier transport in the system. NMD is used to study the carrier transport in a monolayer of organic molecule, and it is found that the dynamics disorder play an important role in the carrier transport of such systems. The same method is also used to study carrier transport in the hybrid perovskite system.
11:00 AM - *ZZ1.05
Understanding Complex Materials at Finite Temperatures by Ab Inito Methods
Tilmann Hickel 1 Biswanath Dutta 1 Albert Glensk 1 Fritz Koermann 1 Blazej Grabowski 1 Joerg U. Neugebauer 1
1Max-Planck-Institut fuuml;r Eisenforschung GmbH Duesseldorf GermanyShow Abstract
Fully parameter-free ab initio methods based on density functional theory are steadily gaining popularity. Their atomistic view on physical processes and the access to chemical trends are attractive for a knowledge-driven development of novel electronic, biological or engineering materials. However, the apparent restriction of the method to ground state properties is a severe challenge for the understanding and prediction of many materials properties, as, e.g., heat capacities and phase diagrams, for which finite temperature effects are decisive. Over the last years we have developed a large range of multi-physics tools to go beyond this limitation. A key challenge was and is the accurate determination of free energies including all relevant excitation mechanisms individually as well as non-adiabatic coupling effects stabilizing certain phases. Within this talk we will discuss some of our recent methodological developments that foster a large-scale screening of material properties even at temperatures where anharmonic lattice vibrations and magnetic disorder become important. The finite-temperature ab initio methods will finally be applied to the calculation of martensitic and intermartensitic phase transitions in Ni-Mn-X Heusler alloys. The predicted chemical trends are important for a tailored design of their magnetocaloric and shape-memory properties.
11:30 AM - ZZ1.06
Computational Screening of Half-Heusler Compounds for Thermoelectric Applications Using Electron-Phonon-Averaged Approximation
Georgy Samsonidze 1 Boris Kozinsky 1
1Robert Bosch LLC Cambridge United StatesShow Abstract
We present a simple and efficient approximation to the quantum mechanical formulation of the electron relaxation time induced by electron-phonon interaction. The approximation is suited for the high temperature regime providing a practical procedure for high-throughput screening of thermoelectric materials. The method is applied to calculate the electronic transport coefficients and to determine the optimal carrier concentration which maximizes the thermoelectric figure of merit ZT at a target temperature. Computational screening of optimized ZT values is performed in the compositional space of half-Heusler compounds selected from materials databases and consisting of cheap earth-abundant elements. The method is validated by demonstrating agreement with the results of the exact electron-phonon calculations and with the experimental data for the currently used compounds. Several new compounds promising for thermoelectric applications are identified, one of which was successfully synthesized by our experimental collaborators . The computational results are examined for the presence of correlations between the ZT values and the material properties of half-Heusler compounds. In particular, we find deviations from the Wiedemann-Franz law in these compounds at low carrier concentrations and high temperatures by directly computing electrical and the electronic part of the thermal conductivities.
 G. Joshi et al., Energy Environ. Sci. 7, 4070 (2014)
11:45 AM - ZZ1.07
Solubility of Hydrogen and Vacancy Concentration in Nickel from First Principles Calculations
Arnaud Metsue 1 Abdelali Oudriss 1 Xavier Feaugas 1
1University of La Rochelle La Rochelle FranceShow Abstract
The incorporation of hydrogen in metals can strongly affect the physical properties of the host matrix and can lead to irreversible damages. Therefore, the solubility of hydrogen in metals is a fundamental data to design new protections preventing hydrogen embrittlement and safety materials. However, the apparent solubility can be influenced by the presence of crystalline defects such as point defects, dislocations or grain boundaries. In particular, it has been suggested that hydrogen promotes the formation of new vacancies, which participates to the mechanisms of degradation of metals (Fukai, 2003, J. Alloys Comp.). In this study, we determine the vacancy and hydrogen concentrations in nickel at thermodynamic equilibrium up to the melting point from a combination of first principles calculations and statistical physic.
First, we determine the solution enthalpy and entropy of the incorporation of H in a perfect crystal. We extend the calculations of these thermodynamic quantities to the formation of H-vacancy clusters where H atom is located in the displacement field generated by the vacancy. We limit the study to the interstitial sites inside and tangent to the vacancy core where the displacement field leads to a significant deformation of the sites (Metsue et al., 2014, Phil. Mag.). The calculations are performed up to the melting point for a wide range of H2 chemical potential where the Gibbs free energy is expressed as a sum of vibration and electronic contributions from the computation of the phonon dispersion curve and the electronic density of states. The latter contribution is required to get a realistic vacancy concentration (Metsue et al., 2014, J. Chem. Phys.) The solution enthalpies and entropies calculated for a H2 fugacity of 1 bar are in good agreement with previous experimental data (Eichenuaer et al., 1965, Z. Metall., Stafford et al., 1974, Acta Met.). In addition, we found that H-rich octahedral sites inside the vacancy core are destabilized at high H2 chemical potential, similarly to fcc Fe (Nazarov et al., 2010, Phys. Rev. B).
Then, we calculate the solubility and the vacancy concentration from the solution and H-vacancy clusters formation Gibbs free energy. We take into account an additional configuration part to the total entropy related to the distribution of H in the interstitial sites and the H-vacancy clusters. A close agreement is found between experiments and the hydrogen concentration calculated for a H2 fugacity of 1 bar. In particular, we show that the electronic excitations lead to a positive deviation in the Arrhenius plot of the solubility at temperatures close to the melting point. The vacancy concentration is calculated for a wide range of H2 chemical potential and we discuss its implications on the deformation of the lattice.
12:15 PM - ZZ1.09
Magnetic Exchange Interactions and Critical Temperature of the Nanolaminate Mn2GaC from First-Principles Supercell Methods
Andreas Thore 1 Bjorn Alling 1 Johanna Rosen 1
1Linkouml;ping University Linkouml;ping SwedenShow Abstract
The magnetic critical order-disorder temperature Tc of a material is a parameter that sets an upper operational limit for magnetic devices. First-principles based methods hold the promise of significantly speeding up the search for new magnetic materials by predicting Tc and thus guide experiments.
In this work, we employ and critically evaluate a first-principles approach based on supercell calculations for predicting Tc. Supercell calculations have the benefit of allowing for straightforward incorporation of structural or vibrational disorder effects on the magnetic interactions. As a model material we use the recently discovered nanolaminate Mn2GaC,1 which belongs to the family of so-called MAX phases (where M is an early transition metal, A an A-group element, and X is C and/or N).
First, we derive the exchange interaction parameters Jij between pairs of atoms i and j of the bilinear Heisenberg Hamiltonian using the novel magnetic direct cluster averaging method (MDCA).2 In this method, the J&’s are calculated through an averaging procedure over a large number of supercells in which the magnetic state has been randomly generated with respect to all magnetic atoms except for those of atoms i and j, for which Jijis sought. We compare the J&’s from the MDCA calculations to the same parameters calculated using the Connolly-Williams structure inversion method, and show that the two methods yield closely matching results.
Secondly, we use the MDCA-derived J's as input parameters in Monte Carlo simulations to calculate the magnetic energy, total magnetic moment, specific heat, magnetic susceptibility as well as Tc. For Mn2GaC, we find Tc = 660 K. The uncertainty in the calculated value of Tc caused by uncertainties in the J&’s is discussed and exemplified in our case by a calculation of the standard deviation, which is 133 K.
1 A. S. Ingason, A. Petruhins, M. Dahlqvist, F. Magnus, A. Mockute, B. Alling, L. Hultman, I. A. Abrikosov, P. O. Å. Persson, and J. Rosen, Materials Research Letters 2, 89 (2014).
2 A. Lindmaa, R. Lizárraga, E. Holmström, I. A. Abrikosov, and B. Alling, Physical Review B 88, 054414 (2013).
Douglas Galvao, Universidade Estadual de Campinas (UNICAMP)
Xingao Gong, Fudan University
Susan Sinnott, University of Florida
Frederic Soisson, CEA Saclay
ZZ4: Modeling Material Damage
Tuesday PM, December 01, 2015
Sheraton, 2nd Floor, Independence West
2:30 AM - ZZ4.01
Atomistic Modeling of Xe Adsorption on UO2 Surfaces
Jack Arayro 1 Fabienne Ribeiro 1 Guy Treglia 2
1Institute of Radioprotection and Nuclear Safety (IRSN) Marseille France2Interdisciplinary Nanoscience Center of Marseille (CINaM) Marseille FranceShow Abstract
Uranium dioxide UO2 is used as a standard fuel in pressurized water reactors (PWR). During fission reactions of uranium intragranular bubbles of xenon are generated. The presence of these bubbles modifies the thermomechanical properties of the fuel. Challenges in terms of safety due to the presence of these bubbles led to extensive work both from experimental and theoretical points of view, in order to better understand the changing of the physical properties and behavior of the fuel.
It is known from the literature that these bubbles are microfaceted, with (111) and (100) surfaces. We then study here simplified systems of xenon on semi infinite UO2 surfaces. In a first step, we assess the relative stability of UO2 surfaces according to their orientation and then to their polarity, by mixing thermostatistical relaxation and analytic formulations within a simple electrostatic model. The main result is that, whereas the (111) surface appears stable by construction and does not involved major reorganization, the polar (100) one is only stabilized through drastic rearrangement of the surface region.
In a second step, we proceed to xenon adsorption on these relaxed surfaces through Monte Carlo simulations in the grand canonical ensemble within semi-empirical potentials. The most striking feature revealed by the simulation is the existence of a phase transition from a dilute xenon phase towards a dense one, in which coexist the FCC, BCC and HCP structures, by increasing the chemical potential. Otherwise, the xenon density is found to increase with the temperature for a given chemical potential.
In a third step, the pressure inside the xenon bubble and in the UO2 matrix has been investigated. In the former case, we show that whatever the xenon structure may be, the pressure increases with the xenon density, but not with the temperature for a fixed density. In what concern the matrix, we will present the pressure profile before and after xenon adsorption. The next step will be to introduce these so obtained results in a micromechanical model, which will allow us to propose a thermomechanical behavior law for the porous UO2.
