NASA Astrophysics Data System (ADS)
Pemmaraju, Sri Chaitanya Das; Prendergast, David
2014-03-01
We present two case studies of first-principles theoretical methods applied in conjunction with experimental core-level spectroscopy measurements to investigate the electronic structure and dynamical processes in molecular and interfacial systems relevant to photoelectrochemical (PEC) technologies. In the first, we study the core-level and valence spectroscopies of two zinc(II)-porphyrin based Donor-pi-Acceptor (D-p-A) dyes using the occupancy-constrained excited electron and core-hole (XCH) approach and time-dependent density functional theory (TDDFT) simulations. In the second, we use constrained DFT and TDDFT to interpret measured transient core-level shifts in time-resolved femtosecond x-ray photoelectron spectroscopy, investigating the dynamics of the electron injection process from a N3 dye molecule chemisorbed onto a ZnO substrate. These studies illustrate the utility of first-principles methods in guiding the design of better PEC materials. This work was performed at the Molecular Foundry, LBNL, supported by the Office of Science, Office of Basic Energy Sciences, of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231.
Infrared Spectroscopy of Functionalized Graphene Sheets from First Principle Calculations
NASA Astrophysics Data System (ADS)
Zhang, Cui; Dabbs, Daniel; Aksay, Ilhan; Car, Roberto; Selloni, Annabella
2014-03-01
Detailed characterization of the structure of functionalized graphene sheets (FGSs) is an important and challenging task which could help to improve the performance of FGS materials for technological applications. We present here first principles calculations for the infrared (IR) spectra of different FGS models aimed at identifying the IR signatures of different functional groups and defect sites on FGSs. We found that vacancies and edges have significant effects on the IR frequencies of the functional groups on FGSs. In particular, hydroxyl groups close to vacancies have higher stretching and lower bending frequencies in comparison to hydroxyls in defect free regions of FGSs. More interestingly, the OH vibrations of carboxyl groups at edges exhibit unique features in the high frequency IR bands, which originate from the interactions with neighboring groups and the relative orientation of the carboxyl with respect to the FGS plane. Our results are supported by experimental IR measurements on FGS powders.
Doppler effects in a left-handed material: a first-principle theoretical study
Sanshui Xiao; Min Qiu
2005-09-01
The Doppler effects for the reflected wave from a moving media are systemically analyzed in this paper. The theoretical formula for the Doppler shift in the left-handed material, which is described by Drude's dispersion model, is presented. This formula is examined by first-principles numerical experiments, which are in agreement with the theoretical results.
Nguyen, Ngoc Linh; Borghi, Giovanni; Ferretti, Andrea; Dabo, Ismaila; Marzari, Nicola
2015-04-24
The determination of spectral properties from first principles can provide powerful connections between microscopic theoretical predictions and experimental data, but requires complex electronic-structure formulations that fall outside the domain of applicability of common approaches, such as density-functional theory. We show here that Koopmans-compliant functionals, constructed to enforce piecewise linearity and the correct discontinuity derivative in energy functionals with respect to fractional occupation-i.e., with respect to charged excitations-provide molecular photoemission spectra and momentum maps of Dyson orbitals that are in excellent agreement with experimental ultraviolet photoemission spectroscopy and orbital tomography data. These results highlight the role of Koopmans-compliant functionals as accurate and inexpensive quasiparticle approximations to the spectral potential. PMID:25955063
NASA Astrophysics Data System (ADS)
Nguyen, Ngoc Linh; Borghi, Giovanni; Ferretti, Andrea; Dabo, Ismaila; Marzari, Nicola
2015-04-01
The determination of spectral properties from first principles can provide powerful connections between microscopic theoretical predictions and experimental data, but requires complex electronic-structure formulations that fall outside the domain of applicability of common approaches, such as density-functional theory. We show here that Koopmans-compliant functionals, constructed to enforce piecewise linearity and the correct discontinuity derivative in energy functionals with respect to fractional occupation—i.e., with respect to charged excitations—provide molecular photoemission spectra and momentum maps of Dyson orbitals that are in excellent agreement with experimental ultraviolet photoemission spectroscopy and orbital tomography data. These results highlight the role of Koopmans-compliant functionals as accurate and inexpensive quasiparticle approximations to the spectral potential.
Exploiting periodic first-principles calculations in NMR spectroscopy of disordered solids.
Ashbrook, Sharon E; Dawson, Daniel M
2013-09-17
Much of the information contained within solid-state nuclear magnetic resonance (NMR) spectra remains unexploited because of the challenges in obtaining high-resolution spectra and the difficulty in assigning those spectra. Recent advances that enable researchers to accurately and efficiently determine NMR parameters in periodic systems have revolutionized the application of density functional theory (DFT) calculations in solid-state NMR spectroscopy. These advances are particularly useful for experimentalists. The use of first-principles calculations aids in both the interpretation and assignment of the complex spectral line shapes observed for solids. Furthermore, calculations provide a method for evaluating potential structural models against experimental data for materials with poorly characterized structures. Determining the structure of well-ordered, periodic crystalline solids can be straightforward using methods that exploit Bragg diffraction. However, the deviations from periodicity, such as compositional, positional, or temporal disorder, often produce the physical properties (such as ferroelectricity or ionic conductivity) that may be of commercial interest. With its sensitivity to the atomic-scale environment, NMR provides a potentially useful tool for studying disordered materials, and the combination of experiment with first-principles calculations offers a particularly attractive approach. In this Account, we discuss some of the issues associated with the practical implementation of first-principles calculations of NMR parameters in solids. We then use two key examples to illustrate the structural insights that researchers can obtain when applying such calculations to disordered inorganic materials. First, we describe an investigation of cation disorder in Y2Ti(2-x)Sn(x)O7 pyrochlore ceramics using (89)Y and (119)Sn NMR. Researchers have proposed that these materials could serve as host phases for the encapsulation of lanthanide- and actinide-bearing radioactive waste. In a second example, we discuss how (17)O NMR can be used to probe the dynamic disorder of H in hydroxyl-humite minerals (nMg2SiO4·Mg(OH)2), and how (19)F NMR can be used to understand F substitution in these systems. The combination of first-principles calculations and multinuclear NMR spectroscopy facilitates the investigation of local structure, disorder, and dynamics in solids. We expect that applications will undoubtedly become more widespread with further advances in computational and experimental methods. Insight into the atomic-scale environment is a crucial first step in understanding the structure-property relationships in solids, and it enables the efficient design of future materials for a range of end uses. PMID:23402741
Kishi, Hiroki; Miyazawa, Miki; Matsushima, Naoki; Yamauchi, Jun
2014-02-21
We investigate the X-ray photoelectron spectroscopy (XPS) binding energies of As 3d in Si for various defects in neutral and charged states by first-principles calculation. It is found that the complexes of a substitutional As and a vacancy in charged and neutral states explain the experimentally observed unknown peak very well.
NASA Astrophysics Data System (ADS)
Pagare, Gitanjali; Jain, Ekta; Abraham, Jisha Annie; Sanyal, S. P.
2015-08-01
The structural and elastic properties of aluminum based some intermetallics, AlX (X = Mg, Co, Rh, Pd and Ir) have been investigated using full potential linearized augmented plane wave (FP-LAPW) method based on density functional theory (DFT). The exchange-correlation term was treated within generalized gradient approximation (GGA). Grounds state properties i.e. lattice constants (a0), bulk modulus (B) and first-order pressure derivative of bulk modulus (B') are presented. Our calculated results for C11, C12 and C44 have been compared with available previous theoretical data. The Young's modulus (G), shear modulus (E), sound wave velocities and Debye temperature are the first theoretical prediction for these compounds. Using Pugh's rule and Cauchy pressure the ductile/brittle character of these compounds are satisfied.
Beccara, Silvio a; Rivalta, Ivan; Cerullo, Giulio
2014-01-01
The ability of non-linear electronic spectroscopy to track folding/unfolding processes of proteins in solution by monitoring aromatic interactions is investigated by first-principle simulations of two-dimensional (2D) electronic spectra of a model peptide. A dominant reaction pathway approach is employed to determine the unfolding pathway of a tetrapeptide, connecting the initial folded configuration with stacked aromatic side chains and the final unfolded state with distant non-interacting aromatic residues. ?-stacking and excitonic coupling effects are included via ab-initio simulations based on multiconfigurational methods within a hybrid QM/MM scheme. We show that linear absorption spectroscopy in the ultraviolet (UV) is unable to resolve the unstacking dynamics characterized by the three-step process: T-shaped?twisted offset stacking?unstacking. Conversely, pump-probe spectroscopy can be used to resolve aromatic interactions by probing in the visible (Vis) the excited state absorptions (ESA) that involve charge transfer (CT) states. 2DUV spectroscopy offers the highest sensitivity to the unfolding process, providing the disentanglement of ESA signals belonging to different aromatic chromophores and high correlation between the conformational dynamics and the quartic splitting. PMID:25145908
Nenov, Artur; Segarra-Martí, Javier; Giussani, Angelo; Conti, Irene; Rivalta, Ivan; Dumont, Elise; Jaiswal, Vishal K; Altavilla, Salvatore Flavio; Mukamel, Shaul; Garavelli, Marco
2015-01-01
The SOS//QM/MM [Rivalta et al., Int. J. Quant. Chem., 2014, 114, 85] method consists of an arsenal of computational tools allowing accurate simulation of one-dimensional (1D) and bi-dimensional (2D) electronic spectra of monomeric and dimeric systems with unprecedented details and accuracy. Prominent features like doubly excited local and excimer states, accessible in multi-photon processes, as well as charge-transfer states arise naturally through the fully quantum-mechanical description of the aggregates. In this contribution the SOS//QM/MM approach is extended to simulate time-resolved 2D spectra that can be used to characterize ultrafast excited state relaxation dynamics with atomistic details. We demonstrate how critical structures on the excited state potential energy surface, obtained through state-of-the-art quantum chemical computations, can be used as snapshots of the excited state relaxation dynamics to generate spectral fingerprints for different de-excitation channels. The approach is based on high-level multi-configurational wavefunction methods combined with non-linear response theory and incorporates the effects of the solvent/environment through hybrid quantum mechanics/molecular mechanics (QM/MM) techniques. Specifically, the protocol makes use of the second-order Perturbation Theory (CASPT2) on top of Complete Active Space Self Consistent Field (CASSCF) strategy to compute the high-lying excited states that can be accessed in different 2D experimental setups. As an example, the photophysics of the stacked adenine-adenine dimer in a double-stranded DNA is modeled through 2D near-ultraviolet (NUV) spectroscopy. PMID:25607949
NASA Astrophysics Data System (ADS)
Ho, C. H.; Huang, Y. S.; Chen, J. L.; Dann, T. E.; Tiong, K. K.
1999-12-01
The electronic structures of ReS2 and ReSe2 single crystals are investigated using a first-principles density-of-states (DOS) calculation, ultraviolet photoelectron spectroscopy (UPS), and electrolyte electroreflectance (EER). The total and partial DOS were calculated by the full-potential linearized-augmented-plane-wave method. From the calculations, the main contribution near the band edge of Re X2 (X=S,Se) is determined to be dominated by the nonbonding Re d orbitals. The valence-band DOS is experimentally verified by the UPS measurements. EER measurements were performed in the energy range of 1.3-6 eV. The EER spectra exhibit sharp derivativelike structures in the vicinity of the band-edge excitonic transitions as well as higher-lying interband transitions. Transition energies are determined accurately. From the experimental and the theoretically calculated results, probable energy-band structures of ReS2 and ReSe2 are constructed.
Zwier, Timothy S.
Theoretical modeling of the OH stretch infrared spectrum of carboxylic acid dimers based on first, Wisconsin 53706-1396 Received 20 September 2002; accepted 28 October 2002 Carboxylic acid dimers serve, and OH bend internal coordinates for the formic acid and benzoic acid dimers. These are then projected
A First-Principles Theoretical Study on the Thermoelectric Properties of the Compound Cu5AlSn2S8
NASA Astrophysics Data System (ADS)
Li, Weijian; Zhou, Chenyi; Li, Liangliang
2015-10-01
A new compound of Cu5AlSn2S8, which contained earth-abundant and environment-friendly elements and had a diamond-like crystal structure, was designed, and its electronic structure and thermoelectric transport properties from 300 K to 700 K were investigated by first-principles calculations, Boltzmann transport equations, and a modified Slack's model. The largest power factors of Cu5AlSn2S8 at 700 K were 47.5 × 1010 W m-1 K-2 s-1 and 14.7 × 1010 W m-1 K-2 s-1 for p- and n-type semiconductors, respectively. The lattice thermal conductivity of Cu5AlSn2S8 was calculated with its shear modulus and isothermal bulk modulus, which were also obtained by first-principles calculations. The lattice thermal conductivity was 0.9-2.2 W m-1 K-1 from 300 K to 700 K, relatively low among thermoelectric compounds. This theoretical study showed that Cu5AlSn2S8 could be a potential thermoelectric material.
Zhou, Hong-Bo; Zhang, Ying; Liu, Yue-Lin; Kohyama, Masanori; Yin, Peng-Gang; Lu, Guang-Hong
2009-04-29
We perform first-principles computational tensile and compressive tests (FPCTT and FPCCT) to investigate the intrinsic bonding and mechanical properties of a ?-TiAl intermetallic compound (L 1(0) structure) using a first-principles total energy method. We found that the stress-strain relations and the corresponding theoretical tensile strengths exhibit strong anisotropy in the [001], [100] and [110] crystalline directions, originating from the structural anisotropy of ?-TiAl. Thus, ?-TiAl is a representative intermetallic compound that includes three totally different stress-strain modes. We demonstrate that all the structure transitions in the FPCTT and FPCCT result from the breakage or formation of bonds, and this can be generalized to all the structural transitions. Furthermore, based on the calculations we qualitatively show that the Ti-Al bond should be stronger than the Ti-Ti bond in ?-TiAl. Our results provide a useful reference for understanding the intrinsic bonding and mechanical properties of ?-TiAl as a high-temperature structural material. PMID:21825422
NASA Astrophysics Data System (ADS)
Zhou, Hong-Bo; Zhang, Ying; Liu, Yue-Lin; Kohyama, Masanori; Yin, Peng-Gang; Lu, Guang-Hong
2009-04-01
We perform first-principles computational tensile and compressive tests (FPCTT and FPCCT) to investigate the intrinsic bonding and mechanical properties of a ?-TiAl intermetallic compound (L 10 structure) using a first-principles total energy method. We found that the stress-strain relations and the corresponding theoretical tensile strengths exhibit strong anisotropy in the [001], [100] and [110] crystalline directions, originating from the structural anisotropy of ?-TiAl. Thus, ?-TiAl is a representative intermetallic compound that includes three totally different stress-strain modes. We demonstrate that all the structure transitions in the FPCTT and FPCCT result from the breakage or formation of bonds, and this can be generalized to all the structural transitions. Furthermore, based on the calculations we qualitatively show that the Ti-Al bond should be stronger than the Ti-Ti bond in ?-TiAl. Our results provide a useful reference for understanding the intrinsic bonding and mechanical properties of ?-TiAl as a high-temperature structural material.
Reeves, Kyle G.; Kanai, Yosuke
2014-07-14
Oxidation state is a powerful concept that is widely used in chemistry and materials physics, although the concept itself is arguably ill-defined quantum mechanically. In this work, we present impartial comparison of four, well-recognized theoretical approaches based on Lowdin atomic orbital projection, Bader decomposition, maximally localized Wannier function, and occupation matrix diagonalization, for assessing how well transition metal oxidation states can be characterized. Here, we study a representative molecular complex, tris(bipyridine)ruthenium. We also consider the influence of water solvation through first-principles molecular dynamics as well as the improved electronic structure description for strongly correlated d-electrons by including Hubbard correction in density functional theory calculations.
Mukamel, Shaul
Two-Dimensional Electronic Spectroscopy of Benzene, Phenol, and Their Dimer: An Efficient First of 2DUV spectra of benzene, phenol, and their dimer (i.e., the minimal models for studying electronic allows for direct comparison with experiments. INTRODUCTION Benzene and phenol are aromatic chromophores
NASA Astrophysics Data System (ADS)
Giarola, M.; Sanson, A.; Rahman, A.; Mariotto, G.; Bettinelli, M.; Speghini, A.; Cazzanelli, E.
2011-06-01
A thorough study of the vibrational dynamics of xenotime YPO4 and its isomorphs, pretulite ScPO4 single crystals, with tetragonal zircon structure, was carried out by means of an integrated approach consisting of both polarized micro-Raman scattering spectroscopy and first-principles calculations. Polarized Raman scattering experiments were performed at room temperature either in the 180° or in the 90° geometry on both samples under different crystal orientations set by a micromanipulator. All the 12 independent components of the polarizability tensor, expected on the basis of the group theory for both YPO4 and ScPO4, were selected in turn and assigned in symmetry. In particular, it was possible to unambiguously identify a B1g mode peaked at 316 cm-1 in YPO4 and two B1g modes peaked at 350 and 677 cm-1 in ScPO4, respectively, all of them never reported before. These observations were corroborated by the results of first-principles calculations, based on density functional theory in the generalized gradient approximation, performed to determine Raman and infrared vibrational modes. In fact, an excellent agreement between computational and experimental results has been found.