2:45 AM - ZZ4.02
Cluster Dynamics in Irradiated UO2: Off-Stoichiometric Considerations for Voids, Loops and the Oxide Matrix
Sarah Khalil 1 Todd Allen 3 Anter El-Azab 2 Ahmed Hamed 2
1UW - Madison Madison United States2Purdue University West Lafayette United States3Idaho National Lab Idaho Falls United StatesShow Abstract
A novel Cluster Dynamics (CD) model that describes the nucleation and evolution of defect clusters in oxides systems has been developed. The model has been used to predict clustering of vacancies and interstitials into voids and dislocation loops, respectively, in irradiated UO2. The model reproduces well a range of experimental data on nucleation and growth behavior and its temperature dependence. A very important feature of this model is its ability to predict the off-stoichiometry (or composition) of defect clusters, allowing, in turn, for the tracking of off-stoichiometry of the matrix. The effect of migration energy of point defects on the concentration and average size of voids has been studied. Also, the effect of irradiation conditions such as irradiation temperature, irradiation dose and dose rate on clusters concentration and composition has been investigated. The preliminary results show that Frenkel defects, as opposed to Schottky defects, dominate the nucleation process in irradiated UO2. Vacancy clusters tend to grow mainly by absorbing oxygen vacancies and the migration energy of uranium vacancies is the rate limiting energy in nucleation and growth of voids. The results also show that, in a stoichiometric UO2 under irradiation, vacancy clusters (voids) tend to have both hypo- and hyper-stoichiometric composition with a higher fraction of hyper-stoichiometric composition clusters. Hyper-stoichiometric cluster compositions indicate that the matrix would become oxygen rich even if the initial state is perfectly stoichiometric.
3:00 AM - *ZZ4.03
The Role of Chemistry and Disorder on Ionic Conductivity in Pyrochlore
Blas P. Uberuaga 1 Romain Perriot 1
1Los Alamos Nat'l Lab Los Alamos United StatesShow Abstract
Complex oxides are being extensively studied as superionic materials (in which ionic conductivity is large) for application as fuel cell and battery materials. Experimental studies have revealed that the ionic conductivity in A2B2O7 pyrochlores is sensitive to the chemical composition of the material, with, in particular, B=Ti pyrochlores exhibiting relatively low ionic conductivities and B=Zr pyrochlores having much higher conductivities. This difference in conductivity has been linked to the tendency of the material to exhibit cation disorder (the swapping of A and B cations). The disordering tendency of the material depends on its chemical composition, such that a change in chemistry is often accompanied by a concurrent change in the level of disorder, leaving some doubt as to the true origin (chemistry or disorder) of the enhancement in conductivity. Meanwhile, cation disorder can be controllably introduced into these materials via irradiation and much work has been done examining the disordering that occurs in pyrochlores as a function of the irradiation dose, as these materials are also proposed for nuclear waste forms. However, the two properties - ionic conductivity and radiation-induced disordering - have not been explicitly connected.
Here, in support of ongoing experimental studies, we examine the independent contributions of chemistry and disorder on ionic conductivity in two pyrochlores, Gd2Ti2O7 and Gd2Zr2O7. Using molecular dynamics and accelerated molecular dynamics, we isolate the role that the B-site chemistry and the A-B disorder have on oxygen ionic conductivity. We examine both structural defects, i.e. vacant oxygen sites relative to the basic fluorite structure, as well as intrinsic defects (interstitials and vacancies) that might be present after irradiation. We find contrasting effects of both disorder and chemistry on the mobility of each type of defect. In particular, disorder always increases the conductivity associated with the structural defects, but low levels of disorder can inhibit the motion of intrinsic defects. We contrast this behavior with that found in AB2O4 spinels, where disorder decreases the mobility of oxygen defects. These results highlight the non-trivial and contrasting effects associated with ionic conductivity in these complex materials.
4:00 AM - ZZ4.04
Non-Adiabatic Aspects of the Initial Stages of Radiation Damage
Magdalena Caro 1 Alfred Correa 2 Alfredo Caro 1
1Los Alamos National Laboratory Los Alamos United States2Lawrence Livermore National Laboratory Livermore United StatesShow Abstract
We report on non-adiabatic aspects of the initial stages of radiation damage, when ions and electrons get out of mutual equilibrium, and energy is exchanged between them, determining the ways radiation energy is dissipated. The hypothesis behind this work is that by understanding the mechanisms of energy dissipation by electrons and ions, we provide a means to manipulate them to reduce the defect production, and quench the damage. Our work describes quantitatively the energy transfer process from electrons to atoms via ionization, a process known as Coulomb explosion.
Recently, we reported on a correlation between nuclear and electronic stopping power that revealed the effects of ionization on the ions dynamics [Correa et al. Phys. Rev. Lett. 108 (2012)069901]. In this work, we use the same TD-DFT methodology to determine the time dependent forces experienced by Ni target atoms as a Ni projectile moves along its trajectory. Similar to our previous observation, we find large differences in the magnitude of momentum transfer as compared to the value given by the adiabatic approximation. This effect is the quantitative signature of the Coulomb explosion (CE). With these results in mind, we discuss the impact CE has on the modification of the energy dissipation pathways in the early stage of defect formation.
Implications of these results in more accurate computer simulations of radiation damage are expected, as both the nuclear and electronic aspects of the problem are both included in the atomic-scale simulations of radiation damage.
Work supported by the Energy Dissipation to Defect Evolution Center (EDDE), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science.
4:15 AM - ZZ4.05
Acceleration of Cr Precipitation in alpha;-Fe by Irradiation
Frederic Soisson 1
1CEA Saclay Gif-sur-Yvette FranceShow Abstract
Iron-chromium alloys are the basis for ferritic and ferritic-martensitic steels that will be used in future fission (generation IV) and fusion nuclear reactors. With Cr contents between typically 8 to 12%, or even 14% in the matrix of some oxide dispersion-strengthened steels, one expects a precipitation of a Cr-rich phase (α&’), leading to the hardening and embritshy;tlement of the materials. For such compositions and at temperatures of interest, the kinetics of precipitation during a thermal ageing is usually very slow, but it can be strongly accelerated under irradiation, due to point defect supersaturation. We present a modeling of the α&’ precipitation under irradiation, based on atomistic kinetic Monte Carlo simulations, with parameters fitted on ab initio calculations. The Monte Carlo simulations are combined with a cluster dynamics model to get an accurate description of the evolution of sink densities, which control the point defect supersaturation. The simulations are used to predict the acceleration factor, depending on the alloy composition, irradiation flux and temperature. They are compared to available experimental results. The possible effects of ballistic mixing (which occurs in displacement cascades) and of the strong interaction between carbon atoms and vacancies, are also discussed.
4:30 AM - ZZ4.06
Dislocation Core Reconstruction Induced by Solute Atom Segregation in bcc Metals
Berengere Luthi 1 Lisa Ventelon 1 David Rodney 2 Francois Willaime 1
1CEA Gif-Sur-Yvette France2Universiteacute; Lyon I Villeurbanne FranceShow Abstract
In order to better understand plasticity in alloys, it is important to describe the deformation mechanisms with accuracy, and in particular to understand how dislocations, responsible for the plastic deformation, interact with solute atoms. Long-range interactions are well described with continuum elasticity theory, whereas short-range interactions depend on atomistic mechanisms. Previous ab initio studies of the ½<111> screw dislocation in body centered cubic (bcc) metals showed that in pure metals, the dislocation core adopts a symmetrical configuration, the easy core configuration, centered on a triangle of first-neighbor <111> atomic columns where helicity is reversed with respect to the bulk. The other core configurations - the asymmetric core, the hard core where the three <111> core atomic columns are at the same altitude, and the split core centered near an atomic column - are all unstable in pure bcc metals .
In this work, we investigate the effect of interstitials solute atoms on the ½<111> screw dislocations in bcc metals using ab initio calculations performed using the VASP code. First considering Fe(C), our DFT calculations show that, when a row of solute atoms is added in the neighborhood of the dislocation core, both the dislocation and the solute atoms reorganize to form a low-energy configuration. We find surprisingly that the dislocation adopts a hard-core configuration with the solute atoms placed at the center of regular trigonal prisms formed by the Fe atoms inside the three <111> core atomic columns . This structure is similar to the building unit of Fe3C cementite. We obtained the same core reconstruction with other solutes (B, N, O) in Fe and in other metals (W, Mo). Within this unexpectedly stabilized hard core, the interaction energy between the dislocation and the solute atoms is strongly attractive and leads in equilibrium conditions at room temperature to a core saturation by solute atoms, even for very low carbon concentrations in bulk. Consequences on the dislocation mobility and relations to dynamical strain ageing will also be discussed.
 L. Dézerald, L. Ventelon, E. Clouet, C. Denoual, D. Rodney and F. Willaime, “Ab initio modeling of the two-dimensional energy landscape of screw dislocations in bcc transition metals”, Phys. Rev. B 89, 024104-13 (2014).
 L. Ventelon, B. Lüthi, E. Clouet, L.Proville, B. Legrand, D. Rodney and F. Willaime, “Dislocation core reconstruction induced by carbon segregation in bcc iron”, submitted to Phys. Rev. B Rapid Com. (in press)
4:45 AM - ZZ4.07
Modeling Radiation Induced Segregation in Fe-Y-O Alloys
Christopher Nellis 1
1Virginia Polytechnic and State University Blacksburg United StatesShow Abstract
Radiation induced segregation of alloying elements in nanostructured ferritic alloys (NFAs), a material used for fuel cladding, results in embrittlement at grain boundaries, which comprises the lifetime of the material. The study models this segregation by the creation, migration, recombination, and annihilation of point defects by electron irradiation using rate theory. A progression was used in the development of the models from simplistic pure iron to binary Fe-Y to the complex Fe-Y-O. The rate theory equations break from previous ternary alloy models in literature by modeling the movement of oxygen, an element preferentially found in the octahedral sites and travels by interstitial diffusion. The simulations from both models showed agreement with literature with enrichment of yttrium and oxygen at sinks such as grain boundaries.
ZZ3: Surfaces and Interfaces in Materials Science
Tuesday AM, December 01, 2015
Sheraton, 2nd Floor, Independence West
9:00 AM - *ZZ3.01
Rapid Prototyping of Phase Diagrams
Axel van de Walle 1
1Brown University Providence United StatesShow Abstract
We present an ab initio computational framework for the Rapid Prototyping of Phase Diagrams (RaPPD) of alloy systems. The approach is based on a pre-generated database of special quasirandom structures (SQS) including, not only simple crystal structures (e.g. fcc, bcc, hcp), but also common intermetallic phases with multiple sublattices. Software tools were developed to directly convert SQS ab initio data into standard thermodynamic database format and combine it to elemental SGTE data, thus enabling rapid and effortless generation and visualization of thermodynamic data for multicomponent systems with standard CALPHAD tools. Interface to widely used interactive graphical visualization tools are also demonstrated. A key aspect of the process is a formal method to calculate the formation energies of mechanically unstable phases (which are surprisingly common) that is consistent with SGTE data regarding such phases. The method is illustrated with applications to Rhenium-based alloys.
ZZ5: Poster Session
Tuesday PM, December 01, 2015
Hynes, Level 1, Hall B
9:00 AM - ZZ5.01
Mechanistic Implication in a New Cellulose Derived Cyclopentenone Derivative Synthesis
Liwei Zhao 1 Nnenna Elechi 1 Hua-Jun Fan 1
1Prairie View Aamp;M University Prairie View United StatesShow Abstract
Liquefaction of biomass is one of the major paths in the utilization of nonfood biomass resources for renewable fuels and chemical feedstocks. However, investigations of the liquefaction of biomass have been limited to mineral acids catalysts which often with unstable compounds; many studies failed to identify the compounds in the lique#64257;ed products. Recently, our work reported a highly efficient simple strategy using 1-(1-alkylsulfonic)-3-methylimidazolium chloride ionic liquid as catalysts to liquefy cellulose in ethylene glycol at 180 °C to produce a stable lique#64257;ed oil with a well-de#64257;ned composition of merely three compounds and identi#64257;cation of a cyclopentenone derivative in a cellulose liquefaction process. The focus of this paper is on the computational modeling investigations of such acidic ionic liquid catalyzed liquefaction of cellulose in ethylene glycol. Theoretical results are qualitatively in agreement with experiments. The calculations not only explain the experimental observations but also provide the insight into the conformational, electronic structural and thermodynamic energetic profile of such interactions.
9:00 AM - ZZ5.02
Filiberto Montiel 1
1Universidad Nacional Autoacute;noma de Meacute;xico Meacute;xico MexicoShow Abstract
Molecular diodes based on charge transfer complexes of fullerene with different porphyrins has been proposed and studied theoretically. Current-voltage characteristics and the rectification ratios (RR) of different molecular diodes were calculated using direct ab initio method at PBE/def2-SVP level of theory with D3 dispersion correction the range from -2 to +2 V.
The rectifying effect in molecular junctions of the form metal|molecule|metal, is defined in terms of the absence of inversion symmetry, I(V)ne;-I(-V), where I and V are the current and the applied voltage, respectively. The dominant factors inducing rectification are geometric asymmetry in the molecular junction and the spatial profile of the electrostatic potential.
The highest RR of 32.4 was determined for the complex of C60 with zinc tetraphenylporphyrin at 0.8 V. Other molecular diodes show lower RR, however, all complexes show RR higher than 1 at all bias voltages. The asymmetric evolutions and alignment of the molecules with the applied bias were found to be essential in generating the molecular diode rectification behavior. Metal nature in metalloporphyrins and the interaction porphyrin - electrode significantly affects RR of molecular diode. Large metal ions like Cd2+ and Ag2+ in metalloporphyrins disfavor rectification creating conducting channels in two directions, while smaller ions Zn2+ and Cu2+ favor rectification increasing interaction between gold electrode and porphyrin macrocycle.
9:00 AM - ZZ5.03
Non-Perturbative Analysis of Impurity Effects on the Kubo Conductivity of Nano to Macroscopic Structures
Vicenta Sanchez 2 Fernando Sanchez 2 Carlos Ramirez 2 Chumin Wang 1
1Universidad Nacional Autonoma de Mexico, Instituto de Investigaciones en Materiales Mexico DF Mexico2Universidad Nacional Autonoma de Mexico Mexico City MexicoShow Abstract
The presence of impurities in solids is a source of many interesting effects, particularly relevant in the conductivity, optical properties and specific heat. For instance, in nanoelectronics, such effects could be useful to develop molecular devices such as novel computer architectures [1,2], chemical  and biomedical sensors . However, the inclusion of impurities breaks the Bloch symmetry, restricting the systems that can be addressed theoretically in an exact way to those of few atoms. In this work, we present an alternative method to study the electrical conductance in real-space by means of a renormalization plus convolution method  applied on the Kubo-Greenwood formula for multidimensional systems of macroscopic size with site and bond impurities. The results shows that the spectral average of the conductivity depends strongly on the location of the site and bond impurities in periodic chains. Particularly, when the distance between impurities follows the Fibonacci sequence, we find that the spectral average falls following a power law as the number of atoms in the system grows . In addition, we demonstrate analytical and numerically the presence of novel ballistic transport states in two and three dimensions, when respectively three lines or planes of site impurities for null chemical potential is present . Finally, we analyze the impurity effects on the conductance spectra of periodic and aperiodic solids with nano to macroscopic length when the number of impurities grows.
This work has been partially supported by UNAM-IN113813. Computations were performed at Miztli of DGTIC, UNAM.
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 F. Patolsky, G. Zheng, O. Hayden, M. Lakadamyali, X. Zhuang, C.M. Lieber, Proc. Natl. Acad. Sci. USA101, 14017 (2004).
 V. Sanchez and C. Wang, Phys. Rev. B70, 144207 (2004).
 V. Sanchez, C. Ramirez, F. Sanchez, C. Wang, Physica B449, 121 (2014).
 C. Wang, C. Ramirez, F. Sanchez, and V. Sanchez, Phys. Status Solidi B, 252, 1370 (2015).
9:00 AM - ZZ5.04
Nucleation, Solidification and Grain Growth in Large-Scale Molecular Dynamics Simulation Performed on Graphics Processing Unit
Yasushi Shibuta 1 Shinji Sakane 2 Tomohiro Takaki 2 Munekazu Ohno 3
1Univ of Tokyo Tokyo Japan2Kyoto Institute of Technology Kyoto Japan3Hokkaido University Sapporo JapanShow Abstract
Recent progress in high-performance computational environments have expanded he range of applications of computational metallurgy is expanding very rapidly . We have performed the large-scale molecular dynamics (MD) simulations, which are performed on graphics processing unit (GPU) to discuss the nature of solidification and related properties [1-5]. Up to now, we have revealed the evolution of the grain boundary groove  and the spontaneous evolution of anisotropy in the solid nucleus in the undercooling melt of iron . In this study, homogeneous nucleation from an undercooled iron melt is investigated by the statistical sampling of million-atom MD simulations. The undercooled iron melt in a cell with a size of 53.4 x 53.4 x 4.3 nm3 (1,037,880 atoms) is isothermally undercooled with various temperatures for 10000 ps under zero pressure by a NPT constant condition. The nucleation rate and the incubation time of nucleation as functions of temperature have characteristic shapes with a nose at the critical temperature. This indicates that thermally activated homogeneous nucleation occurs spontaneously in MD simulations without any inducing factor [1,6].
 Y. Shibuta, M. Ohno, T. Takaki, JOM, article in press. (doi:10.1007/s11837-015-1452-2).
 Y. Shibuta, S. Takamoto, T. Suzuki, ISIJ Int., 48 (2008) 1582.
 Y. Watanabe, Y. Shibuta, T. Suzuki, ISIJ Int., 50 (2010) 1158.
 Y. Shibuta, K. Oguchi, T. Suzuki, ISIJ Int., 52 (2012) 2205.
 Y. Shibuta, K. Oguchi, M. Ohno, Scripta Mater., 86 (2014) 20.
 Y. Shibuta, K. Oguchi, T. Takaki, M. Ohno, submitted.
9:00 AM - ZZ5.05
Phase-Field Modeling on Mechanical Switching in Ferroelectric Heterostructures
Bo Wang 1 Zijian Hong 1 Haidong Lu 2 Chang-Beom Eom 3 Alexei Gruverman 2 Long-Qing Chen 1
1The Pennsylvania State University University Park United States2University of Nebraska Lincoln United States3University of Wisconsin-Madison Madison United StatesShow Abstract
The electromechanical coupling between strain gradients and ferroelectric polarization, known as the flexoelectric effect, provides a new mechanical approach to switch the polarization purely mechanically in ferroelectric thin films. This approach has been experimentally demonstrated recently by imposing a loading force via an atomic force microscope (AFM) tip onto the film surface. The critical force required for mechanical switching depends on several factors, such as film thickness, with or without top electrode, tip radius, static or moving tip, etc. Phase-field modeling serves as an effective method to study the domain structure evolution of ferroelectric films during the polarization switching process. By performing a series of phase field simulations, we study the flexoelectric polarization switching realized by AFM tip pressing against the Graphene/BaTiO3/SrTiO3 heterostructure. Local control of nanoscopic ferroelectric domains is realized in the ferroelectric capacitor structure due to the localization of strain gradients generated by the AFM tip. With 1 nm graphene on top of 19-nm-thick BaTiO3 thin film, the critical force is estimated to be around 2000 nN. It is also shown that the critical force is significantly influenced by loading conditions, misfit strain, graphene thickness and built-in bias. In addition, we have set a limit for the maximal thickness of graphene top electrode in order to realize mechanical switching in the heterostructure, which is predicted to be about 3 nm. The phase-field modeling results show good agreements with experimental observations and give insights to the better control of mechanical switching in ferroelectric heterostructures.
9:00 AM - ZZ5.06
First-Principles Study of Electronic Properties of FeCrxSe Alloys
Sandeep Kumar 1 Surender Kumar 1 Prabhakar P Singh 1
1Indian Institute of Technology Bombay Mumbai IndiaShow Abstract
We have performed first-principles study of electronic properties of FeCrxSe ( x =0.0, 0.01, 0.02, 0.04) alloys using Korringa-Kohn-Rostoker Atomic Sphere Approximation within the coherent potential approximation (KKR-ASA-CPA). We found from our calculations that the excess of Cr into FeSe significantly affects the electronic structure with respect to the parent FeSe. The results have been analyzed in terms of changes in the DOS, PDOS, band structures, Fermi surface, bare Sommerfeld constant and the superconducting transition temperature of FeCr0.01Se , FeCr0.02Se and FeCr0.04Se alloys respectively. Our calculations show that calculated Tc are in good agreement with the experimental results for these alloys.
9:00 AM - ZZ5.07
First-Principles Calculation of Metal-Doped CaAlSiN3: Material Design for New Phosphors
Seunghun Jang 1 Jino Im 1 Bo Keuk Bang 1 Chang Hae Kim 1 Hyunju Chang 1 Ki-jeong Kong 1
1Korea Research Institute of Chemical Technology Daejeon Korea (the Republic of)Show Abstract
Eu-doped CaAlSiN3 (CASN) is widely utilized as an efficient red phosphor; however, the high price of rare-earth metals has driven efforts toward finding non-rare-earth metal dopants. We report first-principles calculations based on density functional theory (DFT) and geared toward identifying new non-rare-earth metal dopants for use in the CASN-based phosphors. We calculated the formation energies, the electronic structures, and the optical absorption spectra of various metal dopants (Eu, Mn, Sn, and Bi) in CASN. The calculated density of states, band structures, and absorption spectra were consistent with previous experimental observations obtained from Eu- and Mn-doped CASN. The DFT calculations suggested that Sn and Bi are promising candidates as non-rare-earth metal dopants in CASN-based phosphors. Our calculations demonstrate that DFT-based first-principles calculations provide a viable tool for finding new phosphor materials.