NASA Astrophysics Data System (ADS)
Choi, Woo Seok; Kim, Dong Geun; Seo, Sung Seok A.; Moon, Soon Jae; Lee, Daesu; Lee, Jung Hyuk; Lee, Ho Sik; Cho, Deok-Yong; Lee, Yun Sang; Murugavel, Pattukkannu; Yu, Jaejun; Noh, Tae W.
2008-01-01
We investigated the electronic structure of multiferroic hexagonal RMnO3 ( R=Gd , Tb, Dy, and Ho) thin films using both optical spectroscopy and first-principles calculations. One of the difficulties in explaining the electronic structures of hexagonal RMnO3 is that they exist in nature with limited rare earth ions (i.e., R=Sc , Y, and Ho-Lu), so a systematic study in terms of the different R ions has been lacking. Recently, our group succeeded in fabricating hexagonal RMnO3 ( R=Gd , Tb, and Dy) using the epitaxial stabilization technique [Adv. Mater. (Weinheim Ger.) 18, 3125 (2006)]. Using artificially stabilized hexagonal RMnO3 , we extended the optical spectroscopic studies on the hexagonal multiferroic manganite system. We observed two optical transitions located near 1.7 and 2.3eV , in addition to the predominant absorption above 5eV . With the help of first-principles calculations, we attributed the low-lying optical absorption peaks to interband transitions from the oxygen states hybridized strongly with different Mn orbital symmetries to the Mn3d3z2-r2 state. As the ionic radius of the rare earth ion increased, we observed a systematic increase of the lowest peak position, which became more evident when compared with previously reported results. We explained this systematic change in terms of a flattening of the MnO5 triangular bipyramid.
Soft modes and anharmonicity in H3[Co (CN )6] : Raman spectroscopy and first-principles calculations
NASA Astrophysics Data System (ADS)
Mishra, K. K.; Chandra, Sharat; Salke, Nilesh P.; Achary, S. N.; Tyagi, A. K.; Rao, Rekha
2015-10-01
In situ high-pressure Raman spectroscopy and ab initio calculations are carried out to investigate the phase stability and the thermal expansion behavior of H3[Co (CN )6] . Raman studies at high pressures in a diamond anvil cell identify soft phonons and phase instability at 2.3 GPa. Evidence of pressure-induced amorphization is found at 11 GPa. The phonon frequencies and eigenvectors obtained from ab initio calculation are used to complement the observed phonon spectra and for assignment of Raman modes. The computed eigenvector displacement patterns indicate that the soft modes correspond to the CN-librational vibrations (Eg mode) of the Co-CN-H-NC-Co linkages and their Grüneisen parameters are found to be negative, in agreement with our measured values. The thermal expansion coefficient (15.6 ×10-6K-1 ) calculated using our computed mode Grüneisen parameters is found to be in good agreement with the reported value (20 ×10-6K-1 ). Temperature-dependent phonon spectra down to 77 K are used to obtain the anharmonicities of different modes.
NASA Astrophysics Data System (ADS)
Honda, Atsushi; Higai, Shin'ichi; Kageyama, Keisuke; Higuchi, Yukio; Shiratsuyu, Kosuke
2015-10-01
We performed first-principles theoretical calculations on microwave dielectric compounds Ba(Zn1/3Ta2/3)O3, to clarify the origin of high Q characteristics in the Zn/Ta ordered structure. It was found that Zn atoms suppress the intrinsic ferroelectric nature of Slater mode vibration in TaO6 octahedra. This results in the improvement of harmonicity in lattice vibration. There are two important mechanisms. One is the compression of TaO6 octahedra by adjacent ZnO6, and then the double-well potential that TaO6 originally has is narrowed to be single-well with higher harmonicity. The other is the weakening of the covalent character of Ta-O bonds by adjacent Zn atoms, which is the origin of the double-well potential. In the fully ordered Ba(Zn1/3Ta2/3)O3, all Ta atoms are adjacent to Zn atoms, where Zn atoms have the maximum effect on improving harmonicity. Thus, highly ordered Ba(Zn1/3Ta2/3)O3 with prolonged heat treatment exhibits a high Q value.
Xiao, Kai; Yoon, Mina; Rondinone, Adam Justin; Payzant, E Andrew; Geohegan, David B
2012-01-01
The deterministic growth of oriented crystalline organic nanowires (CONs) from the vapor-solid chemical reaction (VSCR) between small-molecule reactants and metal nanoparticles has been demonstrated in several studies to date, however the growth mechanism has not yet been conclusively understood. Here, the VSCR growth of M-TCNQF4 (where M is Cu- or Ag-) nanowires is investigated both experimentally and theoretically with time-resolved, in-situ x-ray diffraction (XRD) and first-principles atomistic calculations, respectively, to understand how metals (M) direct the assembly of small molecules into CONs, and what determines the selectivity of a metal for an organic vapor reactant in the growth process. Analysis of the real-time growth kinetics data using a modified Avrami model indicates that the formation of CONs from VSCR follows a one-dimensional ion diffusion-controlled tip growth mechanism wherein metal ions diffuse from a metal film through the nanowire to its tip where they react with small molecules to continue growth. The experimental data and theoretical calculations indicate that the selectivity of different metals to induce nanowire growth depends strongly upon effective charge transfer between the organic molecules and the metal. Specifically, the experimental finding that Cu ions can exchange and replace Ag ions in Ag-TCNQF4 to form Cu-TCNQF4 nanowires is explained by the significantly stronger chemical bond between Cu and TCNQF4 molecules than for Ag, due to the strong spin-dependent electronic contribution of Cu. Understanding how to control the VSCR growth process may enable the synthesis of novel organic nanowires with axial or coaxial p/n junctions for organic nanoelectronics and solar energy harvesting.
Introductory Training on Theoretical Spectroscopy
Botti, Silvana
Introductory Training on Theoretical Spectroscopy The aims of this tutorial are hence to: - give an overview over the ETSF training possibilties - give an overview of the theoretical points of view properties of finite and infinite systems. Scopes The main scope of this introductory training day
NASA Astrophysics Data System (ADS)
Prendergast, David; Pemmaraju, Sri Chaitanya Das
2015-09-01
With the advent of X-ray free electron lasers and table-top high-harmonic-generation X-ray sources, we can now explore changes in electronic structure on ultrafast time scales -- at or less than 1ps. Transient X-ray spectroscopy of this kind provides a direct probe of relevant electronic levels related to photoinitiated processes and associated interfacial electron transfer as the initial step in solar energy conversion. However, the interpretation of such spectra is typically fraught with difficulty, especially since we rarely have access to spectral standards for nonequilibrium states. To this end, direct first-principles simulations of X-ray absorption spectra can provide the necessary connection between measurements and reliable models of the atomic and electronic structure. We present examples of modeling excited states of materials interfaces relevant to solar harvesting and their corresponding X-ray spectra in either photoemission or absorption modalities. In this way, we can establish particular electron transfer mechanisms to reveal detailed working principles of materials systems in solar applications and provide insight for improved efficiency.
Kim, Gunwoo; Griffin, John M.; Blanc, Frédéric; Haile, Sossina M.; Grey, Clare P.
2015-03-03
17O NMR spectroscopy combined with first-principles calculations was employed to understand the local structure and dynamics of the phosphate ions and protons in the paraelectric phase of the proton conductor CsH2PO4. For the room...
Towards first-principles electrochemistry
Dabo, Ismaila
2008-01-01
This doctoral dissertation presents a comprehensive computational approach to describe quantum mechanical systems embedded in complex ionic media, primarily focusing on the first-principles representation of catalytic ...
Wanbayor, Raina; Deak, Peter; Frauenheim, Thomas; Ruangpornvisuti, Vithaya
2011-03-14
First principles density functional theory calculations were carried out to investigate the adsorption and oxidation of CO on the positively charged (101) surface of anatase, as well as the desorption of CO{sub 2} from it. We find that the energy gain on adsorption covers the activation energy required for the oxidation, while the energy gain on the latter is sufficient for the desorption of CO{sub 2}, leaving an oxygen vacancy behind. Molecular dynamics simulations indicate that the process can be spontaneous at room temperature. The oxidation process described here happens only in the presence of the hole. The possibility of a photocatalytic cycle is discussed assuming electron scavenging by oxygen.
Theoretical methods for ultrafast spectroscopy.
Marquardt, Roberto
2013-05-10
Time-resolved spectroscopy in the femtosecond and attosecond time domain is a tool to unravel the dynamics of nuclear and electronic motion in molecular systems. Theoretical insight into the underlying physical processes is ideally gained by solving the time-dependent Schrödinger equation. In this work, methods currently used to solve this equation are reviewed in a compact presentation. These methods involve numerical representations of wavefunctions and operators, the calculation of time evolution operators, the setting up of the Hamiltonian operators and the types of coordinates to be used hereto. The advantages and disadvantages of some methods are discussed. PMID:23606322
Loganathan, B; Chandraboss, V L; Senthilvelan, S; Karthikeyan, B
2015-09-01
The Rh shell of the Au/Pt/Rh trimetallic nanoparticles induces a wide variety of interesting surface reactions by allowing the adsorption of amino acids like L-cysteine (L-Cys). We present a snapshot of theoretical and experimental investigation of L-Cys adsorption on the surface of noble trimetallic Au/Pt@Rh colloidal nanocomposites. Density functional theoretical (DFT) investigations of L-Cys interaction with the Rhodium (Rh) shell of a trimetallic Au/Pt@Rh cluster in terms of geometry, binding energy (E(B)), binding site, energy gap (E(g)), electronic and spectral properties have been performed. L-Cys establishes a strong interaction with the Rh shell. It binds to Rh by the S1-site, which makes a stable L-Cys-Rh surface complex. DFT can be taken as a valuable tool to assign the vibrational spectra of the adsorption of L-Cys on trimetallic Au/Pt@Rh colloidal nanocomposites and mono-metallic Rh nanoparticles. Surface-enhanced infrared spectroscopy (SEIRS) with L-Cys on a Rh6 cluster surface has been simulated for the first time. Experimental information on the L-Cys-Rh surface complex is included to examine the interaction. The experimental spectral observations are in good agreement with the simulated DFT results. Characterization of the synthesized trimetallic Au/Pt@Rh colloidal nanocomposites has been done by high-resolution transmission electron microscopy (HR-TEM) with selected area electron diffraction (SAED) pattern, energy dispersive X-ray (EDX) spectroscopy, dynamic light scattering (DLS) measurements, zeta potential, zeta deviation analysis and UV-visible (UV-Vis) spectroscopic studies. PMID:25650352
2015-01-01
Despite the widespread use of amorphous aluminosilicates (ASA) in various industrial catalysts, the nature of the interface between silica and alumina and the atomic structure of the catalytically active sites are still subject to debate. Here, by the use of dynamic nuclear polarization surface enhanced NMR spectroscopy (DNP SENS) and density functional theory (DFT) calculations, we show that on silica and alumina surfaces, molecular aluminum and silicon precursors are, respectively, preferentially grafted on sites that enable the formation of Al(IV) and Si(IV) interfacial sites. We also link the genesis of Brønsted acidity to the surface coverage of aluminum and silicon on silica and alumina, respectively. PMID:26244620
Xiao, Kai; Yoon, Mina; Rondinone, Adam J; Payzant, Edward A; Geohegan, David B
2012-09-01
The deterministic growth of oriented crystalline organic nanowires (CONs) from the vapor-solid chemical reaction (VSCR) between small-molecule reactants and metal nanoparticles has been demonstrated in several studies to date; however, the growth mechanism has not yet been conclusively understood. Here, the VSCR growth of M-TCNQF(4) (where M is Cu- or Ag-) nanowires is investigated both experimentally and theoretically with time-resolved, in situ X-ray diffraction (XRD) and first-principles atomistic calculations, respectively, to understand how metals (M) direct the assembly of small molecules into CONs, and what determines the selectivity of a metal for an organic vapor reactant in the growth process. Analysis of the real-time growth kinetics data using a modified Avrami model indicates that the formation of CONs from VSCR follows a one-dimensional ion diffusion-controlled tip growth mechanism wherein metal ions diffuse from a metal film through the nanowire to its tip where they react with small molecules to continue growth. The experimental data and theoretical calculations indicate that the selectivity of different metals to induce nanowire growth depends strongly upon effective charge transfer between the organic molecules and the metal. Specifically, the experimental finding that Cu ions can exchange and replace Ag ions in Ag-TCNQF(4) to form Cu-TCNQF(4) nanowires is explained by the significantly stronger chemical bond between Cu and TCNQF(4) molecules than for Ag, due to the strong electronic contribution of Cu d-orbitals near the Fermi level. Understanding how to control the VSCR growth process may enable the synthesis of novel organic nanowires with axial or coaxial p/n junctions for organic nanoelectronics and solar energy harvesting. PMID:22506925
Chamber Clearing First Principles Modeling
Loosmore, G
2009-06-09
LIFE fusion is designed to generate 37.5 MJ of energy per shot, at 13.3 Hz, for a total average fusion power of 500 MW. The energy from each shot is partitioned among neutrons ({approx}78%), x-rays ({approx}12%), and ions ({approx}10%). First wall heating is dominated by x-rays and debris because the neutron mean free path is much longer than the wall thickness. Ion implantation in the first wall also causes damage such as blistering if not prevented. To moderate the peak-pulse heating, the LIFE fusion chamber is filled with a gas (such as xenon) to reduce the peak-pulse heat load. The debris ions and majority of the x-rays stop in the gas, which re-radiates this energy over a longer timescale (allowing time for heat conduction to cool the first wall sufficiently to avoid damage). After a shot, because of the x-ray and ion deposition, the chamber fill gas is hot and turbulent and contains debris ions. The debris needs to be removed. The ions increase the gas density, may cluster or form aerosols, and can interfere with the propagation of the laser beams to the target for the next shot. Moreover, the tritium and high-Z hohlraum debris needs to be recovered for reuse. Additionally, the cryogenic target needs to survive transport through the gas mixture to the chamber center. Hence, it will be necessary to clear the chamber of the hot contaminated gas mixture and refill it with a cool, clean gas between shots. The refilling process may create density gradients that could interfere with beam propagation, so the fluid dynamics must be studied carefully. This paper describes an analytic modeling effort to study the clearing and refilling process for the LIFE fusion chamber. The models used here are derived from first principles and balances of mass and energy, with the intent of providing a first estimate of clearing rates, clearing times, fractional removal of ions, equilibrated chamber temperatures, and equilibrated ion concentrations for the chamber. These can be used to scope the overall problem and provide input to further studies using fluid dynamics and other more sophisticated tools.
McCluskey, Matthew
Hydrogen donors in SnO2 studied by infrared spectroscopy and first-principles calculations W. M; revised manuscript received 8 October 2010; published 3 November 2010 Hydrogen is a potentially important source of n-type conductivity in oxide materials. We have investigated hydrogen in tin oxide SnO2
2015-01-01
17O NMR spectroscopy combined with first-principles calculations was employed to understand the local structure and dynamics of the phosphate ions and protons in the paraelectric phase of the proton conductor CsH2PO4. For the room-temperature structure, the results confirm that one proton (H1) is localized in an asymmetric H-bond (between O1 donor and O2 acceptor oxygen atoms), whereas the H2 proton undergoes rapid exchange between two sites in a hydrogen bond with a symmetric double potential well at a rate ?107 Hz. Variable-temperature 17O NMR spectra recorded from 22 to 214 °C were interpreted by considering different models for the rotation of the phosphate anions. At least two distinct rate constants for rotations about four pseudo C3 axes of the phosphate ion were required in order to achieve good agreement with the experimental data. An activation energy of 0.21 ± 0.06 eV was observed for rotation about the P–O1 axis, with a higher activation energy of 0.50 ± 0.07 eV being obtained for rotation about the P–O2, P–O3d, and P–O3a axes, with the superscripts denoting, respectively, dynamic donor and acceptor oxygen atoms of the H-bond. The higher activation energy of the second process is most likely associated with the cost of breaking an O1–H1 bond. The activation energy of this process is slightly lower than that obtained from the 1H exchange process (0.70 ± 0.07 eV) (Kim, G.; Blanc, F.; Hu, Y.-Y.; Grey, C. P. J. Phys. Chem. C2013, 117, 6504?6515) associated with the translational motion of the protons. The relationship between proton jumps and phosphate rotation was analyzed in detail by considering uncorrelated motion, motion of individual PO4 ions and the four connected/H-bonded protons, and concerted motions of adjacent phosphate units, mediated by proton hops. We conclude that, while phosphate rotations aid proton motion, not all phosphate rotations result in proton jumps. PMID:25732257
Transversity from First Principles in QCD
Brodsky, Stanley J.; /SLAC /Southern Denmark U., CP3-Origins
2012-02-16
Transversity observables, such as the T-odd Sivers single-spin asymmetry measured in deep inelastic lepton scattering on polarized protons and the distributions which are measured in deeply virtual Compton scattering, provide important constraints on the fundamental quark and gluon structure of the proton. In this talk I discuss the challenge of computing these observables from first principles; i.e.; quantum chromodynamics, itself. A key step is the determination of the frame-independent light-front wavefunctions (LFWFs) of hadrons - the QCD eigensolutions which are analogs of the Schroedinger wavefunctions of atomic physics. The lensing effects of initial-state and final-state interactions, acting on LFWFs with different orbital angular momentum, lead to T-odd transversity observables such as the Sivers, Collins, and Boer-Mulders distributions. The lensing effect also leads to leading-twist phenomena which break leading-twist factorization such as the breakdown of the Lam-Tung relation in Drell-Yan reactions. A similar rescattering mechanism also leads to diffractive deep inelastic scattering, as well as nuclear shadowing and non-universal antishadowing. It is thus important to distinguish 'static' structure functions, the probability distributions computed the target hadron's light-front wavefunctions, versus 'dynamical' structure functions which include the effects of initial- and final-state rescattering. I also discuss related effects such as the J = 0 fixed pole contribution which appears in the real part of the virtual Compton amplitude. AdS/QCD, together with 'Light-Front Holography', provides a simple Lorentz-invariant color-confining approximation to QCD which is successful in accounting for light-quark meson and baryon spectroscopy as well as hadronic LFWFs.