9:00 AM - ZZ5.08
An Elemental Quest for Functional Materials: From Metastable Linkage Isomers to Hybrid Halide Perovskites
Jessica Bristow 1 Federico Brivio 1 Keith Tobias Butler 1 Clovis Caetano 1 Jarvist Moore Frost 1 Christopher Hendon 1 Adam J. Jackson 1 Jonathan M. Skelton 1 E. Lora da Silva 1 Katrine L. Svane 1 Ruo Xi Yang 1 Suzanne K. Wallace 1 Lucy Whalley 1 Aron Walsh 1
1University of Bath Bath United KingdomShow Abstract
Building on our understanding of the chemical bond , advances in synthetic chemistry, and large-scale computation, materials design is becoming a reality . We will present our recent progress in this regard across three strands of research: (i) harnessing of meta-stable states induced by temperature, light and pressure ; (ii) the development of electroactive metal-organic frameworks ; (iii) the optimisation of emerging materials for photovoltaics, including kesterite and perovskite structured compounds . A major challenge is the accurate description of finite temperature effects including lattice vibrations and structural disorder, for which we employ many body  and multi-scale approaches . While, we note a number of successes, including the validation of the timescales of orientational disorder in methylammonium lead iodide by quasi-elastic neutron scattering , there remains a significant amount of work left to complete this quest.
This work has benefited from funding by the EPSRC, the ERC, and the Royal Society.
1. L. Pauling, The Nature of the Chemical Bond, Cornell University Press (1960).
2. A. Walsh, Nature Chem. 7, 274 (2015).
3. J. M. Skelton et al, CrystEngComm 17, 383 (2015).
4. C. H. Hendon and A. Walsh, Chem. Sci. 6, 3674 (2015).
5. K. T. Butler, J. M. Frost and A. Walsh, Energy Environ. Sci. 8, 828 (2015).
6. J. M. Skelton et al, APL Mater. 4, 041102 (2015).
7. J. Buckeridge et al, Chem. Mater. 27, 3844 (2015).
8. A. M. A. Leguy et al, Nature Comm. 6, 7134 (2015).
9:00 AM - ZZ5.09
Using Artificial Neural Networks to Predict Processing-Microstructure Relationships in 7xxx-series Aluminum
Ashley Nelson Goulding 1 Hayden McLeod 1 Tom H. Sanders 1 Richard W. Neu 1
1Georgia Institute of Technology Atlanta United StatesShow Abstract
The relationship between processing, mechanical properties, and microstructure of a material is highly complex. Understanding these relationships helps researchers optimize and predict a material's performance. However, existing mathematical and physical mechanism-based models are not always capable of modeling such complex systems to a high degree of accuracy. In particular, there are some systems such as 7xxx series aluminum that are so complex that there has been little to no success using conventional modeling methods. Artificial neural networks (ANNs) offer an alternative method of modeling these relationships. These are highly accurate mathematical models that can predict the cause-effect relationships of complex systems with a small amount of computational power. To use this method, the user needs to identify the primary input and output attributes and have generated empirical data linking these attributes. The ANNs can establish these linkages from the purely empirical data and without any understanding of the physical mechanisms that control the outputs. This makes them well suited for modeling materials and their properties, and they have already found some success in this area. Here we use ANNs to predict the link between processing route attributes, such as solution-treatment temperature, quench rate, and aging-treatment, and the microstructure attributes including grain size, degree of recrystallization, and strengthening precipitate size and volume fraction, of 7050 aluminum.
9:00 AM - ZZ5.10
Grain Growth Modeling and Control with Local Temperature Gradients
Yixuan Tan 1 Chengjian Zheng 1 John Wen 1 Antoinette Maniatty 1
1Rensselaer Polytechnic Institute Troy United StatesShow Abstract
Grain size has an important effect on the performance of metallic materials, and thus, controlling the grain size during processing is a key concern for process designers. Grain growth is a complicated process that is affected by many factors, including temperature, deformation, and microstructural features. In this work, we focused on developing methods to control the local grain size through a combination of model based prediction and feed-forward/feedback control. In this work, the Monte Carlo Potts model is used to predict grain size evolution, and is then coupled to a control algorithm to control the local grain size. In a Monte Carlo grain growth simulation, the physical domain is discretized into N evenly spaced sites, and in each Monte Carlo step, sampling (site selection) is randomly performed N times, with the probability of the grain orientation at a site switching related to the change in energy. Conventionally, the Monte Carlo Potts model is utilized to simulate grain growth assuming a uniform temperature field, and thus, a uniform site selection probability. However, it may be possible, and even desirable, to have temperature gradients at the grain scale. To model grain growth in the presence of a local temperature gradient, a site selection probability function that biases the Monte Carlo sampling based on the local temperature may be used. The primary biased site selection probability function in the literature for handling local temperature variations assumes a grain growth exponent n = 2, where the average grain diameter grows proportional to t1/n, where t is time. However, there is experimental evidence that the grain growth exponent may deviate from n = 2. In this work, a more general site selection probability function is derived that allows for different growth exponents. The Monte Carlo simulation is then linked to a control algorithm to determine the temperature field history to move towards a target microstructure. This work builds an interface for industrial control, allowing strategic temperature manipulation for achieving the desired material microstructure statistics, and therefore systematic advances in reducing the materials development cycle are expected.
9:00 AM - ZZ5.11
A Finite Element Model for the Electrical Microstructure of Rough Electrodes in Multi Layer Ceramic Capacitor Applications
James Peter Heath 1 Julian Dean 1 John Harding 1 Derek Sinclair 1
1University of Sheffield Sheffield United KingdomShow Abstract
We investigate how the physical microstructure of electrode layers in multi layer ceramic capacitors (MLCCs) can influence the electrical microstructure using a three dimensional finite element model. Our finite element code  solves Maxwell&’s equations in time and space for an alternating electric voltage in the milli- to mega- Hertz frequency range across a simple configuration consisting of a ceramic microstructure with planar electrodes on either side. This allows us to compare our results with experimental impedance spectra. The strength of our finite element approach is that we can visualise and measure the distribution of electric field and current density in three dimensions providing information on which microstructural features contribute most to electrical heterogeneity.
In this work we focus on the electrode. We consider both the morphology (electrode roughness) and material heterogeneity (pore and ceramic inclusions within the electrode). Our model consists of rough electrode surfaces with granular ceramic layers. To help analyse our systems we have developed a statistical analysis of conduction pathway lengths, provided by a stream trace of the current density vector field . This links the electrical microstructure and the simulated impedance spectra, allowing for a more detailed explanation of the physical meaning of impedance measurements.
We start with a simple system composed of a homogenous layer of ceramic material with a rough interface between the electrodes similar to the work by Samantaray et al . We add resistive grain boundaries to this model and examine the electrical microstructure to explain changes in the impedance spectra. This approach is repeated for other microstructural features so that their contribution to the electrical response can be studied both in isolation and in combination with each other. Finding the features that dominate the electrical response will enable us to prioritise areas for further development in the optimisation of MLCC devices.
 J.Dean, J.H. Harding and D.C. Sinclair; J. Amer. Ceram. Soc. 97 (2014) 885.
 J.P. Heath, J.Dean, J.H. Harding and D.C. Sinclair; J. Amer. Ceram. Soc. 98 (2015) 1925.
 M.M. Samantaray, A. Gurav, E.C. Dickey and C.A. Randall; J. Amer. Ceram. Soc. 95 (2012) 257.
9:00 AM - ZZ5.12
High-Throughput Testing of Stress Corrosion Cracking Susceptibility in 7050 Aluminum Alloys
Marika Manuud 1 Ashley Nelson Goulding 1 Tom H. Sanders 1 Preet Singh 1 Richard W. Neu 1
1Georgia Institute of Technology Atlanta United StatesShow Abstract
The 7xxx series of aluminum alloys, consisting primarily of aluminum, zinc, magnesium, and copper is of high value to the aerospace industry and accordingly requires a good balance between strength and stress corrosion cracking (SCC) resistance. This work focuses specifically on 7050 aluminum alloys and investigates the effects of 18 different processing treatments on stress corrosion cracking (SCC) susceptibility. Traditional SCC tests are time-consuming and expensive. Therefore, this work explores using potentiodymanic polarization curves as a method of high-throughput SCC testing by quickly obtaining information on corrosion potential, corrosion current density, and open circuit potential for each sample. By combining this information with the relevant characteristics of the grain boundary microstructure, obtained by SEM, the severity of the SCC can be plotted in a style similar to an Ashby Deformation Map. These maps allow for the relative quantitative comparison of SCC as a function of processing methods and their resulting microstructures.
9:00 AM - ZZ5.13
Combined Quantum and Reactive Molecular Dynamics Simulations of Nanocarbon Synthesis by High-Temperature Oxidation of Nanoparticles
Chunyang Sheng 2 1 Rajiv Kalia 1 2 Ying Li 1 3 Aiicniro Nakano 1 2 Kenichi Nomura 1 Pankaj Rajac 2 Kohei Shimamura 4 Fuyuki Shimojo 4 Priya Vashishta 1 2
1University of Southern California Los Angeles United States2University of Southern California Los Angeles United States3Argonne National Lab Argonne United States4Department of Physics, Kumamoto University Kumamoto JapanShow Abstract
High-temperature oxidation of silicon-carbide nanoparticles (nSiC) underlies a wide range of technologies from high-power electronic switches for efficient electrical grid, thermal protection of space vehicles, to self-healing ceramic nanocomposites. Our combined quantum molecular dynamics (QMD) and reactive molecular dynamics (RMD) simulations revealed unexpected formation of nanocarbon products during high-temperature oxidation of nSiC. The nanocarbon with a unique porous geometry may find various applications including supercapacitors, battery electrodes, and biomedical imaging. We first performed small QMD simulations, which were then used to train an RMD force field using a multi-objective genetic algorithm. Subsequently, 112 million-atom RMD simulations were performed to encompass large spatiotemporal scales required for the formation of enough reaction products to assess their geometry.
This research was supported by the Department of Energy (DOE), Office of Science, Basic Energy Sciences, Materials Science and Engineering Division, Grant # DE-FG02-04ER-46130.
9:00 AM - ZZ5.14
Atomistic Understanding and Prediction of Alloying Effect of Si on Yield Strength of Steel
Shuhei Shinzato 1 Masato Wakeda 1 Hajime Kimizuka 1 Shigenobu Ogata 1 2
1Osaka University Osaka Japan2Kyoto University Kyoto JapanShow Abstract
Iron is widely used as structural material and it is well-known that strength of iron significantly increases due to alloying elements such as silicon, even though it contains only a few atomic percent alloying element. However, reason of such highly nonlinear alloying effect has not been fully clarified from atomic level. Yield strength of coarse grained bcc metals is mainly controlled by mobility of screw dislocation as a result of kink nucleation and migration in screw dislocation. Therefore, atomistic understanding of solute atom effect on kink nucleation and migration processes is crucial for understanding of alloying effect, and moreover, predicting yield strength.
In this study, a framework for predicting macroscopic yield stress of dilute Fe-Si alloy is presented. The framework is fully based on atomistic analysis of screw dislocation motion, such as kink nucleation and migration, using newly developed interatomic interaction between Fe and Si based on first-principles density functional theory. Using the interatomic interaction, we found that screw dislocation and solute Si atom have a short-ranged attractive interaction.
Firstly, activation barriers of kink nucleation and migration processes were obtained as a function of applied shear stress using nudged elastic band (NEB) method. Si significantly decreases the activation barrier of kink nucleation process when the kink approaches to the Si atom and vice versa, and its magnitude decreases with increasing applied shear stress. Si also strongly affects to the kink migration process by increasing the activation barrier of kink migration. Based on these atomistic information of activation energy and using transition state theory, we formulated frequencies of kink nucleation and migration as a function of solute concentration, temperature and applied shear stress. Then, eventually yield strength, i.e. critical resolved shear stress (CRSS), was formulated as a function of the frequencies.
Finally, predicted yield strength using this framework was compared with experimental result in various temperatures, solute concentrations and strain rates. Our framework quantitatively reproduces temperature, solute concentration and strain rate dependences of yield strength without using any empirical data.
9:00 AM - ZZ5.15
Hydrogen and Carbon Interactions near Lattice Defects in BCC Iron by Combined Theoretical Methods
Tien Quang Nguyen 1 Hajime Kimizuka 1 Shigenobu Ogata 1 2
1Osaka University Toyonaka Japan2Kyoto University Kyoto JapanShow Abstract
Hydrogen has attracted much attention in iron/steel research since its presence can significantly degrade the mechanical properties of high-strength steel. One of the important issues is the trap state of hydrogen with various defects in steel, involving carbon and vacancy. In addition, the interaction between dislocations and hydrogen is considered to play an important role in hydrogen-related fractures for metals; it has been reported that hydrogen affects the dislocation stability/mobility in iron. However, the effects of carbon on the interaction of hydrogen with dislocation and the role of carbon and hydrogen on the void formation process in iron remain unclear. Hence, at first, within the atomic scale, we performed ab-initio simulations based on Density Functional Theory to investigate the stability and interactions of hydrogen and carbon around point defects in Fe-C-H systems. We found, among others, that as the number of trapped carbon increases, the accumulation of hydrogen around vacancy is reduced and vice versa. Furthermore, we have extended the system to a much larger scale by developing an interatomic potential for Fe-C-H system to model non-equilibrium processes using Molecular Dynamics. The effect of carbon on the distribution of hydrogen near defects, the binding of hydrogen with defects as well as the effects of hydrogen and carbon on the process of nucleation and void formation at various temperatures are analyzed.
9:00 AM - ZZ5.16
Stability of Pt2Ru3 Anode Catalysts against CO in Fuel Cell by the Novel Materials Informatics Method
Shuhei Saito 1 Alam Md Khorshed 1 Hiromitsu Takaba 1
1Kogakuin University Tokyo JapanShow Abstract
Proton exchange membrane fuel cell (PEMFC) have been developed intensively for applications in residential co-generation systems or electric vehicles. Low temperature fuel cells function by converting the energy released in the oxidation of H2 or other hydrogen containing fuels into electrical energy. If pure H2 is used as fuel, Pt is a good anode material, but Pt anodes are deactivated by CO in the H2 fuel. Among various anode catalysts developed, Pt-Ru alloys are still best candidates. The Pt-Ru alloy exhibit both high CO-tolerance and acceptable durability under practical operating conditions. Recently some studies reported that well mixed Pt and Ru in the Pt2Ru3 alloys catalysts can improve the tolerance level of CO poisoning. At the present there is a great challenge to design anode catalysts that can accommodate CO density 300 ppm ~ 500 ppm for the cost reduction and toward larger scale commercialization. CO tolerance mechanisms of monodisperse Pt-Ru nanoparticle supported on high surface area of carbon black investigated by different experimental groups. On the other hand, quantum chemical calculation, investigated the adsorption phenomena of atoms on the catalytic surface area. However, still it is not clear of CO adsorption and its relationship to the structural change of catalysts and changing it sequence. To get desirable performance of the Pt2Ru3 catalyst we need to know exact atomic arrangement of Pt and Ru in the Pt2Ru3 alloys. Therefore in this study, we have applied a quantum chemical calculation and materials informatics to elucidate the behavior of the Pt2Ru3 alloy catalyst against CO at atomic level.
ECS Transactions, 61(13), (2014) 1-6.Md. Khorshed Alam and Hiromitsu Takaba
9:00 AM - ZZ5.17
Half-Metallicity in Armchair Blue Phosphorene Nanoribbons: A First Principles Study
Naresh Alaal 1 3 Nikhil Medhekar 2 Alok Shukla 3
1IITB-Monash Research Academy Mumbai India2Monash University Melbourne Australia3IIT Bombay Mumbai IndiaShow Abstract
We performed first principles spin polarized calculations to study electronic properties of Hydrogen and Fluorine terminated armchair blue phosphorene nanoribbons (ABPNRs). We considered the ABPNRs with fully passivated and partially passivated edges with H and F atoms. We found fully edge hydrogenated and fully edge flourinated ABPNRs are indirect band gap semconductors. But partially edge saturated ABPNRs with H and F atoms exhibit half metallic behavior. Partially edge passivation will introduce new electronic states around the fermi level results into spin-up and spin-down channels. Our results suggest that fully edge passivated ABPNRs have potential to use in semiconducting device applications and partially edge passivated ABPNRs can be used in spintronic applications.
9:00 AM - ZZ5.18
Fast Prediction of Breakdown Strength Enhancement Effect of Functional Groups in Polymer Nanocomposites
Ke Wu 1 Tyree Ratcllif 1 Yanhui Huang 2 Linda S. Schadler 2 Curtis M Breneman 1
1Rensselaer Polytechnic Institute Troy United States2Rensselaer Polytechnic Institute Troy United StatesShow Abstract
Polymer nanocomposites have shown great potential as dielectric materials. It has been found that the introduction of nanoparticles can lead to a significant enhancement in the dielectric breakdown strength. Further improvement has been observed when specific functional groups that have the potential to trap electrons have been grafted to the particle surface. The optimization of these functional groups is a key part of our research effort. At present, there is no well-accepted theory that describes the mechanism behind the observed improvements, although there is general agreement that scattering and trapping of carriers is important.
We are applying quantum mechanical computation as well as material quantitative structure-property relationship (MQSPR) modeling to the optimization of nanodielectric materials. Instead of trying to model the whole process of dielectric breakdown, we have made a limited number of assumptions that are well accepted. The key assumption is that the breakdown occurs via electron avalanche. The breakdown phenomenon starts with electron intrusion, where a small number of free electrons move into the bulk material and induce more free electrons by impact ionization. The foreign species, like the functionalized nanoparticles, may provide additional low energy states, and electrons would be more likely to reside in these states so that the energy distribution of entire injected carrier population could be shifted down at equilibrium. This process could be described as follows: Charged Polymer + Neutral Particle → Neutral Polymer + Charged Particle. The effect of functional groups can be simply estimated by calculating the charge transfer energy cost from charged polymers to neutral particles. The electron affinity (EA) and ionization energy (IE) were used to measure the energy cost for negative and positive charges.
Direct quantum computation of the grafted nanoparticles requires enormous resources and was infeasible for broad studies. In this study, the quantum computation was done using the DFT method b3lyp/6-311++G** on Si(OH)3 based functional groups with only a small contribution to the HOMO/LUMO orbitals from Si(OH)3 observed. The machine learning model was built using partial least square with feature selection.
A clear reverse correlation was observed between breakdown strength of polymer nanocomposite (epoxy with functionalized silica) and EA+IE. MQSPR models for EA and IE were also built. The models demonstrate good predictive capability. The 10-fold cross-validation R2 is 0.93 and 0.85 for EA and IE respectively.
In correlating the energy change between charged matrix polymers and functionalized nanoparticles with the dielectric breakdown strength, it was observed that the breakdown strength increased as the energy change increased. Thus, the energy change could be used as an indicator to predict the breakdown strength change in nanodielectrics due to the addition of functional groups to the nanoparticles.
9:00 AM - ZZ5.20
Scalable GW-BSE Software Development
Minjung Kim 1 Subhasish Mandal 1 Sohrab Ismail-Beigi 1 Qi Li 2 Glenn J Martyna 2 Eric Mikida 3 Eric Bohm 3 Nikhil Jain 3 Laxmikant Kale 3
1Yale University New Haven United States2IBM T. J. Watson Research Center Yorktown Heights United States3University of Illinois at Urbana-Champaign Champaign United StatesShow Abstract
Density functional theory (DFT) has been successful in describing the properties of materials, specically ground state properties, e.g., structural, mechanical, and vibrational properties. To develop and design new functional materials such as photovoltaic devices, however, understanding ground state properties is not always sufficient especially when electrons are excited in the key physical processes. The GW-Bethe Salpeter Equation (GW-BSE) approach is the fully ab initio method of choice for general materials problems involving one- and two-electron excitations (i.e., band properties and optical excitations). However, GW calculations are typically extremely expensive compared to DFT calculations which has limited the regular application of GW to a large-scale materials problem. This is in part due to the computational load typically requiring enormous numbers of FFTs for plane wave bases; separately, the memory requirements for most GW algorithms can be daunting.