First Principles Quantitative Modeling of Molecular Devices
NASA Astrophysics Data System (ADS)
Ning, Zhanyu
In this thesis, we report theoretical investigations of nonlinear and nonequilibrium quantum electronic transport properties of molecular transport junctions from atomistic first principles. The aim is to seek not only qualitative but also quantitative understanding of the corresponding experimental data. At present, the challenges to quantitative theoretical work in molecular electronics include two most important questions: (i) what is the proper atomic model for the experimental devices? (ii) how to accurately determine quantum transport properties without any phenomenological parameters? Our research is centered on these questions. We have systematically calculated atomic structures of the molecular transport junctions by performing total energy structural relaxation using density functional theory (DFT). Our quantum transport calculations were carried out by implementing DFT within the framework of Keldysh non-equilibrium Green's functions (NEGF). The calculated data are directly compared with the corresponding experimental measurements. Our general conclusion is that quantitative comparison with experimental data can be made if the device contacts are correctly determined. We calculated properties of nonequilibrium spin injection from Ni contacts to octane-thiolate films which form a molecular spintronic system. The first principles results allow us to establish a clear physical picture of how spins are injected from the Ni contacts through the Ni-molecule linkage to the molecule, why tunnel magnetoresistance is rapidly reduced by the applied bias in an asymmetric manner, and to what extent ab initio transport theory can make quantitative comparisons to the corresponding experimental data. We found that extremely careful sampling of the two-dimensional Brillouin zone of the Ni surface is crucial for accurate results in such a spintronic system. We investigated the role of contact formation and its resulting structures to quantum transport in several molecular wires and show that interface contacts critically control charge conduction. It was found, for Au/BDT/Au junctions, the H atom in -SH groups energetically prefers to be non-dissociative after the contact formation, which was supported by comparison between computed and measured break-down forces and bonding energies. The H-non-dissociated (HND) junctions give equilibrium conductances from0.054G0 (equilibrium structure) to 0.020G0 (stretched structure) which is within a factor of 2-5 of the measured data. On the other hand, for all H-dissociated contact structures - which were the assumed structures in the literature, the conductance is at least more than an order of magnitude larger that the experimental value. The HND-model significantly narrows down the theory/experiment discrepancy. Finally, a by-product of this work is a comprehensive pseudopotential and atomic orbital basis set database that has been carefully calibrated and can be used by the DFT community at large.
NASA Astrophysics Data System (ADS)
Leng, Xia; Yin, Huabing; Liang, Dongmei; Ma, Yuchen
2015-09-01
Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green's function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments.
Leng, Xia; Yin, Huabing; Liang, Dongmei; Ma, Yuchen
2015-09-21
Organic semiconductors have promising and broad applications in optoelectronics. Understanding their electronic excited states is important to help us control their spectroscopic properties and performance of devices. There have been a large amount of experimental investigations on spectroscopies of organic semiconductors, but theoretical calculation from first principles on this respect is still limited. Here, we use density functional theory (DFT) and many-body Green's function theory, which includes the GW method and Bethe-Salpeter equation, to study the electronic excited-state properties and spectroscopies of one prototypical organic semiconductor, sexithiophene. The exciton energies of sexithiophene in both the gas and bulk crystalline phases are very sensitive to the exchange-correlation functionals used in DFT for ground-state structure relaxation. We investigated the influence of dynamical screening in the electron-hole interaction on exciton energies, which is found to be very pronounced for triplet excitons and has to be taken into account in first principles calculations. In the sexithiophene single crystal, the energy of the lowest triplet exciton is close to half the energy of the lowest singlet one. While lower-energy singlet and triplet excitons are intramolecular Frenkel excitons, higher-energy excitons are of intermolecular charge-transfer type. The calculated optical absorption spectra and Davydov splitting are in good agreement with experiments. PMID:26395713
Rediscovering First Principles through Online Learning.
ERIC Educational Resources Information Center
Kidney, Gary W.; Puckett, Edmond G.
2003-01-01
Describes an evaluation of Web-based instruction at the University of Houston-Clear Lake (Texas) that showed that the design team had been distracted from many first principles of instructional design by the creative chaos on the Web and discusses how self-reflection and role definitions allowed the team to overcome these disappointments and…
Description of charge conjugation from first principles
Lujan-Peschard, C.; Napsuciale, M.
2006-09-25
We construct the charge conjugation operator as a unitary automorphism in the spinor space ((1/2), 0) + (0 (1/2)) from first principles. We calculate its eigenspinors and derive the equation of motion they satisfy. The mapping associated to charge conjugation is constructed from parity eigenstates which are considered as particle and antiparticle.
Interface Structure Prediction from First-Principles
Zhao, Xin; Shu, Qiang; Nguyen, Manh Cuong; Wang, Yangang; Ji, Min; Xiang, Hongjun; Ho, Kai-Ming; Gong, Xingao; Wang, Cai-Zhuang
2014-05-08
Information about the atomic structures at solid–solid interfaces is crucial for understanding and predicting the performance of materials. Due to the complexity of the interfaces, it is very challenging to resolve their atomic structures using either experimental techniques or computer simulations. In this paper, we present an efficient first-principles computational method for interface structure prediction based on an adaptive genetic algorithm. This approach significantly reduces the computational cost, while retaining the accuracy of first-principles prediction. The method is applied to the investigation of both stoichiometric and nonstoichiometric SrTiO3 ?3(112)[1?10] grain boundaries with unit cell containing up to 200 atoms. Several novel low-energy structures are discovered, which provide fresh insights into the structure and stability of the grain boundaries.
Theoretical study of single-molecule spectroscopy and vibrational spectroscopy in condensed phases
Yang, Shilong, 1975-
2005-01-01
In this thesis, theoretical models and computer simulations are employed to study several problems of single-molecule spectroscopy and vibrational spectroscopy in condensed phases. The first part of the thesis concentrates ...
Positron lifetimes in solids from first principles calculations
Sterne, P.A.; O'Brien, J.C.; Howell, R.H. ); Kaiser, J.H. . Dept. of Physics)
1991-08-07
We present a first principles method for calculating positron lifetimes in solids, based on self-consistent calculations using the Linear Muffin-Tin Orbital method. Local density approximations are used for both electron-electron and electron-positron interactions. Results are presented for a variety of elemental metals and vacancies to demonstrate the reliability of this approach. Theoretical calculations of positron lifetimes can be used to interpret experimental data. As an examples of this, we interpret our experimental lifetime data for the oxide superconductor Ba{sub 1-x}K{sub x}BiO{sub 3} using calculations based on this method. 12 refs., 3 figs.
Origin of Spinel Nanocheckerboards via First Principles.
Kornbluth, Mordechai; Marianetti, Chris A
2015-06-01
Self-organizing nanocheckerboards have been experimentally fabricated in Mn-based spinels but have not yet been explained with first principles. Using density-functional theory, we explain the phase diagram of the ZnMn_{x}Ga_{2-x}O_{4} system and the origin of nanocheckerboards. We predict total phase separation at zero temperature and then show the combination of kinetics, thermodynamics, and Jahn-Teller physics that generates the system's observed behavior. We find that the {011} surfaces are strongly preferred energetically, which mandates checkerboard ordering by purely geometrical considerations. PMID:26196630
Theoretical and experimental investigation of polarization spectroscopy
Hanna, Sherif Fayez
2001-01-01
, Sweden. Polarization spectroscopy saturation curves in the co-propagating beam geometry from the excitation of OH A ²[]?-X²[] (0,0) at the Q?(8) line for sub-atmospheric pressures have been fitted to the proposed model. The model proposed in this work...
Iron diffusion from first principles calculations
NASA Astrophysics Data System (ADS)
Wann, E.; Ammann, M. W.; Vocadlo, L.; Wood, I. G.; Lord, O. T.; Brodholt, J. P.; Dobson, D. P.
2013-12-01
The cores of Earth and other terrestrial planets are made up largely of iron1 and it is therefore very important to understand iron's physical properties. Chemical diffusion is one such property and is central to many processes, such as crystal growth, and viscosity. Debate still surrounds the explanation for the seismologically observed anisotropy of the inner core2, and hypotheses include convection3, anisotropic growth4 and dendritic growth5, all of which depend on diffusion. In addition to this, the main deformation mechanism at the inner-outer core boundary is believed to be diffusion creep6. It is clear, therefore, that to gain a comprehensive understanding of the core, a thorough understanding of diffusion is necessary. The extremely high pressures and temperatures of the Earth's core make experiments at these conditions a challenge. Low-temperature and low-pressure experimental data must be extrapolated across a very wide gap to reach the relevant conditions, resulting in very poorly constrained values for diffusivity and viscosity. In addition to these dangers of extrapolation, preliminary results show that magnetisation plays a major role in the activation energies for diffusion at low pressures therefore creating a break down in homologous scaling to high pressures. First principles calculations provide a means of investigating diffusivity at core conditions, have already been shown to be in very good agreement with experiments7, and will certainly provide a better estimate for diffusivity than extrapolation. Here, we present first principles simulations of self-diffusion in solid iron for the FCC, BCC and HCP structures at core conditions in addition to low-temperature and low-pressure calculations relevant to experimental data. 1. Birch, F. Density and composition of mantle and core. Journal of Geophysical Research 69, 4377-4388 (1964). 2. Irving, J. C. E. & Deuss, A. Hemispherical structure in inner core velocity anisotropy. Journal of Geophysical Research 116, B04307 (2011). 3. Buffett, B. A. Onset and orientation of convection in the inner core. Geophysical Journal International 179, 711-719 (2009). 4. Bergman, M. Measurements of electric anisotropy due to solidification texturing and the implications for the Earth's inner core. Nature 389, 60-63 (1997). 5. Deguen, R. & Cardin, P. Thermochemical convection in Earth's inner core. Geophysical Journal International 187, 1101-1118 (2011). 6. Reaman, D. M., Daehn, G. S. & Panero, W. R. Predictive mechanism for anisotropy development in the Earth's inner core. Earth and Planetary Science Letters 312, 437-442 (2011). 7. Ammann, M. W., Brodholt, J. P., Wookey, J. & Dobson, D. P. First-principles constraints on diffusion in lower-mantle minerals and a weak D'' layer. Nature 465, 462-5 (2010).
Phonon-phonon interactions: First principles theory
NASA Astrophysics Data System (ADS)
Gibbons, T. M.; Bebek, M. B.; Kang, By.; Stanley, C. M.; Estreicher, S. K.
2015-08-01
We present the details of a method to perform molecular-dynamics (MD) simulations without thermostat and with very small temperature fluctuations ±?T starting with MD step 1. It involves preparing the supercell at the time t = 0 in physically correct microstates using the eigenvectors of the dynamical matrix. Each initial microstate corresponds to a different distribution of kinetic and potential energies for each vibrational mode (the total energy of each microstate is the same). Averaging the MD runs over many initial microstates further reduces ?T. The electronic states are obtained using first-principles theory (density-functional theory in periodic supercells). Three applications are discussed: the lifetime and decay of vibrational excitations, the isotope dependence of thermal conductivities, and the flow of heat at an interface.
Numerical Inductance Calculations Based on First Principles
Shatz, Lisa F.; Christensen, Craig W.
2014-01-01
A method of calculating inductances based on first principles is presented, which has the advantage over the more popular simulators in that fundamental formulas are explicitly used so that a deeper understanding of the inductance calculation is obtained with no need for explicit discretization of the inductor. It also has the advantage over the traditional method of formulas or table lookups in that it can be used for a wider range of configurations. It relies on the use of fast computers with a sophisticated mathematical computing language such as Mathematica to perform the required integration numerically so that the researcher can focus on the physics of the inductance calculation and not on the numerical integration. PMID:25402467
Accurate Thermal Conductivities from First Principles
NASA Astrophysics Data System (ADS)
Carbogno, Christian
2015-03-01
In spite of significant research efforts, a first-principles determination of the thermal conductivity at high temperatures has remained elusive. On the one hand, Boltzmann transport techniques that include anharmonic effects in the nuclear dynamics only perturbatively become inaccurate or inapplicable under such conditions. On the other hand, non-equilibrium molecular dynamics (MD) methods suffer from enormous finite-size artifacts in the computationally feasible supercells, which prevent an accurate extrapolation to the bulk limit of the thermal conductivity. In this work, we overcome this limitation by performing ab initio MD simulations in thermodynamic equilibrium that account for all orders of anharmonicity. The thermal conductivity is then assessed from the auto-correlation function of the heat flux using the Green-Kubo formalism. Foremost, we discuss the fundamental theory underlying a first-principles definition of the heat flux using the virial theorem. We validate our approach and in particular the techniques developed to overcome finite time and size effects, e.g., by inspecting silicon, the thermal conductivity of which is particularly challenging to converge. Furthermore, we use this framework to investigate the thermal conductivity of ZrO2, which is known for its high degree of anharmonicity. Our calculations shed light on the heat resistance mechanism active in this material, which eventually allows us to discuss how the thermal conductivity can be controlled by doping and co-doping. This work has been performed in collaboration with R. Ramprasad (University of Connecticut), C. G. Levi and C. G. Van de Walle (University of California Santa Barbara).
Theoretical Calculations of Atomic Data for Spectroscopy
NASA Technical Reports Server (NTRS)
Bautista, Manuel A.
2000-01-01
Several different approximations and techniques have been developed for the calculation of atomic structure, ionization, and excitation of atoms and ions. These techniques have been used to compute large amounts of spectroscopic data of various levels of accuracy. This paper presents a review of these theoretical methods to help non-experts in atomic physics to better understand the qualities and limitations of various data sources and assess how reliable are spectral models based on those data.
Theoretical Sum Frequency Generation Spectroscopy of Peptides
2015-01-01
Vibrational sum frequency generation (SFG) has become a very promising technique for the study of proteins at interfaces, and it has been applied to important systems such as anti-microbial peptides, ion channel proteins, and human islet amyloid polypeptide. Moreover, so-called “chiral” SFG techniques, which rely on polarization combinations that generate strong signals primarily for chiral molecules, have proven to be particularly discriminatory of protein secondary structure. In this work, we present a theoretical strategy for calculating protein amide I SFG spectra by combining line-shape theory with molecular dynamics simulations. We then apply this method to three model peptides, demonstrating the existence of a significant chiral SFG signal for peptides with chiral centers, and providing a framework for interpreting the results on the basis of the dependence of the SFG signal on the peptide orientation. We also examine the importance of dynamical and coupling effects. Finally, we suggest a simple method for determining a chromophore’s orientation relative to the surface using ratios of experimental heterodyne-detected signals with different polarizations, and test this method using theoretical spectra. PMID:25203677
Efficient first-principles electronic dynamics
NASA Astrophysics Data System (ADS)
Liang, Wenkel; Chapman, Craig T.; Li, Xiaosong
2011-05-01
An efficient first-principles electronic dynamics method is introduced in this article. The approach we put forth relies on incrementally constructing a time-dependent Fock/Kohn-Sham matrix using active space density screening method that reduces the cost of computing two-electron repulsion integrals. An adaptive stepsize control algorithm is developed to optimize the efficiency of the electronic dynamics while maintaining good energy conservation. A selected set of model dipolar push-pull chromophore molecules are tested and compared with the conventional method of direct formation of the Fock/Kohn-Sham matrix. While both methods considered herein take on identical dynamical simulation pathways for the molecules tested, the active space density screening algorithm becomes much more computationally efficient. The adaptive stepsize control algorithm, when used in conjunction with the dynamically active space method, yields a factor of ˜3 speed-up in computational cost as observed in electronic dynamics using the time dependent density functional theory. The total computational cost scales nearly linear with increasing size of the molecular system.
Phonon Engineering in Metals from First Principles
NASA Astrophysics Data System (ADS)
Lanzillo, Nicholas; Thomas, J.; Watson, E. B.; Washington, M.; Nayak, Saroj K.
2013-03-01
The electron-phonon interaction in metallic systems controls the electronic transport properties, including both electrical and thermal resistivity. The effect of compressive strain on the electron-phonon interaction in metals is investigated using first-principles density functional theory, and we propose various ways to ``engineer'' this interaction for various technological applications. In particular, we show that by applying compressive strain on the FCC crystals of Al, Cu, Ag and Au, the net electron-phonon scattering rate decreases and likewise the electrical resistivity decreases with increasing pressure. This trend is corroborated by experimental measurements of the resistance of a 0.5 mm diameter high-purity Al wire pressurized up to 2 GPa in a solid-media pressure apparatus at room temperature. The rate of the decrease in electrical resistivity as a function of pressure as determined by experiment is matched by the rate predicted by theory. Our simulations show that Al nanowires have the same response to strain as the bulk crystal; the net electron-phonon scattering can be reduced through compressive strain. Modifying the electron-phonon interaction in metallic structures shows great promise for future nano-electronic devices.
First principle study of sodium decorated graphyne
NASA Astrophysics Data System (ADS)
Sarkar, Utpal; Bhattacharya, Barnali; Seriani, Nicola
2015-11-01
We present first-principles calculations of the electronic properties of Na-decorated graphyne. This structure of the graphyne family is a direct band gap semiconductor with a band gap of 0.44 eV in absence of sodium, but Na-decorated graphyne compounds are metallic, and can then be employed as carbon-based conductors. Metallization is due to charge donation from sodium to carbon. Pristine graphyne is more stable than Na-decorated graphyne, therefore is seems probable that, if this material should be employed as electrode in Na-ion batteries, it would lead to the formation of metallic sodium rather than well dispersed sodium ions. On the other side, this property might be useful if graphyne is employed in water desalination. Finally, the abrupt change from a semiconducting to a metallic state in presence of a small amount of sodium might be exploited in electronics, e.g. for the production of smooth metal-semiconductor interfaces through spatially selective deposition of sodium.
First-principles study of point defects in thorium carbide
NASA Astrophysics Data System (ADS)
Pérez Daroca, D.; Jaroszewicz, S.; Llois, A. M.; Mosca, H. O.
2014-11-01
Thorium-based materials are currently being investigated in relation with their potential utilization in Generation-IV reactors as nuclear fuels. One of the most important issues to be studied is their behavior under irradiation. A first approach to this goal is the study of point defects. By means of first-principles calculations within the framework of density functional theory, we study the stability and formation energies of vacancies, interstitials and Frenkel pairs in thorium carbide. We find that C isolated vacancies are the most likely defects, while C interstitials are energetically favored as compared to Th ones. These kind of results for ThC, to the best authors' knowledge, have not been obtained previously, neither experimentally, nor theoretically. For this reason, we compare with results on other compounds with the same NaCl-type structure.
Optimized Materials From First Principles Simulations: Are We There Yet?
Galli, G; Gygi, F
2005-07-26
In the past thirty years, the use of scientific computing has become pervasive in all disciplines: collection and interpretation of most experimental data is carried out using computers, and physical models in computable form, with various degrees of complexity and sophistication, are utilized in all fields of science. However, full prediction of physical and chemical phenomena based on the basic laws of Nature, using computer simulations, is a revolution still in the making, and it involves some formidable theoretical and computational challenges. We illustrate the progress and successes obtained in recent years in predicting fundamental properties of materials in condensed phases and at the nanoscale, using ab-initio, quantum simulations. We also discuss open issues related to the validation of the approximate, first principles theories used in large scale simulations, and the resulting complex interplay between computation and experiment. Finally, we describe some applications, with focus on nanostructures and liquids, both at ambient and under extreme conditions.
A first-principles model for orificed hollow cathode operation
NASA Technical Reports Server (NTRS)
Salhi, A.; Turchi, P. J.
1992-01-01
A theoretical model describing orificed hollow cathode discharge is presented. The approach adopted is based on a purely analytical formulation founded on first principles. The present model predicts the emission surface temperature and plasma properties such as electron temperature, number densities and plasma potential. In general, good agreements between theory and experiment are obtained. Comparison of the results with the available related experimental data shows a maximum difference of 10 percent in emission surface temperature, 20 percent in electron temperature and 35 percent in plasma potential. In case of the variation of the electron number density with the discharge current a maximum discrepancy of 36 percent is obtained. However, in the case of the variation with the cathode internal pressure, the predicted electron number density is higher than the experimental data by a maximum factor of 2.
Microscopic Dynamics of Supercooled Liquids from First Principles
NASA Astrophysics Data System (ADS)
Janssen, Liesbeth M. C.; Reichman, David R.
2015-11-01
The transition from a liquid to a glass remains one of the most poorly understood phenomena in condensed matter physics, and still no fully microscopic theory exists that can describe the dynamics of supercooled liquids in a quantitative manner over all relevant time scales. Here, we present a theoretical framework that yields near-quantitative accuracy for the time-dependent correlation functions of a glass-forming system over a broad density range. Our approach requires only simple static structural information as input and is based entirely on first principles. Owing to its ab initio nature, the framework offers a unique platform to study the relation between structure and dynamics in glass-forming matter, and paves the way towards a systematically correctable and ultimately fully quantitative theory of microscopic glassy dynamics.
A first-principle calculation of the XANES spectrum of Cu2+ in water
NASA Astrophysics Data System (ADS)
La Penna, G.; Minicozzi, V.; Morante, S.; Rossi, G. C.; Stellato, F.
2015-09-01
The progress in high performance computing we are witnessing today offers the possibility of accurate electron density calculations of systems in realistic physico-chemical conditions. In this paper, we present a strategy aimed at performing a first-principle computation of the low energy part of the X-ray Absorption Spectroscopy (XAS) spectrum based on the density functional theory calculation of the electronic potential. To test its effectiveness, we apply the method to the computation of the X-ray absorption near edge structure part of the XAS spectrum in the paradigmatic, but simple case of Cu2+ in water. In order to keep into account the effect of the metal site structure fluctuations in determining the experimental signal, the theoretical spectrum is evaluated as the average over the computed spectra of a statistically significant number of simulated metal site configurations. The comparison of experimental data with theoretical calculations suggests that Cu2+ lives preferentially in a square-pyramidal geometry. The remarkable success of this approach in the interpretation of XAS data makes us optimistic about the possibility of extending the computational strategy we have outlined to the more interesting case of molecules of biological relevance bound to transition metal ions.
Two-Dimensional Electronic Spectroscopy Using Incoherent Light: Theoretical Analysis
Turner, Daniel B; Sutor, Erika J; Hendrickson, Rebecca A; Gealy, M W; Ulness, Darin J
2012-01-01
Electronic energy transfer in photosynthesis occurs over a range of time scales and under a variety of intermolecular coupling conditions. Recent work has shown that electronic coupling between chromophores can lead to coherent oscillations in two-dimensional electronic spectroscopy measurements of pigment-protein complexes measured with femtosecond laser pulses. A persistent issue in the field is to reconcile the results of measurements performed using femtosecond laser pulses with physiological illumination conditions. Noisy-light spectroscopy can begin to address this question. In this work we present the theoretical analysis of incoherent two-dimensional electronic spectroscopy, I(4) 2D ES. Simulations reveal diagonal peaks, cross peaks, and coherent oscillations similar to those observed in femtosecond two-dimensional electronic spectroscopy experiments. The results also expose fundamental differences between the femtosecond-pulse and noisy-light techniques; the differences lead to new challenges and opp...
Ethanol adsorbed on ice: A first-principles study C. Thierfelder*
Schmidt, Wolf Gero
Ethanol adsorbed on ice: A first-principles study C. Thierfelder* Centre of Theoretical Chemistry of ethanol molecules on the ice Ih basal plane. Apart from smooth surfaces, also substrate models simulation for ethanol adsorbed on ice using the TIP4P potential16 for the water-water interaction. Recent
First principles calculations for modern ceramic science and engineering.
Tanaka, Isao; Oba, Fumiyasu
2008-02-13
The free energy of compounds can be theoretically obtained as a function of temperature, pressure and chemical potentials by a combination of a first principles method including phonon calculations and statistical approaches using cluster expansion and Monte Carlo simulations. The information is quite useful in ceramic science and engineering since experimental data are not abundantly available. As an example of phonon calculations, results for graphite in comparison to diamond are presented. The free energy difference among polymorphs of Ga(2)O(3) is shown as a function of temperature as well. Theoretical calculations of x-ray absorption near edge structures (XANES) and electron energy loss near edge structures (ELNES) are also demonstrated. Proper inclusion of the core-hole effect is mandatory in the calculation. For 3d transition element L(2,3) XANES/ELNES, a configuration interaction approach to take account of the correlation among the core-hole and the excited electron satisfactorily reproduces experimental spectra. As an example, results for Mn-doped ZnO are shown. PMID:21693877
Phonon Thermal Transport in Thermoelectric Materials from First Principles
NASA Astrophysics Data System (ADS)
Broido, David
2013-03-01
Breakthroughs in nanoscience and materials fabrication technology have led to the creation of materials with very low lattice thermal conductivity, a requirement for high thermoelectric efficiency. There is now an unprecedented need for quantitative, predictive theoretical approaches to provide fundamental understanding of lattice thermal transport in thermoelectric materials and insight into the design and development of new materials for enhanced thermoelectric applications. In this talk, I will describe our atomistic first principles approach for calculating lattice thermal conductivity of materials, which combines a complete solution of the Boltzmann transport equation for phonons with harmonic and anharmonic interatomic forces determined from density functional theory. I will present an overview of this theoretical approach along with some of our recent calculated results for a range of test materials such as Si, Ge and III-V compounds. I will also discuss results for thermoelectric alloys such as SixGe1-x and Mg2SixSn1-x and nanoparticle embedded in alloy thermoelectric (NEAT) materials. Finally, I will discuss insights gained from this effort such as the importance of anharmonic coupling of acoustic and optic phonon modes. This research was supported in part by NSF Grants CBET-1066634, CBET-1066404, by DARPA, by the S3TEC, an Energy Frontier Research Center funded by the US DOE, office of Basic Energy Sciences under award N0. DE-FG02-09ER46577, and by an EU IRG Grant.
First Principle Study of Sodium Nanoclusters
NASA Astrophysics Data System (ADS)
Saxena, Prabodh Sahai; Srivastava, Pankaj; Shrivastava, Ashwani Kumar
2011-12-01
The structural and electronic properties of small Nan (n = 2-5) nanoclusters have been investigated by employing an ab-initio self-consistent density functional theory in the local density approximation. The total energy, binding energy, bond length and HOMO-LUMO gap are calculated in large energy interval for various isomeric forms of sodium nanoclusters. The results are compared with the other theoretical calculations.
First Principles Calculations for X-ray Resonant Spectra and Elastic Properties
Yongbin Lee
2006-05-01
In this thesis, we discuss applications of first principles methods to x-ray resonant spectra and elastic properties calculation. We start with brief reviews about theoretical background of first principles methods, such as density functional theory, local density approximation (LDA), LDA+U, and the linear augmented plane wave (LAPW) method to solve Kohn-Sham equations. After that we discuss x-ray resonant scattering (XRMS), x-ray magnetic circular dichroism (XMCD) and the branching problem in the heavy rare earths Ledges. In the last chapter we discuss the elastic properties of the second hardest material AlMgB{sub 14}.
Designing Interactive Learning Environments: An Approach from First Principles
ERIC Educational Resources Information Center
Scott, Bernard; Cong, Chunyu
2007-01-01
Purpose: Today's technology supports the design of more and more sophisticated interactive learning environments. This paper aims to argue that such design should develop from first principles. Design/methodology/approach: In the paper by first principles is meant: learning theory and principles of course design. These principles are briefly…
NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study
Bevilaqua, Rochele C. A.; Miranda, Caetano R.; Rigo, Vagner A.; Veríssimo-Alves, Marcos
2014-11-28
The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.
NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.
Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R
2014-11-28
The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955
First principles characterization of silicate sites in clay surfaces.
Alvim, Raphael S; Miranda, Caetano R
2015-02-21
Aluminosilicate clays like Montmorillonite (MMT) and Muscovite Mica (MT) have siloxane cavities on the basal plane. The hydroxyl groups localized in these cavities and van der Waals (vdW) forces contribute significantly to adsorption processes. However, the basal sites are found to be difficult to characterize experimentally. Here, (001) surfaces of MMT and MT clays were investigated using first-principles calculations to understand how these silicate surface sites are influenced by hydroxyl groups and the effective role of inner layer vdW interactions. Based on density-functional theory (DFT) within the generalized gradient approximation (GGA), different types of exchange-correlation functionals were tested to check the effect of vdW dispersion correction. Noncontact atomic force microscopy (nc-AFM), X-ray absorption spectroscopy (XAS) in the near-edge region and solid-state nuclear magnetic resonance (SS-NMR) spectroscopy were simulated. In both clays, the oxygen surface sites are directly affected by the intralayer interaction through hydroxyl groups. Our results indicated that the chemical environment of the hydroxyl groups is distinct in the MMT and MT structures. The vdW correction was essential for a better description of the surface oxygen sites and correctly describes the similarity between both clays. Particularly, the bulk apical oxygen sites in the MT structure are less influenced by vdW interaction. Compared to MMT, the silicon surface sites of MT are more sensitive to the intralayer changes in Si-Oapical-Al and with less effect of the hydroxyl groups. These results provide a clear understanding of influence of the siloxane cavity on the oxygen and silicon surface sites in aluminosilicates. PMID:25592132
First principles study of biomineral hydroxyapatite
NASA Astrophysics Data System (ADS)
Slepko, Alexander
2010-03-01
Hydroxyapatite (HA) [Ca10(PO4)6(OH)2] is one of the most abundant materials in mammal bone. It crystallizes within the spaces between the tropocollagen chains and strengthens the bone tissue. The mineral content of human bone increases with age reaching a maximum value from which it starts to decrease leading to diseases such as osteomalacia. Therefore, an emergent application of this study is bone repair and the production of synthetic bone. Despite its importance, little is known about the growth of HA crystallites in bones. Nor is it well understood how the HA attaches to protein chains and interacts with the surrounding aqueous solution. Using density functional theory (DFT) we calculate the theoretical ground state structure, electronic and vibration properties of hexagonal HA. We find several low energy structures and analyze the energy barriers for spontaneous phase transitions. We calculate the phonon density of states and study the surface energetics for different orientations. We identify the surfaces with highest reactivity using the frontier orbital approach and analyze interactions between these surfaces and water molecules/amino acids.
First-principles theory of multipolar order in actinide dioxides
NASA Astrophysics Data System (ADS)
Magnani, Nicola; Suzuki, Michi-To; Oppeneer, Peter M.
2014-08-01
Magnetic phase transitions that involve multipolar degrees of freedom have been widely studied during the last couple of decades, challenging the common approximation which assumes that the physical properties of a magnetic material could be effectively described by purely dipolar degrees of freedom. Due to the complexity of the problem and to the large number of competing interactions involved, the simple (fcc) crystal structure of the actinide dioxides made them the ideal playground system for such theoretical and experimental studies. In the present paper, we summarize our recent attempts to provide an ab initio description of the ordered phases of UO2, NpO2, and AmO2 by means of state-of-the-art LDA+U first-principles calculations. This systematic analysis of the electronic structures is here naturally connected to the local crystalline fields of the 5f states in the actinide dioxide series. Related to these we find that the mechanisms which lead to the experimentally observed insulating ground states work in distinctly different ways for each compound. xml:lang="fr"
First principles Tafel kinetics of methanol oxidation on Pt(111)
NASA Astrophysics Data System (ADS)
Fang, Ya-Hui; Liu, Zhi-Pan
2015-01-01
Electrocatalytic methanol oxidation is of fundamental importance in electrochemistry and also a key reaction in direct methanol fuel cell. To resolve the kinetics at the atomic level, this work investigates the potential-dependent reaction kinetics of methanol oxidation on Pt(111) using the first principles periodic continuum solvation model based on modified-Poisson-Boltzmann equation (CM-MPB), focusing on the initial dehydrogenation elementary steps. A theoretical model to predict Tafel kinetics (current vs potential) is established by considering that the rate-determining step of methanol oxidation (to CO) is the first Csbnd H bond breaking (CH3OH(aq) ? CH2OH* + H*) according to the computed free energy profile. The first Csbnd H bond breaking reaction needs to overcome a large entropy loss during methanol approaching to the surface and replacing the adsorbed water molecules. While no apparent charge transfer is involved in this elementary step, the charge transfer coefficient of the reaction is calculated to be 0.36, an unconventional value for charge transfer reactions, and the Tafel slope is deduced to be 166 mV. The results show that the metal/adsorbate interaction and the solvation environment play important roles on influencing the Tafel kinetics. The knowledge learned from the potential-dependent kinetics of methanol oxidation can be applied in general for understanding the electrocatalytic reactions of organic molecules at the solid-liquid interface.
First principles molecular dynamics without self-consistent field optimization
Souvatzis, Petros; Niklasson, Anders M. N.
2014-01-28
We present a first principles molecular dynamics approach that is based on time-reversible extended Lagrangian Born-Oppenheimer molecular dynamics [A. M. N. Niklasson, Phys. Rev. Lett. 100, 123004 (2008)] in the limit of vanishing self-consistent field optimization. The optimization-free dynamics keeps the computational cost to a minimum and typically provides molecular trajectories that closely follow the exact Born-Oppenheimer potential energy surface. Only one single diagonalization and Hamiltonian (or Fockian) construction are required in each integration time step. The proposed dynamics is derived for a general free-energy potential surface valid at finite electronic temperatures within hybrid density functional theory. Even in the event of irregular functional behavior that may cause a dynamical instability, the optimization-free limit represents a natural starting guess for force calculations that may require a more elaborate iterative electronic ground state optimization. Our optimization-free dynamics thus represents a flexible theoretical framework for a broad and general class of ab initio molecular dynamics simulations.