We describe our collaborative efforts to develop new software and new algorithms that permit GW calculations to be performed on large-scale parallel computers efficiently. We illustrate calculations of the dielectric screening matrix which is one of the most expensive parts of a GW calculation. Our approach uses a real-space representation of the polarizability that avoids extensive use of FFTs, and we compare its behavior to the more conventional G-space GW approaches. The self-energy correction calculations via both real-space approach and eigendecomposition method of dielectric matrix are presented as well. We also summarize the capabilities of our highly scalable Car-Parinello ab initio molecular dynamics simulation package "OpenAtom"  which our GW software is being interfaced. We briefly describe how OpenAtom leverages the Charm++ parallel libraries [2, 3] to achieve admirable parallel scaling on large problems as well as signicantly reduce the complexity of software parallelization from the viewpoint of the scientic user.
 E. Bohm, A. Bhatele, L. V. Kale, M. E. Tuckerman, S. Kumar, J. A. Gunnels and G. J. Martyna: "Fine grained parallelization of the Car-Parrinello ab initio MD method on Blue Gene/L" IBM J. RES. & DEV. VOL. 52 NO. 1/2, 2008.
 G. Martyna, E. Bohm, R. Venkataraman, L. Kale, and A. Bhatele: Chapter 5: OpenAtom: Ab-initio Molecular Dynamics for Petascale Platforms, BOOK: Parallel Science and Engineering Applications: The Charm++ Approach
9:00 AM - ZZ5.21
Elucidating the Structural Disruption of Crystallized Tristearin Using Mixtures of Nanodiamonds and Surfactants
Zak Elliot Hughes 1 Tiffany Walsh 1
1Deakin University Geelong AustraliaShow Abstract
An understanding of the structure and properties of the aqueous interface of fats, or triacylglycerols (TAGs), is important for a number of applications including food processing, nanomedicine (via the implementation of solid-lipid nanoparticles) and laundry detergents. The effective removal of crystallized TAGs from fabrics and other surfaces can be expensive in both time and energy, requiring high temperatures (330K+) even with modern detergents. Recently, however, it has been shown that employing nanodiamonds (NDs) in combination with an anionic surfactant (sodium dodecylbenzene sulfonate, SDBS) can lead to the removal of tristearin (TS), a model fatty acid, at room temperatures. While raising significant prospects for the use NDs in cold-water laundering products, the precise mechanism for the action of NDs and surfactants at the TS-aqueous interface is still uncertain. Molecular dynamics (MD) simulations of these systems can provide important information about the interactions of the different components at the atomistic level, and give clues to the optimization of these ND/surfactant formulations for improved performance.
For the first time, the TS-aqueous interface has been characterized using MD simulations. The lipids form an ordered gel phase, with the fatty acid tails packing in a hexagonal arrangement. In the presence of SDBS, the structure of the TAG phase shows no sign of structural instability, despite the ability of surfactant molecules to embed within the TS bilayer. However, in the combined presence of NDs and SDBS, the structure of the TS bilayer is disrupted. We find that the surface charge density on the NDs is a major factor in the complex interplay of the interactions between the different species. Our findings provide guidance for the development of energy-efficient solutions for the low-temperature removal of crystallized fats, as well as advancing our understanding of the important TAG-aqueous interface.
 Almeida, A and Souto, E; Solid lipid nanoparticles as a drug delivary system for peptides and proteins, Adv. Drug Del. Rev.,2007, 59, 478-490.
 Cui, X., et al.; Nanodiamond promotes surfactant-mediated triglyceride removal from a hydrophobic surface at of below room temperature, ACS Appl. Mater. Interfaces, 2012, 4, 3225-3252.
 Hughes, Z.E. and Walsh, T.R.; Tristearin bilayers: Structure of the aqueous interface and stability in the presence of surfactants, RSC Advances, 2015, 5, 49933-49943.
9:00 AM - ZZ5.22
Improving the AC Ballistic Conductivity in Branched Nanowires: A Renormalization Plus Convolution Approach
Chumin Wang 1 Carlos Ramirez 2 Fernando Sanchez 2 Vicenta Sanchez 2
1Universidad Nacional Autonoma de Mexico, Instituto de Investigaciones en Materiales Mexico DF Mexico2Universidad Nacional Autonoma de Mexico Mexico City MexicoShow Abstract
The electronic transport in solids with a large number of impurities is still an unclear issue, where the interference between the electronic wavefunction and aperiodic potentials has multiple consequences. Recently, branched nanowires with designed three-dimensional (3D) morphology have been obtained, and they have wide applications in energy conversion and storage devices . Nonlinear electrical properties of branched nanowires have been also reported . Since the presence of impurities avoids the use of the Bloch theorem as well as the reciprocal lattice, such system should be addressed in the real space. In this work, a renormalization plus convolution method developed for the Kubo-Greenwood formula  is used to calculate the electronic transport in branched nanowires. We report enhancements to the ballistic AC conductivity when periodically or quasiperiodically placed Fano-Anderson impurities are introduced to an otherwise periodic nanowires, which is connected to two semi-infinite periodic leads at its ends . Moreover, the temperature variation analysis suggests the possibility to observe these resonant AC conducting peaks for specific electronic filling and applied electric field oscillating frequency even at room temperature. Experimentally, the chemical potential position in the band structure of a nanowire can be modified by an applied gate voltage . Finally, the AC conductance spectra of nanotubes with Fano-Anderson impurities will also be presented.
This work has been partially supported by UNAM-IN113714. Computations were performed at Miztli of DGTIC, UNAM.
 C. Cheng and H.J. Fan, Nano Today7, 327 (2012).
 D.B. Suyatin, et al., Nano Lett.8, 1100 (2008).
 V. Sanchez and C. Wang, Phys. Rev. B70, 144207 (2004).
 V. Sanchez and C. Wang, Phil. Mag.95, 326 (2015).
 J. Moon, et al., Nano Lett.13, 1196 (2013).
9:00 AM - ZZ5.23
"Pentahexoctiterdquo; A New 2D Allotrope of Carbon
Babu Ram 1 Aaditya Manjanath 1 Abhishek Kumar Singh 1
1Indian Institute of Science Bangalore IndiaShow Abstract
Since, the discovery of graphene, 2D materials has attracted immense interest among the scientific community. It has given a new route to explore the carbon based 2D materials. Carbon can exists in several hybridization states, which gives it an unique ability to adopt novel atomic arrangements such as rings, sheets, tubes, and solids. In this study, we report a new sp2 hybridized 2D allotrope "pentahexoctite” made out of 5-6-8 rings of carbon. This planar sheet has Cmm symmetry and phonon calculation confirms its dynamical stability. It has mechanical strength comparable with that of graphene. Interestingly, this 2D sheet is metallic and has band structure with combinations of direction dependent flat as well as dispersive bands. In addition, carbon nanotubes (CNTs) are generated out of this sheet, shows chirality-dependent electronic and mechanical properties. Along with these remarkable properties, the "pentahexoctite" sheet joins the family of 2D allotropes of carbon. 
1. Babu Ram Sharma, Aaditya Manjanath, and Abhishek K. Singh, Sci. Rep. 4, 7164 (2014
9:00 AM - ZZ5.24
Modeling and Simulation Method for Triboelectric Nanogenerators-- A New Mecahnical Energy Harvesting Device
Simiao Niu 1 Zhong Lin Wang 1
1Georgia Inst of Tech Atlanta United StatesShow Abstract
The tremendous development of portable electronics and sensor networks makes it an urgent requirement to develop sustainable and stable energy sources for them. Recently, triboelectric nanogenerators (TENGs) based on contact electrification and electrostatic induction have shown unique merits including large output power, high efficiency, low weight, cost effective materials, and simple fabrication. Requirements for continuing improving their output performance demand rational design and careful optimization of both materials and structures of TENGs. Thus a thorough theoretical understanding of TENGs and their systematical simulation method is completely urgent in the whole research field.
In this research, we developed the first theoretical governing equation (V-Q-x relationship) and the first lumped-parameter equivalent circuit model for TENGs. Then the first systematical simulation tool and method for TENGs is built, which includes the complex coupling of both electrostatic and circuit simulation. Utilizing this simulation tool, the load characteristics of TENGs have been clearly uncovered. When TENGs are connected with resistive loads, a “three-working-region” behavior is shown because of the impedance match between the generator and the load. There exists an optimum load resistance to maximize the generator energy output, which can be carefully controlled by the TENG structural parameter and the frequency of the external mechanical motion. Besides, when TENGs are utilized to charge a capacitor in a periodic external motion, it is equivalent to utilizing a DC voltage source with an internal resistance to charge the capacitor. Same as the resistive load, there exists an optimum load capacitance under which the maximum energy can be stored. This optimum load capacitance is proportional to both the inherent TENG capacitance and the charging cycle number.
With the developed theoretical model and simulation method, optimized performance of triboelectric nanogenerators has been reached. The attached-electrode contact-mode and sliding-mode TENGs need to maintain the minimum gap size to be much smaller than their effective dielectric thickness. The electrostatic shield effect of the primary electrode is the main design consideration of single-electrode TENGs. Contact-mode freestanding TENGs have superior linear characteristics and sliding-mode freestanding TENGs have excellent height tolerance of the moving object. For the most-complicated grating structure, an optimum number of grating units and an optimum unit aspect ratio due to the edge effect can be calculated with my model. The theory presented here is the first interpretation and analysis of the TENGs&’ working principle, clearly showing its unique operation characteristics, which will be able to serve as important guidance for rational design of the device structure as a power source in specific applications and self-powered systems. 
1. S. Niu, Z. L. Wang, Nano Energy, 2015, 14, 161.
9:00 AM - ZZ5.25
Phase Diagram Assisted Development of Nd-Mg-Ni Hydrogen Storage Alloys
Qun Luo 1 Qian Li 1 Kuo-Chih Chou 1
1Shanghai University Shanghai ChinaShow Abstract
We focus on the development of novel hydrogen storage alloys of Nd-Mg-Ni system because their attractive kinetic properties promoted by catalytic elements Nd and Ni. Searching for the Mg-based multicomponent compound and synthesizing it are significant for in-situ formation of ultrafine NdHx-MgH2-Ni/Mg2NiH4 composites with excellent hydrogen storage properties. In order to find out the best composition of addition, the phase equilibria at the Mg-rich corner is constructed by Calphad-type thermodynamic calculations and verified by a series of equilibrated alloys at 400 and 500 °C. There are four ternary compounds existing in the Mg-rich corner: Nd4Mg80Ni8, Nd16Mg96Ni12, NdMg5Ni and NdMg2Ni. The crystal structure of Nd4Mg80Ni8 and Nd16Mg96Ni12 are characterized by the synchrotron powder X-ray diffraction (SR-PXRD). Nd4Mg80Ni8 has the crystal structure of space group I41/amd with lattice parameters of a = b = 11.2743 Å and c = 15.9170 Å, while Nd16Mg96Ni12 has the crystal structure of space group of Cmc21 with lattice parameters of a = 15.3422 Å, b = 21.6750 Å and c = 9.4868 Å. The hydrogenation of the compounds leads to the decomposition of this compound into nanocomposites of Mg2NiH4, MgH2 and NdH2. Among the four compounds, the Nd4Mg80Ni8 shows the largest hydrogen capacity of 5.18 wt.% H2 at 350 °C under 4 MPa H2. The hydriding and dehydriding kinetic properties of those ternary compounds are enhanced greatly compared with other Mg-riched Nd-Mg-Ni alloys. Furthermore, the hydriding/dehydriding (H/D) kinetics are systematically investigated by the Chou kinetic model to compare the H/D rates and analyze the kinetic mechanism.