Theoretical Study of the Vibrational Spectroscopy of the Ethyl Radical
NASA Astrophysics Data System (ADS)
Tabor, Daniel P.; Sibert, Edwin. L. Sibert, Iii
2013-06-01
The rich spectroscopy of the ethyl radical has attracted the attention of several experimental and theoretical investigations. The purpose of these studies was to elucidate the signatures of hyperconjugation, torsion, inversion, and Fermi coupling in the molecular spectra. Due to the number of degrees of freedom in the system, previous theoretical studies have implemented reduced-dimensional models. Our ultimate goal is a full-dimensional theoretical treatment of the vibrations using both Van Vleck and variational approaches. The methods will be combined with the potential that we have calculated using the CCSD(T) method on the cc-pVTZ basis set. In this talk we will discuss our initial work, which builds up from these reduced-dimensional models. Our calculations use coordinates that exploit the system's G_{12} PI symmetry in a simple fashion. By systematically adding more degrees of freedom to our model, we can determine the effects of specific couplings on the spectroscopy. T. Häber, A. C. Blair, D. J. Nesbitt and M. D. Schuder J. Chem. Phys. {124}, 054316, (2006). G .E. Douberly, unpublished. R. S. Bhatta, A. Gao and D. S. Perry J. Mol. Struct.: THEOCHEM {941}, 22, (2010).
First Principles Modeling for Research and Design of New Materials
Ceder, Gerbrand
First principles computation can be used to investigate an design materials in ways that can not be achieved with experimental means. We show how computations can be used to rapidly capture the essential physics that ...
Inelastic transport In molecular junctions from first principles
Kim, Sejoong, Ph. D. Massachusetts Institute of Technology
2012-01-01
This work is dedicated to development of a first-principle approach to study electron-vibration interactions on quantum transport properties. In the first part we discuss a general implementation for inelastic transport ...
Ballistic Transport in Nanostructures from First-Principles Simulations
Marzari, Nicola
We developed and implemented a first-principles based theory of the Landauer ballistic conductance, to determine the transport properties of nanostructures and molecular-electronics devices. Our approach starts from a ...
Design of water-splitting photocatalysts by first principles computations
Wu, Yabi
2014-01-01
This thesis focuses on the design of novel inorganic water-splitting photocatalysts for solar applications using first principles computations. Water-splitting photocatalysts are materials that can photo-catalyze the ...
Time-dependent first-principles approaches to PV materials
Miyamoto, Yoshiyuki
2013-12-10
Computational scheme for designing photovoltaic (PV) materials is presented. First-principles electron dynamics of photo-excitation and subsequent electron-hole splitting is performed based on the time-dependent density functional theory. Photo-induced enhancement of dipole moment was observed in a polar crystal and a donor-acceptor molecular pair. These experiences will pave a way to design PV material from first-principles simulations.
First-principles studies of multiferroic and magnetoelectric materials
Fang, Yue-Wen; Tong, Wen-Yi; Zhu, Wan-Jiao; Shen, Xin; Gong, Shi-Jing; Wan, Xian-Gang; Duan, Chun-Gang
2015-01-01
Multiferroics are materials where two or more ferroic orders coexist owing to the interplay between spin, charge, lattice and orbital degrees of freedom. The explosive expansion of multiferroics literature in recent years demon-strates the fast growing interest in this field. In these studies, the first-principles calculation has played a pioneer role in the experiment explanation, mechanism discovery and prediction of novel multiferroics or magnetoelectric materials. In this review, we discuss, by no means comprehensively, the extensive applications and successful achievements of first-principles approach in the study of multiferroicity, magnetoelectric effect and tunnel junc-tions. In particular, we introduce some our recently developed methods, e.g., the orbital selective external potential (OSEP) method, which prove to be powerful tools in the finding of mechanisms responsible for the intriguing phe-nomena occurred in multiferroics or magnetoelectric materials. We also summarize first-principles studies o...
Transport and first-principles study of novel thermoelectric materials
NASA Astrophysics Data System (ADS)
Chi, Hang
Thermoelectric materials can recover waste industrial heat and convert it to electricity as well as provide efficient local cooling of electronic devices. The efficiency of such environmentally responsible and exceptionally reliable solid state energy conversion is determined by the dimensionless figure-of-merit ZT = alpha2 sigmaT/kappa, where alpha is the Seebeck coefficient, sigma is the electrical conductivity, kappa is the thermal conductivity, and T is the absolute temperature. The goal of the thesis is to (i) illustrate the physics to achieve high ZT of advanced thermoelectric materials and (ii) explore fundamental structure and transport properties in novel condensed matter systems, via an approach combining comprehensive experimental techniques and state-of-the-art first-principles simulation methods. Thermo-galvanomagnetic transport coefficients are derived from Onsager's reciprocal relations and evaluated via solving Boltzmann transport equation using Fermi-Dirac statistics, under the relaxation time approximation. Such understanding provides insights on enhancing ZT through two physically intuitive and very effective routes: (i) improving power factor PF = alpha2sigma; and (ii) reducing thermal conductivity kappa, as demonstrated in the cases of Mg2Si1-xSnx solid solution and Ge/Te double substituted skutterudites CoSb3(1-x)Ge1.5x Te1.5x, respectively. Motivated by recent theoretical predictions of enhanced thermoelectric performance in highly mismatched alloys, ZnTe:N molecular beam epitaxy (MBE) films deposited on GaAs (100) substrates are carefully examined, which leads to a surprising discovery of significant phonon-drag thermopower (reaching 1-2 mV/K-1) at ~13 K. Further systematic study in Bi2Te3 MBE thin films grown on sapphire (0001) and/or BaF2 (111) substrates, reveal that the peak of phonon drag can be tuned by the choice of substrates with different Debye temperatures. Moreover, the detailed transport and structure studies of Bi2-xTl xTe3 single crystals demonstrate that thallium doping leads to a bulk insulating state for such a topological insulator, which opens an avenue for further investigations of transport phenomena related to surface states. Finally, using the combined theoretical and experimental approaches, a new layered transition metal dichalcogenide type of ground state of Cu 2Se is proposed, which exhibits extraordinary weak anti-localization type of magnetoresistance at liquid helium temperatures.
Urban Growth Simulation From "First Principles" Claes Andersson
Rasmussen, Steen
presented in this paper are particularly important in relation to "urban sprawl", an important aspectUrban Growth Simulation From "First Principles" Claes Andersson EES-6 MS T003, Los Alamos National, roger@plato.ucs.mun.ca (December 5, 2001) General and mathematically transparent models of urban growth
Understanding nano-materials from first principles Leeor Kronik
Adler, Joan
Understanding nano-materials from first principles Leeor Kronik Department of Materials and Interfaces, Weizmann Institute of science, Rehovoth 76100 Nano-sized materials often exhibit exciting new traditional solid-state physics models are applicable to the intermediate nano- size range. As a result, first
FIRST-PRINCIPLES MOLECULAR DYNAMICS Roberto Car1
Giannozzi, Paolo
. Car et al. elements such as hydrogen; classical or ab initio path integral approaches can1.4 FIRST-PRINCIPLES MOLECULAR DYNAMICS Roberto Car1 , Filippo de Angelis2 , Paolo Giannozzi3 in the last two decades as a powerful tool to probe the properties of matter at the microscopic scale
COMMUNICATION First Principles Prediction of Protein Folding Rates
Goddard III, William A.
may fold by a faster, alternative mechanism. This method can be applied to any protein for whichCOMMUNICATION First Principles Prediction of Protein Folding Rates Derek A. Debe and William A studies have demonstrated that many small, single-domain proteins fold via simple two-state kinetics. We
Zhu, G.; Lewandowski, A.
2012-11-01
A new analytical method -- First-principle OPTical Intercept Calculation (FirstOPTIC) -- is presented here for optical evaluation of trough collectors. It employs first-principle optical treatment of collector optical error sources and derives analytical mathematical formulae to calculate the intercept factor of a trough collector. A suite of MATLAB code is developed for FirstOPTIC and validated against theoretical/numerical solutions and ray-tracing results. It is shown that FirstOPTIC can provide fast and accurate calculation of intercept factors of trough collectors. The method makes it possible to carry out fast evaluation of trough collectors for design purposes. The FirstOPTIC techniques and analysis may be naturally extended to other types of CSP technologies such as linear-Fresnel collectors and central-receiver towers.
Atomic-scale structures in complex solids by Z-contrast STEM and first-principles theory
Pennycook, S.J.; Pantelides, S.T.; Maiti, A. |; Chisholm, M.F.; Yan, Y.
1998-02-01
Modern high-resolution scanning transmission electron microscopes are capable of forming electron probes below 2{angstrom}, sufficiently small to allow an atomic resolution Z-contrast image to be formed from many materials. Such images, formed with a high angle annular detector, are incoherent in nature, and can be described as a convolution of the probe intensity profile with an object function peaked sharply at the atomic sites. Unlike phase contrast microscopy, there is no phase problem associated with an incoherent image, and direct inversion to the projected atomic structure is possible. A quantitative method for structure retrieval is maximum entropy analysis, although under Scherzer incoherent conditions the probe tails are small, and peaks in the image intensity correspond closely to atomic positions. In such cases, an intuitive structure determination may be possible. Electron energy loss spectroscopy (EELS) may also be performed simultaneously, using the Z-contrast image to position the probe over selected atomic columns, providing complementary information on composition and electronic structure. On the theoretical side, present-day computers are now capable of electronic structure calculations that can be used to determine the preferred atomic arrangements in complex systems. Both first-principles and semiempirical approaches have been developed with complementary capabilities. Here the authors present several examples where a synergistic approach combining Z-contrast STEM, spatially resolved EELS and theoretical results have led to the elucidation of complex atomic structures. The ability to determine atomic structures experimentally to high accuracy provides both a perfect starting point for theoretical calculations and an ideal test of theoretical predictions. Theoretical studies can explore the new dimensions of time and energy. This combined approach leads to a detailed and comprehensive picture of complex atomistic mechanisms.
Angle-resolved photoemission and first-principles studies of topological thin films
NASA Astrophysics Data System (ADS)
Bian, Guang
Topological insulators are electronic materials that have a bulk band gap like an ordinary insulator but have protected conducting states on their edge or surface. The exotic electronic properties of topological materials are of great interest for spin-related electronics and quantum computation. In this thesis research, the combination of angleresolved photoemission spectroscopy (ARPES) and first principles calculation is used to examine the electronic properties of topological thin films and 2D electronic systems with large spin-orbit splitting. The topological thin films are prepared in situ by molecular beam epitaxy (MBE) method and characterized by experimental tools such as reflection high-energy electron diffraction (RHEED) and low energy electron diffraction (LEED). The systems investigated in this thesis include topological Sb, Bi2Te3, Be2Se 3 thin films, Bi films, and Bi/Ag surface alloy. Topological Sb films have been successfully fabricated on Si(111) substrates. By examining the connection pattern between surface states and the quantum well bulk states, our photoemission spectra show clearly the topological order of the Sb films. When topological films become ultrathin, the quantum tunneling effect breaks the degeneracy at the Dirac point of the topological surface bands, resulting in a gap. Our ARPES mapping of the surface band structure of a 4-BL Sb film reveals no energy gap at the Dirac point. This lack of tunneling gap can be explained by a strong interfacial bonding between the film and the substrate. The topological order of topological materials is a robust quantity, but the topological surface states themselves can be highly sensitive to the boundary conditions. Specifically, the surface states of Bi2Se3 and Bi2Te3 form a single Dirac cone at the zone center. Our first-principles calculations based on a slab geometry show that, upon hydrogen termination of either face of the slab, the Dirac cone associated with this face is replaced by three Dirac cones centered at the time-reversal-invariant M¯ points at the zone boundary. The critical behavior of the TI film near the quantum critical point is also studied theoretically. When the strength of the spin-orbit coupling (SOC) is tuned across the critical point, the topological surface states, while protected by symmetry in the bulk limit, can be missing completely in topological films even at large film thicknesses. We have observed, using angle-resolved photoemission, a structural phase transformation of Bi films deposited on Si(111)-(7x7). Films with thicknesses 20 to ~100 A, upon annealing, first order into a metastable pseudocubic (PC) phase and then transform into a stable rhombohedral (RH) phase with very different topologies for the quantum well subband structures. The PC phase shows a surface band with a maximum near the Fermi level at G , whereas the RH phase shows a Dirac-like subband around M¯ along K¯ -- M¯ -- K¯ . The formation of the metastable phase over a wide thickness range can be attributed to a surface nucleation mechanism. Finally, we have studied the electronic structure of the Bi/Ag surface alloy, a system possessing a huge Rashba splitting in its surface bands. The Bi/Ag surface alloy is prepared by depositing Bi onto ultrathin Ag films followed by annealing. The electronic structure of the system is measured using circular angle resolved photoemission spectroscopy (CARPES). The results reveal two interesting phenomena: the hybridization of spin polarized surface states with Ag bulk quantum well states and the umklapp scattering by the perturbed surface potential. In addition, our CARPES spectra show clearly a unique dichroism pattern which is closely related to the spin texture of this 2D strongly spin-orbit coupled electron system.
Theoretical foundations of MHD spectroscopy in Madison Plasma Dynamo Experiment
NASA Astrophysics Data System (ADS)
Siller, Robert; Khalzov, Ivan; Forest, Cary
2014-10-01
We develop a theoretical basis of active MHD spectroscopy for Madison Plasma Dynamo Experiment (MPDX). This new diagnostic is based on an analysis of incompressible shear Alfven modes and compressible acoustic modes for spherical plasmas, and the influence of plasma flow on the corresponding eigen-spectrum. Alfven modes in plasma are assumed to be excited in the presence of an external axial magnetic field. The mode frequencies depend on the distribution of plasma parameters. Inverting this dependence for a given (experimentally measured) set of modes, we are able to infer the spatial structure of plasma characteristics. We demonstrate this inversion technique by determining the rigid plasma rotation from the splitting of the low-frequency resonance Alfven modes driven by a localized antenna. Compressible acoustic waves in plasma are assumed to be excited with and without the presence of an external magnetic field. For the acoustic waves we determine the velocity dependence of the normal mode spectrum and magnetic field structure. We consider the feasibility of using the developed diagnostic in MPDX.
First principles molecular dynamics of molten NaCl
NASA Astrophysics Data System (ADS)
Galamba, N.; Costa Cabral, B. J.
2007-03-01
First principles Hellmann-Feynman molecular dynamics (HFMD) results for molten NaCl at a single state point are reported. The effect of induction forces on the structure and dynamics of the system is studied by comparison of the partial radial distribution functions and the velocity and force autocorrelation functions with those calculated from classical MD based on rigid-ion and shell-model potentials. The first principles results reproduce the main structural features of the molten salt observed experimentally, whereas they are incorrectly described by both rigid-ion and shell-model potentials. Moreover, HFMD Green-Kubo self-diffusion coefficients are in closer agreement with experimental data than those predicted by classical MD. A comprehensive discussion of MD results for molten NaCl based on different ab initio parametrized polarizable interionic potentials is also given.
First-principles modeling of hard and soft matter
NASA Astrophysics Data System (ADS)
Car, Roberto
2013-03-01
Electronic and atomistic processes are key to bio-inspired functional materials and nanocatalysts for energy applications. This talk will review recent simulation studies and discuss the challenges that first-principles quantum mechanical approaches face when addressing these issues. Supported by DOE-DE-FG02-06ER-46344, DOE-DE-SC0008626, DOE-DE-SC0005180, and NSF-CHE-0956500.
First-principles calculations of the thermal expansion of metals
NASA Astrophysics Data System (ADS)
Quong, Andrew A.; Liu, Amy Y.
1997-10-01
We present first-principles calculations of the thermal expansion of several simple metals (Al, Li, and Na) within the quasiharmonic approximation. Linear-response theory is used to determine the volume-dependent phonon frequencies within the density-functional framework. Our results indicate that the treatment of anharmonic effects at the quasiharmonic level provides a remarkably good description of the structural and elastic properties of these materials up to their melting points.
Materials Databases Infrastructure Constructed by First Principles Calculations: A Review
Lin, Lianshan
2015-10-13
The First Principles calculations, especially the calculation based on High-Throughput Density Functional Theory, have been widely accepted as the major tools in atom scale materials design. The emerging super computers, along with the powerful First Principles calculations, have accumulated hundreds of thousands of crystal and compound records. The exponential growing of computational materials information urges the development of the materials databases, which not only provide unlimited storage for the daily increasing data, but still keep the efficiency in data storage, management, query, presentation and manipulation. This review covers the most cutting edge materials databases in materials design, and their hotmore »applications such as in fuel cells. By comparing the advantages and drawbacks of these high-throughput First Principles materials databases, the optimized computational framework can be identified to fit the needs of fuel cell applications. The further development of high-throughput DFT materials database, which in essence accelerates the materials innovation, is discussed in the summary as well.« less
Understanding and Predicting Thiolated Gold Nanoclusters from First Principles
Jiang, Deen
2010-01-01
This is an exciting time for studying thiolated gold nanoclusters. Single crystal structures of Au{sub 102}(SR){sub 44} and Au{sub 25}(SR){sub 18}{sup -} (-SR being an organothiolate group) bring both surprises and excitement in this field. First principles density functional theory (DFT) simulations turn out to be an important tool to understand and predict thiolated gold nanoclusters. In this review, I summarize the progresses made by us and others in applying first principles DFT to thiolated gold nanoclusters, as inspired by the recent experiments. First, I will give some experimental background on synthesis of thiolated gold nanoclusters, followed by a description of the recent experimental breakthroughs. Then I will introduce the superatom complex concept as a way to understand the electronic structure of thiolated gold nanoclusters or smaller nanoparticles. Next, I will describe in detail how first principles DFT is used to understand the Au-thiolate interface, predict structures for Au{sub 38}(SR){sub 24}, screen good dopants for the Au{sub 25}(SR){sub 18}{sup -} cluster, design the smallest magic thiolated gold cluster, and demonstrate the need for the trimer protecting motif. I will conclude with a grand challenge: the real time monitoring of nucleation of thiolated gold nanoclusters.
Pascal, Tod A; Boesenberg, Ulrike; Kostecki, Robert; Richardson, Thomas J; Weng, Tsu-Chien; Sokaras, Dimosthenis; Nordlund, Dennis; McDermott, Eamon; Moewes, Alexander; Cabana, Jordi; Prendergast, David
2014-01-21
We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li2SO4, Li2O, Li3N, and Li2CO3 using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions. PMID:25669363
Pascal, Tod A.; Prendergast, David; Boesenberg, Ulrike; Kostecki, Robert; Richardson, Thomas J.; Weng, Tsu-Chien; Sokaras, Dimosthenis; Nordlund, Dennis; McDermott, Eamon; Moewes, Alexander; Cabana, Jordi; Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60605
2014-01-21
We elucidate the role of room-temperature-induced instantaneous structural distortions in the Li K-edge X-ray absorption spectra (XAS) of crystalline LiF, Li{sub 2}SO{sub 4}, Li{sub 2}O, Li{sub 3}N, and Li{sub 2}CO{sub 3} using high resolution X-ray Raman spectroscopy (XRS) measurements and first-principles density functional theory calculations within the eXcited electron and Core Hole approach. Based on thermodynamic sampling via ab initio molecular dynamics simulations, we find calculated XAS in much better agreement with experiment than those computed using the rigid crystal structure alone. We show that local instantaneous distortion of the atomic lattice perturbs the symmetry of the Li 1s core-excited-state electronic structure, broadening spectral line-shapes and, in some cases, producing additional spectral features. The excellent agreement with high-resolution XRS measurements validates the accuracy of our first-principles approach to simulating XAS, and provides both accurate benchmarks for model compounds and a predictive theoretical capability for identification and characterization of multi-component systems, such as lithium-ion batteries, under working conditions.
First-principles investigation of Nitrosyl formation in zirconia
Yu, Z.G.; Zhang, J.; Singh, David J; Wu, Ping
2012-01-01
We report first-principles calculations aimed at understanding the properties of nitrogen in ZrO{sub 2}. We find that interstitial N occurs covalently bonded to O in the form of NO units, in contrast to previous expectations of a N substitutional for O. This reveals a different chemistry for N in ZrO{sub 2} and perhaps other highly stable oxide species. This leads to a natural oxygen vacancy formation mechanism in ZrO{sub 2} in the presence of nitrogen.
Diffusion in thorium carbide: A first-principles study
NASA Astrophysics Data System (ADS)
Pérez Daroca, D.; Llois, A. M.; Mosca, H. O.
2015-12-01
The prediction of the behavior of Th compounds under irradiation is an important issue for the upcoming Generation-IV nuclear reactors. The study of self-diffusion and hetero-diffusion is a central key to fulfill this goal. As a first approach, we obtained, by means of first-principles methods, migration and activation energies of Th and C atoms self-diffusion and diffusion of He atoms in ThC. We also calculate diffusion coefficients as a function of temperature.
First principles calculations of shock compressed fluid helium.
Militzer, B
2006-10-27
The properties of hot dense helium at megabar pressures are studied with two first principles computer simulation techniques: path integral Monte Carlo simulation and density functional molecular dynamics. The simulations predict that the compressibility of helium is substantially increased by electronic excitations that are present in the hot fluid at thermodynamic equilibrium. A maximum compression ratio of 5.24(4)-fold the initial density was predicted for 360 GPa and 150,000 K. This result distinguishes helium from deuterium, for which simulations predicted a maximum compression ratio of 4.3(1). Hugoniot curves for statically precompressed samples are also discussed. PMID:17155480
Hybrid perovskites for photovoltaics: Insights from first principles
NASA Astrophysics Data System (ADS)
Filippetti, A.; Mattoni, A.
2014-03-01
The methylammonium lead iodide perovskites at the core of recently proposed solar cells with exceptionally large quantum conversion efficiency are studied by first-principles methods. Large absorption coefficients (0.03-0.04 nm-1 for wavelength ˜500 nm) and small effective masses suited for both n-type and p-type transport are obtained as a consequence of their peculiar structural and electronic characteristics. In particular, the presence of a direct gap between highly dispersed Pb(6s)-I(5p) valence bands and Pb(6p) conduction bands is the key ingredient at the basis of their excellent performance in photovoltaic applications.
Pentaprismane and hypostrophene from first-principles, with plane waves
NASA Astrophysics Data System (ADS)
Jenkins, S. J.; King, D. A.
2000-02-01
We present results of first-principles plane wave density functional studies of the polycyclic hydrocarbons pentaprismane and hypostrophene, which demonstrate, for the first time, that a plane wave basis can be successfully deployed with such strained molecules. Calculated structural parameters are found to be in good agreement with previous quantum chemical calculations and X-ray diffraction data (where available). A series of calculations for related C 10H 10 isomers, in which the five-fold rings of pentaprismane and hypostrophene are cleaved progressively further apart, are also reported. The way is now open for the calculation of the properties of these complex molecules on surfaces.
Comparative study of Ti and Ni clusters from first principles
Lee, B; Lee, G W
2007-08-20
Icosahedral clusters in Ti and Ni are studied with first-principles density functional calculations. We find significant distortion on the Ti icosahedron caused by the strong interaction between surface atoms on the icosahedron but not between the center atom and surface atoms, whereas no such distortion is observed on Ni clusters. In addition, distortion becomes more severe when atoms are added to the Ti13 cluster resulting in short bonds. Such distorted icosahedra having short bonds are essentially to explain the structure factor of Ti liquid obtained in experiment.
Large impurity effects in rubrene crystals: First-principles calculations
Tsetseris, L.; Pantelides, Sokrates T.
2008-01-01
Carrier mobilities of rubrene films are among the highest values reported for any organic semiconductor. Here, we probe with first-principles calculations the sensitivity of rubrene crystals on impurities. We find that isolated oxygen impurities create distinct peaks in the electronic density of states consistent with observations of defect levels in rubrene and that increased O content changes the position and shape of rubrene energy bands significantly. We also establish a dual role of hydrogen as individual H species and H impurity pairs create and annihilate deep carrier traps, respectively. The results are relevant to the performance and reliability of rubrene-based devices.
First-Principles Molecular Structure Search with a Genetic Algorithm.
Supady, Adriana; Blum, Volker; Baldauf, Carsten
2015-11-23
The identification of low-energy conformers for a given molecule is a fundamental problem in computational chemistry and cheminformatics. We assess here a conformer search that employs a genetic algorithm for sampling the low-energy segment of the conformation space of molecules. The algorithm is designed to work with first-principles methods, facilitated by the incorporation of local optimization and blacklisting conformers to prevent repeated evaluations of very similar solutions. The aim of the search is not only to find the global minimum but to predict all conformers within an energy window above the global minimum. The performance of the search strategy is (i) evaluated for a reference data set extracted from a database with amino acid dipeptide conformers obtained by an extensive combined force field and first-principles search and (ii) compared to the performance of a systematic search and a random conformer generator for the example of a drug-like ligand with 43 atoms, 8 rotatable bonds, and 1 cis/trans bond. PMID:26484612
First-Principles Study of Ferromagnetic Heusler Alloys: An Overview
NASA Astrophysics Data System (ADS)
Picozzi, Silvia
A particularly attractive class of materials for spintronic applications is represented by half-metals (i.e., materials showing carriers at the Fermi level 100% spin-polarized), among which ferromagnetic Heusler alloys occupy a prominent position. Here, we present a review of first-principles calculations based on the density functional theory, focusing in particular on i) several mechanisms that are predicted to destroy half-metallicity and ii) magneto-optical properties such as the Kerr rotation. We show that defect-induced states at the Fermi level in Co-based Heusler-alloys such as Co2MnSican drastically reduce the degree of spin-polarization, pointing to the necessity of keeping point-defects under control during experimental growth. In the context of spin-injection into mainstream semiconductors, interface states are also predicted to be induced by the junction between a full-Heusler and GaAs. A careful analysis of the magneto-optical Kerr effect is performed for several Co-based full-Heusler alloys. Although the size of the Kerr rotation is found to be of the order of 0.5° and therefore not technologically appealing, we show that first-principles calculations can be efficiently used as a tool to predict novel half-metals with large Kerr angles.
First-Principles Informed Thermodynamics of CRUD Deposition
NASA Astrophysics Data System (ADS)
O'Brien, Christopher John
The recent emphasis in the United States on developing abundant domestic sources of energy, together with an increasing awareness of the environmental hazards of fossil fuels, has led to a fresh look at the challenges of nuclear energy within the science and engineering community. One of these challenges is controlling the precipitation of porous oxide deposits onto the nuclear fuel rod cladding from the primary coolant during operation of pressurized light-water reactors (PWRs). These deposits, called CRUD (an acronym for Chalk River Unidentified Deposits), are a major concern to reactor operation because they reduce fuel lifetime and efficiency by reducing heat transfer to the coolant, promote corrosion, and depress neutron flux. This dissertation provides fundamental insights into the process by which CRUD is formed in PWRs by providing a framework linking the results of first-principles calculations to experimental data. The technique developed to facilitate the investigation is referred to as Density Functional Theory (DFT) referenced semi-empirical thermodynamics; It links 0K first-principles calculations with high temperature thermodynamics by redefining the reference chemical potentials of the constituent elements. The technique permits aqueous chemistry to be incorporated into thermodynamic calculations and allows for the prediction of temperature and pressure dependent free energies of materials that are experimentally inaccessible or have not yet been measured. The ability to extend accurate first-principles calculations to high temperatures and aqueous environments allows the stability of crystal surfaces, calculated with DFT techniques, to be predicted at conditions representative of an operating PWR. Accurate values of surface energies are used in fulfilling the principal goal of this dissertation, which is to investigate the aqueous thermodynamics of formation of nickel oxide (NiO) and nickel ferrite (NiFe 2O4) crystallites as representative CRUD components. Specifically, this dissertation investigates the thermodynamics of the homogeneous nucleation of crystallites and proposes a mechanism for their agglomeration. This work also contributes to a more complete understanding of CRUD by generating improved thermodynamic data to enable modeling of the incorporation of boron into CRUD through the formation of Bonaccordite (Ni2FeBO5) which has formed in PWRs operating at high-power conditions.
Thermodynamics of Magnetic Systems from First Principles: WL-LSMS
Eisenbach, Markus; Zhou, Chenggang; Nicholson, Don M; Brown, Greg; Larkin, Jeffrey M; Schulthess, Thomas C
2010-01-01
Density Functional calculations have proven to be a powerful tool to study the ground state of many materials. For finite temperatures the situation is less ideal and one is often forced to rely on models with parameters either fitted to zero temperature first principles calculations or experimental results. This approach is especially unsatisfacory in inhomogeneous systems, nano particles, or other systems where the model parameters could vary significantly from one site to another. Here we describe a possible solution to this problem by combining classical Monte Carlo calculations the Wang-Landau method in this case with a firs principles electronic structure calculation, specifically our locally selfconsistent multiple scallering code (LSMS). The combined code shows superb scaling behavior on massively parallel computers. The code sustained 1.836 Petaflop/s on 223232 cores of the Cray XT5 jaguar system at Oak Ridge.
First principle study of manganese doped cadmium sulphide sheet
Kumar, Sanjeev; Kumar, Ashok; Ahluwalia, P. K.
2014-04-24
First-principle electronic structure calculations for cadmium sulphide (CdS) sheet in hexagonal phase, with Manganese substitution and addition, as well as including the Cd defects, are investigated. The lattice constants calculated for CdS sheet agrees fairly well with results reported for thin films experimentally. The calculations of total spin density of states and partial density of states in different cases shows substantial magnetic dipole moments acquired by the sheet. A magnetic dipole moment 5.00612 ?{sub B} and band gap of the order 1 eV are found when cadmium atom is replaced by Manganese. The magnetism acquired by the sheet makes it functionally important candidate in many applications.
First-principles study of optical properties of barium titanate
NASA Astrophysics Data System (ADS)
Cai, Meng-Qiu; Yin, Zhen; Zhang, Ming-Sheng
2003-10-01
The optical properties of perovskite barium titanate in the core-level spectra are investigated by the first principles under scissor approximation. There are nine peaks at the curve of the imaginary part of dielectric function. The optical spectra are assigned to interband contribution from O 2p valence bands to Ti 3d conduction bands in the low-energy region and outer core electron excitation (core level excitation) from near valence band semicore levels Ba 5p and O 2s to conduction band in the high-energy region. In contrast to the calculated results by the tight-binding linear muffin-tin orbitals method, our results are in better agreement with the experimental results.
Ferroelectric Transitions at Ferroelectric Domain Walls Found from First Principles
NASA Astrophysics Data System (ADS)
Wojde?, Jacek C.; Íñiguez, Jorge
2014-06-01
We present a first-principles study of model domain walls (DWs) in prototypic ferroelectric PbTiO3. At high temperature the DW structure is somewhat trivial, with atoms occupying high-symmetry positions. However, upon cooling the DW undergoes a symmetry-breaking transition characterized by a giant dielectric anomaly and the onset of a large and switchable polarization. Our results thus corroborate previous arguments for the occurrence of ferroic orders at structural DWs, providing a detailed atomistic picture of a temperature-driven DW-confined transformation. Beyond its relevance to the field of ferroelectrics, our results highlight the interest of these DWs in the broader areas of low-dimensional physics and phase transitions in strongly fluctuating systems.
First-principles calculations of Pt surface phonon dispersion curves
NASA Astrophysics Data System (ADS)
Hong, Sampyo; Rahman, Talat S.; Heid, Rolf; Bohnen, Klaus Peter
2003-03-01
We have calculated dispersion curves for surface phonons of Pt(100), Pt(110) and Pt(111), using first-principles, total energy calculations based on a mixed-basis set and norm-conserving pseudopotentials. Linear response theory and the harmonic approximation of lattice dynamics are also invoked. For bulk Pt our calculations show the experimentally observed anomaly along (110) direction, and the calculated relaxations on the three surfaces are also in agreement with previous results. The dispersion of the Rayleigh wave and the resonance modes on Pt(111) are in good agreement with data from He scattering measurements. Our results of phonon dispersion for Pt(100) and Pt(110) are for their unreconstructed surfaces. The richness in the phonon disersion curves for the three surfaces will be compared and conclusions presented about the changes in the surface force constants from the bulk values. The propensity of two of the surfaces to reconstruct will also be discussed.
Properties of molten sodium under pressure from first principles theory.
NASA Astrophysics Data System (ADS)
Raty, Jean-Yves; Schwegler, Eric; Bonev, Stanimir
2006-03-01
Recent measurements of the melting curve of sodium [1] have found a sharp decline in the melting temperatures from 1000 to 300 K in the pressure range from 30 to 120 GPa. In this study, we investigate the stability and structural properties of solid and liquid sodium at high pressure and temperature using first principles molecular dynamics. The experimental melting curve is reproduced from 0 to 120 GPa. The local structure of the liquid is found to be strongly correlated to the multiple finite temperature crystalline phases of sodium. Based on a quantitative analysis of the structural and electronic properties of the solid and liquid phases, we propose an explanation for the unusual melting curve and a new perspective on the phase diagram of sodium. [1] Gregoryantz et al., Phys. Rev. Lett. 94, 185502 (2005).
Vibrational and Thermophysical Properties of PETN from First Principles
NASA Astrophysics Data System (ADS)
Gonzalez, Joseph; Landerville, Aaron; Oleynik, Ivan
2015-06-01
Thermophysical properties are urgently sought as input for meso- and continuum-scale modeling of energetic materials (EMs). However, empirical data in this regard are often limited to specific pressures and temperatures. Such modeling of EMs can be greatly improved by inclusion of thermophysical properties over a wide range of pressures and temperatures, provided such data could be reliably obtained from theory. We demonstrate such a capability by calculating the equation of state, heat capacities, coefficients of thermal expansion, and Gruneissen parameters for pentaerythritol tetranitrate (PETN) using first-principles density functional theory, which includes proper description of van der Waals interactions and zero-point and thermal free energy contributions to pressure, the latter being calculated using the quasi-harmonic approximation. Further, we investigate the evolution of the vibration spectrum of PETN as a function of pressure.
Carbon-rich icosahedral boron carbide designed from first principles
Jay, Antoine; Vast, Nathalie; Sjakste, Jelena; Duparc, Olivier Hardouin
2014-07-21
The carbon-rich boron-carbide (B{sub 11}C)C-C has been designed from first principles within the density functional theory. With respect to the most common boron carbide at 20% carbon concentration B{sub 4}C, the structural modification consists in removing boron atoms from the chains linking (B{sub 11}C) icosahedra. With C-C instead of C-B-C chains, the formation of vacancies is shown to be hindered, leading to enhanced mechanical strength with respect to B{sub 4}C. The phonon frequencies and elastic constants turn out to prove the stability of the carbon-rich phase, and important fingerprints for its characterization have been identified.
NMR shifts for polycyclic aromatic hydrocarbons from first-principles
Thonhauser, Timo; Ceresoli, Davide; Marzari, Nicola N.