9:00 AM - ZZ5.26
Nano-Deformation Mechanisms in Bone Tissue in Tension and Compression
Baptiste Depalle 2 Zhao Qin 1 Markus Buehler 1
1MIT Cambridge United States2Imperial College London London United KingdomShow Abstract
Despite been made of simple elements, bone tissue gets its remarkable mechanical performance from a complex hierarchical organization. Through a fine tuned structure, this nanocomposite material combines the best properties of a strong and stiff mineral phase embedded in a soft yet tough organic matrix. Whereas bone nanostructure is well documented, the mechanisms that allow bone tissue to achieve its outstanding mechanical behavior remain unclear. In this study, we developed a coarse-grained molecular model of bone tissue to explore the intricate relationship between its nanostructure and mechanics. We used this model to study the role of extrafibrillar mineralization on the tissue&’s mechanical response under both tension and compression.
A simple bead spring or “coarse-grained” model is used to represent bone tissue. The geometry of the coarse-grained model is based on previous full atomistic simulations. In the simplified coarse-grained representation, one collagen bead represents about 180 atoms. The collagen molecules are replicated in order to form a fibrils of diameter d = 40 nm. The fibrils are mineralized in silico by filling the gaps in the model with hydroxyapatite elements. The extrafibrillar mineral is made of elongated plate-like crystal of thickness t=0.8 or 2.5 nm aligned to the collagen fibrils. The crystals are surrounded by a hydrated layer. A total of four crystals is created between every fibrils.
After equilibration, the model presents the main features seen experimentally. Individual crystals can be discerned as the hydrated layer surrounding the crystals prevents them from merging. The characteristic banding pattern of the collagen fibrils is also conserved. The response of the model in compression is in very good agreement with experiments performed on bone nanopillars. Increasing the crystal thickness from 0.8 to 2.5 nm leads to significant increase in the axial elastic modulus (8.6 vs 15.7 GPa) and strength (0.19 vs 0.53 GPa). The thickness of the crystals play a role in the deformation mechanisms of the tissue. For thin crystals, the crystal phase deforms by axial buckling. By contrast, a structure with thicker crystal collapse in a catastrophic Euler type buckling. The structure presents some signs of delamination between the mineral crystals and dislocations inside the crystals. In tension, the model for thickness of 0.8 and 2.5 nm exhibit similar elastic properties as in compression (9.8 vs 15.6 GPa). Yield stress arise at 0.39 and 0.46 GPa and can be related to collagen-mineral interactions.
The model developed here shed some light on the deformation mechanisms of bone tissue. Tissue elasticity and compressive strength are directly dependent on the amount of mineral and crystal thickness. The yielding properties in tension are related to collagen-mineral and mineral-mineral interactions. Identifying bone behavior at the nanoscale is essential to developing guidelines for the engineering of mineralized tissues.
9:00 AM - ZZ5.27
Continuum Free Energy Based Discrete Element Models of Elastic Materials
Mahendaran Uchimali 1 Balkrishna Rao 1 Srikanth Vedantam 1
1IIT Madras Chennai IndiaShow Abstract
The current numerical models to predict the mechanical behaviour of materials can be classified into two approaches namely continuum models and discrete element models (DEM). While continuum models have been studied in great detail, some aspects such as incorporating the effect of microstructural features such as grains texture, cracks and other defects proves difficult. As an alternative, DEM are gaining importance.
Discrete element methods describe the material in terms of lumped masses interacting through constitutively prescribed forces. DEM are taken to describe length and time scales in between molecular dynamics (MD) and continuum models. Thus the interaction potentials between the lumped masses do not arise from physical arguments as in MD. Most commonly, the interactions have been taken to occur through linear springs. The main difficulty in this approach lies in extending the models to inelastic deformations. There has been no systematic approach to developing inelastic interaction elements.
In this work we propose a discrete element model which may be able to overcome these limitations and handle elastic as well as inelastic problems. In our approach, the domain is discretised into lumped masses and the interaction forces are derived from the continuum strain energy density function. The deformation of the lattice element is described in terms of a Lagrangian strain and corresponding forces are obtained from the continuum strain energy density function. We believe this will allow discrete element methods to be generalised to describe inelastic material behaviour. In this work, we reproduce standard results of Elasticity in order to describe and validate the approach in detail.
ZZ3: Surfaces and Interfaces in Materials Science
Tuesday AM, December 01, 2015
Sheraton, 2nd Floor, Independence West
9:30 AM - ZZ3.02
Water Clustering in Amorphous Polyimide by MD Simulations
Eleanor Coyle 1 Katherine Sebeck 1 John Kieffer 1
1University of Michigan Ann Arbor United StatesShow Abstract
Accurate modelling of hydration in polymers can provide critical information, as the presence of water influences the structure, and electrical and mechanical properties. Previous studies of the hydration of polyimide have only considered systems of fully polymerized, monodisperse polyimide chains, neglecting any possible effects from residual monomers and a stable intermediate reaction step, poly(amic acid). Atomistic studies of polyimide are conducted using structures generated using a newly developed dynamic polymerization technique that combines molecular dynamics and Monte Carlo methods. This technique results in a more realistic structure and allows for tracking both the network structure and the hydration behavior as the system polymerizes. The final system is used to investigate the effects of water concentration and water model parameters on hydration behavior.
9:45 AM - ZZ3.03
Comparing the Recombination of Water Ions at a Solid-Liquid Interface to the Bulk
John Andrew Kattirtzi 1 Adam P Willard 1
1MIT Cambridge United StatesShow Abstract
A detailed atomic understanding of how a solid-liquid interface affects a chemical reaction can greatly assist in guiding the design and engineering of next generation catalytic materials. One reaction of particular interest, due to its relation to water-splitting and aqueous proton transport, is the auto-ionization of water. This process results in water ions that will subsequently recombine to water. Here, we present the results of an ab initio molecular dynamics study aimed at characterizing the recombination reaction in the environment of an electrochemical double-layer. Previous studies have demonstrated that a perfectly ordered Pt electrode, in contact with liquid water, can support long-lived nanoscale heterogeneity in the density and mobility of water molecules at the interface. We discuss the effect of this heterogeneity on the recombination dynamics of water ions. We investigate this by using QM/MM simulations where the solid and its interactions with the water molecules are treated classically, whilst the water molecules are treated at the DFT level. The simulations compare the water ion recombination mechanism and reaction times at the interface to that of the bulk liquid.
10:00 AM - ZZ3.04
Multiscale Computation of Surface Segregation Effect on Nanomaterial Properties
Guofeng Wang 1 Zhenyu Liu 1 Yinkai Lei 1
1Univ of Pittsburgh Pittsburgh United StatesShow Abstract
Surface segregation refers to the phenomenon that chemical composition at the surface of alloy materials differs from the corresponding value in their bulk region. Knowledge on surface segregation is pertinent to various engineering applications such as adsorption, wetting, oxidation, corrosion, electrical contact, friction and wear, crystal growth, and catalysis. In this presentation, we reported our research on accurately predicting the influence of surface segregation on the functional properties of nanostructured alloy materials using a multiscale computation technique. The employed multiscale computational approach consists of three hierarchical components: (1) developing reliable interatomic potentials for alloys with the modified embedded atom method based on the first-principles computation data, (2) applying these atomic interaction potentials to determine the chemical composition of extended and nanoparticle surfaces of alloys using the atomistic Monte Carlo method, and (3) evaluating properties of surface-segregated nanomaterials using the first-principles and/or mesoscale computation methods. We have successfully applied our multiscale computation to design catalytic and magnetic nanoparticles.
Case I: Platinum (Pt) alloys are the most active catalysts for oxygen reduction reaction (ORR) occurring in proton exchange membrane fuel cells. The surface chemical composition in these catalysts determines the electronic structure and further their catalytic performance for ORR. In the present study, we used our multiscale computation method to elaborate the relation between the surface composition, electronic structure, reaction pathway, and reaction rate of ORR on nanosegregated Pt alloy catalysts.
Case II: For both FePt and CoPt nanoparticles, our multiscale model predicted that it was energetically favorable to exchange the surface Fe and/or Co atoms with the interior Pt atoms and thus to induce the Pt surface segregation. Comparing the magnetic properties of bulk-terminated and surface-segregated nanoparticles, we found that the surface segregation processes in the FePt and CoPt nanoparticles could cause a decrease in their total magnetic moments, a change in their (easy and/or hard) magnetization axes, and a reduction in their magnetic anisotropy.
Hence, our computational approach is a valuable tool for computational design of novel functional nanomaterials.
10:15 AM - ZZ3.05
Multiscale Model for Interlayer Dislocations in Bilayer Materials
Shuyang Dai 1 Yang Xiang 3 David J Srolovitz 1 2
1University of Pennsylvania Philadelphia United States2University of Pennsylvania Philadelphia United States3Hong Kong University of Science and Technology Hong Kong ChinaShow Abstract
In this paper, we first present a general multiscale model based upon the generalized Peierls-Nabarro model to describe the interlayer dislocations in bilayer materials. In our model, the bilayer material is divided into two linear elastic 2D sheets which are used to describe each individual layer, the strains in each sheet can be relaxed by both in-plane elastic deformation and also by out-of-plane buckling; the deformation of 2D sheets can be described by classical linear elastic thin plate theory. The interface between these two sheets has a relative displacement in the presence of dislocations, and the two sheets are connected by a nonlinear potential. In our model, a 3-dimensional version of generalized stacking-fault energy (GSFE) which obtained from first principle calculation is used to describe the interlayer bonding between the two sheets. The structure and deformation of the bilayer with a dislocation is determined by the force balance between the local stresses in the sheets and the restoring force from the interlayer bonding. We apply this approach to determine the structure and energetics of four interlayer dislocations in bilayer graphene: edge, screw, 30o, and 60o (these angles represent the Burgers vector direction relative to the line direction). A pronounced buckling is formed at the position of partial dislocation to relax the strain induced by edge component of a partial dislocation. We determine the buckling amplitude, in-plane strain distributions, partial dislocation structures, core widths and dislocation energies. We found the dislocation core width in buckled structure decreases as the increase of edge component of its Burgers vector, which is different from the flat case. The results from our multiscale model provides an excellent quantitative match to the atomistic results. From these results, we construct a simple analytical model to describe the buckling and in-plane deformation of bilayer graphene with dislocations of arbitrary Burgers vector and demonstrate that the analytical model is in excellent agreements with the simulation results.