2009-09-03
We present first-principles, density-functional theory calculations of the NMR chemical shifts for polycyclic aromatic hydrocarbons, starting with benzene and increasing sizes up to the one- and two-dimensional infinite limits of graphene ribbons and sheets. Our calculations are performed using a combination of the recently developed theory of orbital magnetization in solids, and a novel approach to NMR calculations where chemical shifts are obtained from the derivative of the orbital magnetization with respect to a microscopic, localized magnetic dipole. Using these methods we study on equal footing the 1H and 13C shifts in benzene, pyrene, coronene, in naphthalene, anthracene, naphthacene, and pentacene, and finally in graphene, graphite, and an infinite graphene ribbon. Our results show very good agreement with experiments and allow us to characterize the trends for the chemical shifts as a function of system size.
First principles modeling of panchromatic dyes for solar cells applications.
NASA Astrophysics Data System (ADS)
di Felice, Rosa; Calzolari, Arrigo; Dong, Rui; Buongiorno Nardelli, Marco
2013-03-01
The state-of-the-art dye in Grätzel solar cells, N719, exhibits a total solar-to-electric conversion efficiency of 11.2%. However, it severely lacks absorption in the red and the near infrared regions of the electromagnetic spectrum, which represent more than 70% of the solar radiation spectrum. Using calculations from first principles in the time-dependent domain, we have studied the electronic and optical response of a novel class of panchromatic sensitizers that can harvest solar energy efficiently across the visible and near infrared regions, which have been recently synthesized [A. El-Shafei, M. Hussain, A. Atiq, A. Islam, and L. Han, J. Mater. Chem. 22, 24048 (2012)]. Our calculations show that, by tuning the properties of antenna groups, one can achieve a substantial improvement of the optical properties.
Helium diffusion in olivine based on first principles calculations
NASA Astrophysics Data System (ADS)
Wang, Kai; Brodholt, John; Lu, Xiancai
2015-05-01
As a key trace element involved in mantle evolution, the transport properties of helium in the mantle are important for understanding the thermal and chemical evolution of the Earth. However, the mobility of helium in the mantle is still unclear due to the scarcity of measured diffusion data from minerals under mantle conditions. In this study, we used first principles calculations based on density functional theory to calculate the absolute diffusion coefficients of the helium in olivine. Using the climbing images nudged elastic band method, we defined the diffusion pathways, the activation energies (Ea), and the prefactors. Our results demonstrate that the diffusion of helium has moderate anisotropy. The directionally dependent diffusion of helium in olivine can be written in Arrhenius form as follows.
Electronic Stopping Power in LiF from First Principles
Pruneda, J. M.; Sanchez-Portal, D.; Artacho, Emilio
2007-12-07
Using time-dependent density-functional theory we calculate from first principles the rate of energy transfer from a moving proton or antiproton to the electrons of an insulating material, LiF. The behavior of the electronic stopping power versus projectile velocity displays an effective threshold velocity of {approx}0.2 a.u. for the proton, consistent with recent experimental observations, and also for the antiproton. The calculated proton/antiproton stopping-power ratio is {approx}2.4 at velocities slightly above the threshold (v{approx}0.4 a.u.), as compared to the experimental value of 2.1. The projectile energy loss mechanism is observed to be extremely local.
Hydrogen storage in LiH: A first principle study
Banger, Suman Nayak, Vikas Verma, U. P.
2014-04-24
First principles calculations have been performed on the Lithium hydride (LiH) using the full potential linearized augmented plane wave (FP-LAPW) method within the framework of density functional theory. We have extended our calculations for LiH+2H and LiH+6H in NaCl structure. The structural stability of three compounds have been studied. It is found that LiH with 6 added Hydrogen atoms is most stable. The obtained results for LiH are in good agreement with reported experimental data. Electronic structures of three compounds are also studied. Out of three the energy band gap in LiH is ?3.0 eV and LiH+2H and LiH+6H are metallic.
Auger recombination in sodium-iodide scintillators from first principles
McAllister, Andrew; Åberg, Daniel; Schleife, André; Kioupakis, Emmanouil
2015-04-06
Scintillator radiation detectors suffer from low energy resolution that has been attributed to non-linear light yield response to the energy of the incident gamma rays. Auger recombination is a key non-radiative recombination channel that scales with the third power of the excitation density and may play a role in the non-proportionality problem of scintillators. In this work, we study direct and phonon-assisted Auger recombination in NaI using first-principles calculations. Our results show that phonon-assisted Auger recombination, mediated primarily by short-range phonon scattering, dominates at room temperature. We discuss our findings in light of the much larger values obtained by numerical fits to z-scan experiments.
First-principles statistical mechanics for heterogeneous catalysis
NASA Astrophysics Data System (ADS)
Reuter, Karsten
2006-03-01
We present a first-principles approach to heterogeneous catalysis that quantitatively describes the activity over a wide range of realistic environmental situations of varying temperatures and pressures. Within a first-principles statistical mechanics setup [1], density-functional theory is first used together with transition state theory to accurately obtain the energetics of all relevant processes. Subsequently the statistical mechanics problem is solved by kinetic Monte Carlo simulations. This two-step approach enables us to gain microscopic insight into the system, following its full dynamics from picoseconds up to seconds and explicitly considering the detailed statistical interplay of all elementary processes, i.e., by fully accounting for the correlations, fluctuations and spatial distributions of the chemicals at the catalyst surface. In the application to CO oxidation at a RuO2(110) model catalyst, we compute the composition and structure of the catalyst surface in reactive environments ranging from ultra- high vacuum to technologically relevant conditions with pressures of the order of atmospheres and elevated temperatures [2]. For all these conditions the obtained conversion rates are in unprecedented quantitative agreement with existing experimental data. The catalytic activity is narrowly peaked in environments, where the surface kinetics builds a disordered and dynamic adsorbate composition at the surface. In the full concert of the large number of processes occurring in this active state, the chemical reaction with the most favorable energy barrier contributes only little to the overall CO2 production. [1] K. Reuter, D. Frenkel, and M. Scheffler, Phys. Rev. Lett. 93, 116105 (2004). [2] K. Reuter and M. Scheffler, Phys. Rev. B, submitted.
NASA Astrophysics Data System (ADS)
Bianco, Raffaello; Calandra, Matteo; Mauri, Francesco
2015-09-01
We study the charge-density-wave phase in TiSe2 by using first-principles density functional theory calculations with the harmonic approximation for the electron-phonon coupling. We consider several local functionals and both experimental and theoretical cell parameters. The results obtained are very sensitive to the cell parameters used. However, we show that, if the experimental cell is used, harmonic calculations are able to reproduce not only the structural instability of TiSe2 but also the effective distortion observed in the experiments, irrespective of the local functional used. If the experimental cell is used, the energy profile obtained by displacing the atoms is independent of the local functional considered too. With the semiempirical functional Grimme B97-D, aimed at describing better the van der Waals forces coupling the TiSe2 layers, the theoretical cell is in agreement with the experimental one and the structural analysis gives results analogous to the ones obtained with the experimental cell. We also present a study of the electronic structure evolution under the charge-density-wave deformation. In particular, we apply the unfolding technique in order to compare the calculated energy bands for the distorted structure with angle-resolved photoemission spectroscopy (ARPES) data taken at low temperature. In order to obtain a better agreement between ARPES and the calculated bands, both at high and low temperature, we investigate the effect of the correlation on the electrons of the localized Ti-3 d orbitals by using the LDA + U method. We show that within this approximation the electronic bands for both the undistorted and distorted structure are in good agreement with ARPES. On the other hand, U eliminates the phonon instability of the system. A possible explanation for this counterintuitive result is proposed. Particularly, the possibility of taking into account the dependence of the parameter U on the atomic positions is suggested.
Theoretical study of the spectroscopy of Al2(+)
NASA Technical Reports Server (NTRS)
Rosi, Marzio; Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.
1991-01-01
The electronic states of Al2(+) below about 40,000/cm are studied using a CASSCF/MRCI approach in a large Gaussian basis set. The computed spectroscopic constants, excitation energies, Einstein coefficients, and radiative lifetimes should give insight into the spectroscopy of this ion.
Theoretical Modeling for the X-ray Spectroscopy of Iron-bearing MgSiO3 under High Pressure
NASA Astrophysics Data System (ADS)
Wang, X.; Tsuchiya, T.
2012-12-01
The behaviors of iron (Fe) in MgSiO3 perovskite, including valence state, spin state, and chemical environments, at high pressures are of fundamental importance for more detailed understanding the properties of the Earth's lower mantle. The pressure induced spin transition of Fe-bearing MgO and MgSiO3 are detected often by using high-resolution K-edge X-ray emission spectroscopy (XES) [1,2,3] and confirmed by theoretical simulations. [4,5] Since the Fe K-edge XES is associated to the 3p orbital, which is far from the valence orbitals (3d and 4s), it provides no information about its coordination environments. However, the Fe L-edge XES and X-ray absorption spectroscopy (XAS) can directly present the distribution and intensity of Fe-3d character. To identify both the spin states and the coordination environments of iron-bearing MgSiO3, we systematically investigate the L-edge XAS, XES and X-ray photoelectron (XPS) spectroscopy of Fe2+- and Fe3+-bearing MgSiO3 under high pressure by using the first-principles density functional method combined with the slater-transition method. Our results show that Fe2+ and Fe3+ can be distinguished easily by taking the XPS spectra. The spin transition of Fe2+ and Fe3+ can also be clearly certified by XAS and XES. Interestingly, the broadness of L-edge XES of Fe changes depending on the iron position, meaning that its coordination environment might also be distinguishable by using high-resolution XES measurements. Research supported by the Ehime University G-COE program and KAKENHI. [1] James Badro, Guillaume Fiquet, FranÇois Guyot, Jean-Pascal Rueff, Viktor V. Struzhkin, György VankÓ, and Giulio Monaco. Science 300, 789 (2003), [2] James Badro, Jean-Pascal Rueff, György VankÓ, Giulio Monaco, Guillaume Fiquet, and FranÇois Guyot, Science 305, 383 (2004), [3] Jung-Fu Lin, Viktor V. Struzhkin, Steven D. Jacobsen, Michael Y. Hu, Paul Chow, Jennifer Kung, Haozhe Liu, Ho-kwang Mao, and Gussell J. Hemley, Nature 436, 377 (2005). [4] Taku Tsuchiya, Renata M. Wentzcovitch, Cesar R.S. da Silva, and Stefano de Gironcoli, Phys. Rev. Lett. 96, 198501 (2006). [4] Han Hsu, Peter Blaha, Matteo Cococcioni, and Renata M. Wentzcovitch, Phys. Rev. Lett. 106, 118501 (2011).
Spectroscopy of light hydrogenic atoms: a theoretical approach \\Lambda
Pachucki, Krzysztof
2S [3] and 2S \\Gamma 4S [4] two--photon transition in hydrogen by the HË?ansch group in Garching (T.W. HË?ansch contribution to this proceedings), the 2S \\Gamma 8S transition by Biraben et al. in Paris [5 precision hydrogen spectroscopy is described by HË?ansch in his contribution to this Workshop, I concentrate
Niu, J. G.; Zhan, Q.; Geng, W. T.
2014-06-15
Despite well documented first-principles theoretical determination of the low migration energy (0.06 eV) of a single He in tungsten, fully quantum mechanical calculations on the migration of a He pair still present a challenge due to the complexity of its trajectory. By identifying the six most stable configurations of the He pair in W and decomposing its motion into rotational, translational, and rotational-translational routines, we are able to determine its migration barrier and trajectory. Our density functional theory calculations demonstrate a He pair has three modes of motion: a close or open circular two-dimensional motion in (100) plane with an energy barrier of 0.30 eV, a snaking motion along [001] direction with a barrier of 0.30 eV, and a twisted-ladder motion along [010] direction with the two He swinging in the plane (100) and a barrier of 0.31 eV. The graceful associative movements of a He pair are related to the chemical-bonding-like He-He interaction being much stronger than its migration barrier in W. The excellent agreement with available experimental measurements (0.24–0.32 eV) on He migration makes our first-principles result a solid input to obtain accurate He-W interatomic potentials in molecular dynamics simulations.
A first-principles study of Spin Polarized Transport in a Molecular wire
NASA Astrophysics Data System (ADS)
Pati, R.; Senapati, L.; Ajayan, P. M.; Nayak, S. K.
2003-03-01
The controlled transport of electrons/holes through a single molecule attached to electrodes forms the foundation of molecular electronics. When the contact is a magnetic material, the problem becomes even more interesting as the spin configuration in the contact plays a crucial role in the transport. The role of electron spins, in addition to charge, in controlling the device characteristics was discovered a long time ago, and has been studied in magnetic/nonmagnetic heterostructures. But thus far, no first principles theoretical study is carried out to address the problem of spin assisted transport in the case of molecular wire. Using first-principles density functional theory and the Landauer-Büttiker formalism, we have studied the spin-polarized transport in a benzene-1-4-dithiolate molecule sandwiched between two Ni cluster layers, followed by non-magnetic gold contacts. Our calculation reveals that for a parallel alignment of the spins at opposite ends of the molecular wire the conductance is significantly higher as compared to that in the anti-parallel alignment.
Carbon impurity dissolution and migration in bcc Fe-Cr: First-principles calculations
NASA Astrophysics Data System (ADS)
Sandberg, Nils; Henriksson, Krister O. E.; Wallenius, Jan
2008-09-01
First-principles density-functional theory calculations for C solution enthalpies, Hsol , and diffusion activation enthalpies, Hdiff , in body-centered-cubic Fe and Cr are presented. The results for C in Fe compare well with experiments, provided that the effect of magnetic disordering is accounted for. Likewise, in Cr, the calculated Hsol and Hdiff agree well with available experiments. In both materials, the deviation between calculated enthalpies and critically assessed experimental enthalpies are less than 0.05 eV. Further, first-principles calculations for the interaction energies between a solute (e.g., a Cr atom in bcc Fe) and an interstitial C atom are presented. The results are in conflict with those inferred from internal friction (IF) experiments in disordered Fe-Cr-C alloys. A simple model of C relaxation in disordered Fe-Cr is used to compare theoretical and experimental IF curves directly. The results suggest that a more extensive study of the energetic, thermodynamic, and kinetic aspects of C migration in Fe-Cr is needed.
Experimental and first-principles study of ferromagnetism in Mn-doped zinc stannate nanowires
Deng Rui; Zhou Hang; Qin Jieming; Wan Yuchun; Jiang Dayong; Liang Qingcheng; Li Yongfeng; Wu, Tom; Yao Bin; Liu Lei
2013-07-21
Room temperature ferromagnetism was observed in Mn-doped zinc stannate (ZTO:Mn) nanowires, which were prepared by chemical vapor transport. Structural and magnetic properties and Mn chemical states of ZTO:Mn nanowires were investigated by X-ray diffraction, superconducting quantum interference device (SQUID) magnetometry and X-ray photoelectron spectroscopy. Manganese predominantly existed as Mn{sup 2+} and substituted for Zn (Mn{sub Zn}) in ZTO:Mn. This conclusion was supported by first-principles calculations. Mn{sub Zn} in ZTO:Mn had a lower formation energy than that of Mn substituted for Sn (Mn{sub Sn}). The nearest neighbor Mn{sub Zn} in ZTO stabilized ferromagnetic coupling. This observation supported the experimental results.
TOPICAL REVIEW: First principles studies of multiferroic materials
NASA Astrophysics Data System (ADS)
Picozzi, Silvia; Ederer, Claude
2009-07-01
Multiferroics, materials where spontaneous long-range magnetic and dipolar orders coexist, represent an attractive class of compounds, which combine rich and fascinating fundamental physics with a technologically appealing potential for applications in the general area of spintronics. Ab initio calculations have significantly contributed to recent progress in this area, by elucidating different mechanisms for multiferroicity and providing essential information on various compounds where these effects are manifestly at play. In particular, here we present examples of density-functional theory investigations for two main classes of materials: (a) multiferroics where ferroelectricity is driven by hybridization or purely structural effects, with BiFeO3 as the prototype material, and (b) multiferroics where ferroelectricity is driven by correlation effects and is strongly linked to electronic degrees of freedom such as spin-, charge-, or orbital-ordering, with rare-earth manganites as prototypes. As for the first class of multiferroics, first principles calculations are shown to provide an accurate qualitative and quantitative description of the physics in BiFeO3, ranging from the prediction of large ferroelectric polarization and weak ferromagnetism, over the effect of epitaxial strain, to the identification of possible scenarios for coupling between ferroelectric and magnetic order. For the second class of multiferroics, ab initio calculations have shown that, in those cases where spin-ordering breaks inversion symmetry (e.g. in antiferromagnetic E-type HoMnO3), the magnetically induced ferroelectric polarization can be as large as a few µC cm-2. The examples presented point the way to several possible avenues for future research: on the technological side, first principles simulations can contribute to a rational materials design, aimed at identifying spintronic materials that exhibit ferromagnetism and ferroelectricity at or above room temperature. On the fundamental side, ab initio approaches can be used to explore new mechanisms for ferroelectricity by exploiting electronic correlations that are at play in transition metal oxides, and by suggesting ways to maximize the strength of these effects as well as the corresponding ordering temperatures.