11:00 AM - ZZ3.06
Hydrodeoxygenation (HDO) of Acetone to Propylene on a MoO3 (010) Surface by Density Functional Theory
Beat Buesser 1 Manish Shetty 1 Yuriy Roman-Leshkov 1 William H. Green 1
1Massachusetts Institute of Technology Cambridge United StatesShow Abstract
Biomass pyrolysis with subsequent upgrading of pyrolysis oil (also known as bio-oil) into liquid hydrocarbons is one of the major strategies of utilizing biomass for renewable energies. However, a significant challenge with bio-oil is its high oxygen content, which makes it unsuitable for combustion applications before blending with conventional transportation fuels. Hydro-deoxygenation (HDO) is a major route of upgrading bio-oil by lowering its oxygen content. Recently, Roman-Leshkov and co-workers have shown MoO3 to be active for HDO of bio-oil model compounds at atmospheric pressures and temperatures of only 573-673 K and evidence for the occurrence of a reverse Mars van Krevelen mechanism involving oxygen vacancies has been found.
In this study, we have performed Density Functional Theory (DFT) calculations on the acetone (CH3COCH3) hydro-deoxygenation to propylene (CH3CHCH2) as a model reaction to gain insights into the thermodynamics and energetics of oxygen vacancy formation on MoO3 surfaces and subsequent deoxygenation pathways. A perfect O-terminated α-MoO3 (010) surface represented by a 4 x 3 x 4 supercell is reduced to generate a terminal oxygen defect site in the presence of H2. Hydrogen dissociatively adsorbs on adjacent surface oxygen sites and combines to form a water molecule. CH3COCH3 adsorbs at the oxygen deficient Mo site through a O-Mo bond and dehydrogenates to form CH3COCH2 by transfer of a hydrogen atom to an adjacent terminal oxygen site. The hydroxyl (OH) then hydrogenates the secondary carbon atom to form CH3CHOCH2. The reaction pathways for the conversion of CH3COCH3 to CH3CHCH2 are investigated with a Nudged Elastic Band (NEB) method that allows us to search for unknown transition states and reaction mechanisms. This results in the discovery of a new low transition state reaction mechanism for the deoxygenation step. The deoxygenation then releases CH3CHCH2 into the gas phase and regenerates the terminal oxygen atom on the Mo site by completing the reoxidation of the reduced MoO3 (010) surface back to perfect O-terminated MoO3 (010) surface.
11:15 AM - *ZZ3.07
Surface and Interface as Foundation to Realizing Designer Materials
Hideaki Kasai 1 Ryan Lacdao Arevalo 2 Mary Clare Sison Escano 3
1National Institute of Technology, Akashi amp; Institute of Industrial Science, The University of Tokyo Akashi, Hyogo Japan2Philippine Normal University Manila Philippines3University of Fukui Fukui JapanShow Abstract
To meet the ever-increasing demand for large-scale integration and cost-effective technologies, basic components of devices are getting smaller, with size ranging from the nanometer-scale to atomic-scale. Quantum effects are thus important in the modeling of the systems within these scales. With rapid progress in computing power of present supercomputers in Japan, computational materials design, CMD® techniques [1-2] with quantum effects integration, have paved way for new materials and mechanisms  .
In this meeting, we will present some case studies of CMD® application on surface and interfaces which resulted to understanding of (1) switching mechanism of transition metal oxide (TMO)-based resistance random access memories (RRAMs) [4,5]; (2) origin of magnetic anisotropy of Co/Ni multilayers for magnetic recording devices : (3) dynamics of hydrogen in surface and interfaces for hydrogen storage using our own computational code NANIWA series [7,8].
Furthermore, our computational modeling of systems has gone beyond drawing the mechanisms of experimentally studied/synthesized materials. Here, we present new materials out of rational design alone using CMD® techniques. Specifically, we show less and non-precious metal-based NOx reduction catalysts using DFT and KMC simulations for automobile industry (case study 4) [9,10]. Comparison with the conventional pure precious metal catalysts and the origin of the differences will be discussed.
 H. Kasai, H. Akai, and H. Yoshida, Keisanki Materials Design Nyumon, Osaka University Press, Osaka (2005).
 H. Kasai and M. Tsuda, Computational Materials Design Case Study 1: Intelligent/Directed Materials Design for Polymer Electrolyte Fuel Cells and Hydrogen Storage Applications, Osaka University Press, Osaka (2008).
 Patent list: http://www.dyn.ap.eng.osaka-u.ac.jp/web/patent.php.
 H. Kishi, A. A. A. Sarhan, M. Sakaue, S. M. Aspera, M.Y. David, H. Nakanishi, H. Kasai, Y. Tamai, S. Ohnishi,and N. Awaya, Jpn. J. Appl. Phys. 50, 071101 (2011).
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 K. Kojima, W. A. Dino, M. Suzuki, T. Yasue, K. Kudo, N. Akutsu, E. Bauer, T. Koshikawa, and H. Kasai, J.Vac. Soc. Jpn. 56, 139 (2013).
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 H. Kasai, W. A. Dino, and A. Okiji, Surf. Sci. Rep. 43,1 (2001).
 H. Kishi, A. A. B. Padama, R. L. Arevalo, J. L. V. Moreno, H. Kasai, M. Taniguchi, M. Uenishi, H. Tanaka and Y. Nishihata, J. Phys.: Condens. Matter 24, 262001(2012).
 R. Arevalo, MCS Escaño, H. Kasai. J. Vac. Sci. & Tech. 33 021402 (2015).
11:45 AM - ZZ3.08
Surface Oxide Effect on the Adsorption of PMDA-ODA on Cu(111)
Jong-Hun Park 1 Ji-Hwan Lee 1 Aloysius Soon 1
1Yonsei University Seoul Korea (the Republic of)Show Abstract
In this new age of flexible electronics, highly durable (and yet flexible) printed circuit boards (PCBs) are especially critical to the operation of such bendable electronic devices. From a materials&’ perspective, the adhesive properties of the aromatic polyimide layer to the metal surface very much determines the overall long-term performance of such devices . Given its high mechanical strength, and thermal and chemical resistance, poly(pyromellitic dianhydride oxydianiline) (PMDA-ODA) has been the choice polymeric substrate for the copper in these flexible PCBs [2-3]. To date, the poor adhesion in PMDA-ODA/Cu hybrid-interface has led to the limitations of its use as flexible and bendable PCB materials [4-5]. Despite of the significant demands for the improvement of PMDA-ODA/Cu hybrid-interface, there is still no clear principle for the early stage of the adsorption of organic film on metal surface.
In this work, using first-principles density-functional theory (including van der Waals force corrections), we study the fundamental physio-chemical properties of the molecular fragments of PMDA-ODA on both pristine Cu(111), as well as oxidic O/Cu(111). We make the selection of the adsorption models in the case of each fragment and surface by comparing binding energies of the molecular fragments at various adsorption sites. Henceforth we analyze the adsorption structures and the electronic structure of chosen models. Our results indeed show that the accurate picture of the adsorption models of PMDA-ODA moieties on Cu surfaces and may pave the road to explore this hybrid-interface by offering an increase understanding of the physio-chemical reaction on metal surface.
 B. Noh, J. Yoon, and S. Jung, Int. J. Adhes. Adhes.30, 30 (2010)
 M. Ramos, Vacuum 64, 255 (2002)
 Y. Takagi, Y. Gunjo, H. Toyoda , and H. Sugai, Vacuum83, 501 (2009)
 R.F. Saraf, J.M. Roldan, T. Derderian, IBM J. Res. Dev.38, 441 (1994)
 S. Bang, K. Kim, H. Jung, T. Kim a, S. Jeon a, J. Seol, Thin Solid Films558, 405 (2014)
12:00 PM - ZZ3.09
First-Principles Elucidation of Facet-Selective, Epitaxially Stabilized Anatase and Rutile TiO2 Thin Films on (001), (101), and (111) (Ba, Sr)TiO3 Perovskite Surfaces
Zhongnan Xu 1 Paul Salvador 2 John Kitchin 1
1Carnegie Mellon University Pittsburgh United States2Carnegie Mellon University Pittsburgh United StatesShow Abstract
Epitaxial stabilization of thin films is a powerful technique for growing novel materials with advanced functionality. While metastable structures can be kinetically stabilized, its relative thermodynamic stability also governs its ease of synthesis. The thermodynamic stability of a thin film can be modeled by a simple continuum model that incorporates energetic contributions from the substrate-film interface, film surface, and substrate-induced strain of the film. Accurate predictions of these contributions can accelerate the discovery of new thin film materials. We use density functional theory (DFT) to elucidate experimental observations of epitaxial growth of rutile and anatase TiO2 on (Ba, Sr)TiO3 perovskite (001), (101), and (111) surfaces. We do this by calculating epitaxial interface energies, surface energies, and substrate-induced strain energies of the film and insert these quantities into a simple continuum model to evaluate thin film stability. Our DFT calculations explain a number of observed phenomenon related the preferential growth of TiO2 rutile or the metastable anatase phase. These phenomenon include the strong/weak epitaxial stabilization of anatase on the (Ba, Sr)TiO3 (001)/(101) surface, respectively, as well as the strong epitaxial stabilization of rutile on the (Ba, Sr)TiO3 (111) surface. Our results demonstrate that interface energies calculated from first principles can explain the facet-selective growth of TiO2 on perovskite surfaces. We discuss ways to use our method to predict the epitaxial stability of new materials.
12:15 PM - ZZ3.10
Computational Prediction of TiO2 (rutile) Grain Boundary Energies Using Reactive MD Potentials
Patrick Shamberger 1 Jennifer Wohlwend 2 3 Ajit Roy 2 Andrey Voevodin 2
1Texas Aamp;M University College Station United States2Air Force Research Laboratory Wright Patterson AFB United States3Universal Technology Corporation Dayton United StatesShow Abstract