First principle active neutron coincidence counting measurements of uranium oxide
NASA Astrophysics Data System (ADS)
Goddard, Braden; Charlton, William; Peerani, Paolo
2014-03-01
Uranium is present in most nuclear fuel cycle facilities ranging from uranium mines, enrichment plants, fuel fabrication facilities, nuclear reactors, and reprocessing plants. The isotopic, chemical, and geometric composition of uranium can vary significantly between these facilities, depending on the application and type of facility. Examples of this variation are: enrichments varying from depleted (~0.2 wt% 235U) to high enriched (>20 wt% 235U); compositions consisting of U3O8, UO2, UF6, metallic, and ceramic forms; geometries ranging from plates, cans, and rods; and masses which can range from a 500 kg fuel assembly down to a few grams fuel pellet. Since 235U is a fissile material, it is routinely safeguarded in these facilities. Current techniques for quantifying the 235U mass in a sample include neutron coincidence counting. One of the main disadvantages of this technique is that it requires a known standard of representative geometry and composition for calibration, which opens up a pathway for potential erroneous declarations by the State and reduces the effectiveness of safeguards. In order to address this weakness, the authors have developed a neutron coincidence counting technique which uses the first principle point-model developed by Boehnel instead of the "known standard" method. This technique was primarily tested through simulations of 1000 g U3O8 samples using the Monte Carlo N-Particle eXtended (MCNPX) code. The results of these simulations showed good agreement between the simulated and exact 235U sample masses.
First-principles investigation of electrochemical properties of gold nanoparticles
NASA Astrophysics Data System (ADS)
Batista, Ronaldo J. C.; Mazzoni, Mário S. C.; Chacham, H.
2010-02-01
A first-principles formalism is employed to investigate the effects of size and structure on the electronic and electrochemical properties of Au nanoparticles with diameters between 0.8 and 2.0 nm. We find that the behavior of the ionization potentials (IPs) and the electron affinities (EAs) as a function of cluster size can be separated into many-body and single-electron contributions. The many-body part is only (and continuously) dependent on particle size, and can be very well described in terms of the capacitance of classical spherical conductors for clusters with more the 55 atoms. For smaller clusters, molecule-like features lead the capacitance and fundamental gap to differ systematically from those of a classical conductor with decreasing size. The single-electron part fluctuates with particle structure. Upon calculating the neutral chemical potential ?0 = (IP+EA)/2, the many-body contributions cancel out, resulting in fluctuations of ?0 around the bulk Au work function, consistent with experimental results. The values of IP and EA changes upon functionalization with thiolated molecules, and the magnitude of the observed changes does not depend on the length of the alkane chain. The functionalization can also lead to a transition from metallic to non-metallic behavior in small nanoparticles, which is consistent with experimental observations.
Thermal conductivity of silicene from first-principles
Xie, Han; Bao, Hua E-mail: hua.bao@sjtu.edu.cn; Hu, Ming E-mail: hua.bao@sjtu.edu.cn
2014-03-31
Silicene, as a graphene-like two-dimensional material, now receives exceptional attention of a wide community of scientists and engineers beyond graphene. Despite extensive study on its electric property, little research has been done to accurately calculate the phonon transport of silicene so far. In this paper, thermal conductivity of monolayer silicene is predicted from first-principles method. At 300?K, the thermal conductivity of monolayer silicene is found to be 9.4?W/mK and much smaller than bulk silicon. The contributions from in-plane and out-of-plane vibrations to thermal conductivity are quantified, and the out-of-plane vibration contributes less than 10% of the overall thermal conductivity, which is different from the results of the similar studies on graphene. The difference is explained by the presence of small buckling, which breaks the reflectional symmetry of the structure. The flexural modes are thus not purely out-of-plane vibration and have strong scattering with other modes.
Solubility of nonelectrolytes: a first-principles computational approach.
Jackson, Nicholas E; Chen, Lin X; Ratner, Mark A
2014-05-15
Using a combination of classical molecular dynamics and symmetry adapted intermolecular perturbation theory, we develop a high-accuracy computational method for examining the solubility energetics of nonelectrolytes. This approach is used to accurately compute the cohesive energy density and Hildebrand solubility parameters of 26 molecular liquids. The energy decomposition of symmetry adapted perturbation theory is then utilized to develop multicomponent Hansen-like solubility parameters. These parameters are shown to reproduce the solvent categorizations (nonpolar, polar aprotic, or polar protic) of all molecular liquids studied while lending quantitative rigor to these qualitative categorizations via the introduction of simple, easily computable parameters. Notably, we find that by monitoring the first-order exchange energy contribution to the total interaction energy, one can rigorously determine the hydrogen bonding character of a molecular liquid. Finally, this method is applied to compute explicitly the Flory interaction parameter and the free energy of mixing for two different small molecule mixtures, reproducing the known miscibilities. This methodology represents an important step toward the prediction of molecular solubility from first principles. PMID:24773531
Transport Properties of Nanoscale Materials by First-principles Calculations
NASA Astrophysics Data System (ADS)
Mizuseki, Hiroshi; Belosludov, Rodion V.; Lee, S.-U.; Kawazoe, Yoshiyuki
2009-03-01
Molecular devices are potential candidates for the next step towards nanoelectronic technology. Our group has covered a wide range of nanoscale wires, which have potential application in molecular electronics using first-principles calculations and nonequilibrium Green's function formalism [1]. Our target materials are supramolecular enamel wires (covered wires) [2], connection between organic molecules and metal electrodes, self-assembled nanowires on silicon surface [3], porphyrin [4], phthalocyanine, metallocene [5], fused-ring thiophene molecules, length dependence of conductance in alkanedithiols and so on. Namely, we have investigated a relationship of the energy levels of delocalized frontier orbitals (HOMO and LUMO) and Fermi level of metal electrodes and estimate the electronic transport properties through atomic and molecular wires using Green's function approach. References [1] http://www-lab.imr.edu/˜mizuseki/nanowire.html [2] R. V. Belosludov, A. A. Farajian, H. Baba, H. Mizuseki, and Y. Kawazoe, Jpn. J. Appl. Phys., 44, 2823 (2005). [3] R. V. Belosludov, A. A. Farajian, H. Mizuseki, K. Miki, and Y. Kawazoe, Phys. Rev. B, 75, 113411 (2007). [4] S.-U. Lee, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, Small 4 (2008) 962. [5] S.-U Lee, R. V. Belosludov, H. Mizuseki, and Y. Kawazoe, J. Phys. Chem. C. 111 (2007) 15397.
Electronic band engineering in epitaxial graphene: First principles calculations
NASA Astrophysics Data System (ADS)
Sirikumara, Hansika Iroshini
In this research work, we have investigated the band engineering of epitaxial graphene using first principles calculations. Epitaxial graphene on SiC (0001) surface is modified by using different methods such as intercalation, doping, passivation and oxidation. The calculations are done using Density functional theory which is implemented in quantum espresso package. In the presence of H intercalation, epitaxial graphene is shown to have p type behavior with monolayer graphene. However this behavior is different for multilayer epitaxial graphene systems, and it depended on the concentration of the H atoms. When epitaxial graphene is intercalated with Ge atoms, the Ge atoms make clusters and these clusters are responsible for the electronic properties of the epitaxial graphene systems. As a result of oxidation of epitaxial SiC surface, the graphene layer is mostly stable on the surface for both silicates and oxynitrides structures. For silicate/SiC configurations, the epitaxial graphene is shown to be less n type. For oxynitrides/ SiC configurations, epitaxial graphene is shown to be neutral. In the presence of oxygen intercalation with silicate/SiC, epitaxial graphene is shown to have p type behavior. These systematic studies of epitaxial graphene will opens up great potential for electronic applications. Additionally the resultant models can be used to guide further studies.
Electronic Structure and Ionicity of Actinide Oxides from First Principles
Petit, Leon; Svane, Axel; Szotek, Zdzislawa; Temmerman, Walter M; Stocks, George Malcolm
2010-01-01
The ground-state electronic structures of the actinide oxides AO, A{sub 2}O{sub 3}, and AO{sub 2} (A=U, Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f-electron localization, which for AO{sub 2} and A{sub 2}O{sub 3} is found to follow the stoichiometry, namely, corresponding to A{sup 4+} ions in the dioxide and A{sup 3+} ions in the sesquioxides. In contrast, the A{sup 2+} ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.
Electronic structure and ionicity of actinide oxides from first principles
Petit, L.; Svane, A.; Szotek, Z.; Temmerman, W. M.; Stocks, G. Malcolm
2010-01-07
The ground-state electronic structures of the actinide oxides AO , A{sub 2} O{sub 3} , and AO{sub 2} (A=U , Np, Pu, Am, Cm, Bk, and Cf) are determined from first-principles calculations, using the self-interaction corrected local spin-density approximation. Emphasis is put on the degree of f -electron localization, which for AO{sub 2} and A{sub 2} O{sub 3} is found to follow the stoichiometry, namely, corresponding to A{sup 4+} ions in the dioxide and A{sup 3+} ions in the sesquioxides. In contrast, the A{sup 2+} ionic configuration is not favorable in the monoxides, which therefore become metallic. The energetics of the oxidation and reduction in the actinide dioxides is discussed, and it is found that the dioxide is the most stable oxide for the actinides from Np onward. Our study reveals a strong link between preferred oxidation number and degree of localization which is confirmed by comparing to the ground-state configurations of the corresponding lanthanide oxides. The ionic nature of the actinide oxides emerges from the fact that only those compounds will form where the calculated ground-state valency agrees with the nominal valency expected from a simple charge counting.
Chemistry and Deformation: First Principles Studies of Local Plasticity
NASA Astrophysics Data System (ADS)
Woodward, Christopher
2011-03-01
In order to understand the how chemistry influences deformation, an adequate description of the strain field near the center of dislocations (i.e. the core) is required. Continuum level descriptions of deformation ignore this short-range coupling between dislocations and the local atomic lattice. Interactions at this scale are non-linear and can strongly influence plastic deformation in fcc and bcc metals. Here, density functional theory is used in conjunction with a flexible boundary condition method to calculate the equilibrium dislocation core structure in a variety of bcc and fcc metals. The problem is divided into two parts: a solution for the nonlinear dislocation-core region and a solution for the long-range elastic response. Solving these individual problems is straightforward and by iteratively coupling the two solutions we can efficiently solve for the strain field in all space. Chemical effects, in the form of local solute-dislocation interactions, can also be calculated using this method. Derived solute-dislocation interactions are used to inform new models of solution hardening (and softening) in bcc Mo-X (X=Re, Pt) and fcc Al-X (X=Mg, Cr, Si, Cu) alloys. Currently, solute dislocation interactions are being assessed in bcc Fe-H alloys using this first principles technique.
First principles study of native defects in InI
NASA Astrophysics Data System (ADS)
Biswas, Koushik; Du, Mao-Hua
2011-06-01
Heavy-metal halide semiconductors have attracted much interest recently for their potential applications in radiation detection because the large atomic numbers (high Z) of their constituent elements enable efficient radiation absorption and their large band gaps allow room temperature operation. However, defect properties of these halides and their connection to carrier transport are little known. In this paper, we present first-principles calculations on native defects in InI, which is a promising material for applications in room temperature radiation detection. The important findings are: (1) anion and cation vacancies (Schottky defects) form the dominant low-energy defects that can pin the Fermi level close to midgap, leading to high resistivity that is required for a good radiation detector material; (2) the anion vacancy in InI induces a deep electron trap, which should reduce electron mobility-lifetime product in InI; (3) low diffusion barriers of vacancies could be responsible for the observed polarization phenomenon at room temperature.
Auger recombination in scintillator materials from first principles
NASA Astrophysics Data System (ADS)
McAllister, Andrew; Kioupakis, Emmanouil; Åberg, Daniel; Schleife, André
2015-03-01
Scintillators convert high energy radiation into lower energy photons which are easier to detect and analyze. One of the uses of these devices is identifying radioactive materials being transported across national borders. However, scintillating materials have a non-proportional light yield in response to incident radiation, which makes this task difficult. One possible cause of the non-proportional light yield is non-radiative Auger recombination. Auger recombination can occur in two ways - direct and phonon-assisted. We have studied both types of Auger recombination from first principles in the common scintillating material sodium iodide. Our results indicate that the phonon-assisted process, assisted primarily by short-range optical phonons, dominates the direct process. The corresponding Auger coefficients are 5 . 6 +/- 0 . 3 ×10-32cm6s-1 for the phonon-assisted process versus 1 . 17 +/- 0 . 01 ×10-33cm6s-1 for the direct process. At higher electronic temperatures the direct Auger recombination rate increases but remains lower than the phonon-assisted rate. This research was supported by the National Science Foundation CAREER award through Grant No. DMR-1254314 and NA-22. Computational Resources provide by LLNL and DOE NERSC Facility.
Safeguards First Principles Initiative at the Nevada Test Site
Geneva Johnson
2007-07-08
The Material Control and Accountability (MC&A) program at the Nevada Test Site (NTS) was selected as a test bed for the Safeguards First Principles Initiative (SFPI). The implementation of the SFPI is evaluated using the system effectiveness model and the program is managed under an approved MC&A Plan. The effectiveness model consists of an evaluation of the critical elements necessary to detect, deter, and/or prevent the theft or diversion of Special Nuclear Material (SNM). The modeled results indicate that the MC&A program established under this variance is still effective, without creating unacceptable risk. Extensive performance testing is conducted through the duration of the pilot to ensure the protection system is effective and no material is at an unacceptable risk. The pilot was conducted from January 1, 2007, through May 30, 2007. This paper will discuss the following activities in association with SFPI: 1. Development of Timeline 2. Crosswalk of DOE Order and SFPI 3. Peer Review 4. Deviation 5. MC&A Plan and Procedure changes 6. Changes implemented at NTS 7. Training 8. Performance Test
Ions in solutions: Determining their polarizabilities from first-principles
NASA Astrophysics Data System (ADS)
Molina, John J.; Lectez, Sébastien; Tazi, Sami; Salanne, Mathieu; Dufrêche, Jean-François; Roques, Jérôme; Simoni, Eric; Madden, Paul A.; Turq, Pierre
2011-01-01
Dipole polarizabilities of a series of ions in aqueous solutions are computed from first-principles. The procedure is based on the study of the linear response of the maximally localized Wannier functions to an applied external field, within density functional theory. For most monoatomic cations (Li ^+, Na ^+, K ^+, Rb ^+, Mg ^{2+}, Ca ^{2+} and Sr ^{2+}) the computed polarizabilities are the same as in the gas phase. For Cs ^+ and a series of anions (F ^-, Cl ^-, Br ^- and I ^-), environmental effects are observed, which reduce the polarizabilities in aqueous solutions with respect to their gas phase values. The polarizabilities of H ^+_(aq), OH ^-_(aq) have also been determined along an ab initio molecular dynamics simulation. We observe that the polarizability of a molecule instantaneously switches upon proton transfer events. Finally, we also computed the polarizability tensor in the case of a strongly anisotropic molecular ion, UO _2^{2+}. The results of these calculations will be useful in building interaction potentials that include polarization effects.
A new model of spongy icing from first principles
NASA Astrophysics Data System (ADS)
Blackmore, R. Z.; Makkonen, L.; Lozowski, E. P.
2002-11-01
A new icing model has been developed to predict the sponginess (liquid fraction) and growth rate of freshwater ice accretions growing under a surface film of unfrozen water. This model is developed from first principles and does not require experimental sponginess data to tune the model parameters. The model identifies icing conditions that include no accretion, dry accretion, glaze accretion, spongy nonshedding, and spongy shedding regimes. It is a steady state model for a stationary vertical cylinder intercepting horizontally directed spray. The model predicts both the accretion mass growth flux and the accretion sponginess. The model results suggest that spongy shedding and spongy nonshedding regimes are common under the high liquid flux conditions typical of freshwater ship icing. Moreover, the unfrozen liquid incorporated into the spongy ice matrix can substantially increase the ice accretion load over that which would be predicted purely thermodynamically. Despite differences in the experimental setup, the model's performance compares well with two independent freshwater experimental data sets for icing on horizontal rotating cylinders. The model performs well in its prediction of both accretion sponginess and growth rate. The model predicts sponginess with a variation in liquid mass fraction of about 0.2-0.5, over the range of air temperature of 0°C to -30°C, in agreement with observations.
First-principles Simulations and the Criticality of Calving Glaciers
NASA Astrophysics Data System (ADS)
Vallot, D.; Åström, J. A.; Schäfer, M.; Welty, E.; O'Neel, S.; Bartholomaus, T. C.; Liu, Y.; Riikilä, T.; Zwinger, T.; Timonen, J.; Moore, J.
2014-12-01
The algoritm of a first principles calving-simulation computer-code is outlined and demonstrated. The code is particle-based and uses Newtonian dynamics to simulate ice-fracture, motion and calving. The code can simulate real-size glacier but is only able to simualte individual calving events within a few tens of minutes in duration. The code couples to the Elmer/Ice ice flow-simulation code: Elmer is employed to produce various glacier geomteries, which are then tested for stability using the particle code. In this way it is possible to pin-point the location of calving fronts. The particle simulation code and field observations are engaged to investigate the criticality of calving glaciers. The calving mass and inter-event waiting times both have power-law distributions with the same critical exponents as found for Abelian sand-pile models. This indicate that calving glaciers share characteristics with Self-Organized Critical systems (SOC). This would explain why many glacier found in nature may become unstable as a result of even minor changes in their environment. An SOC calving glacier at the critical point will display so large fluctuations in calving rate that it will render the concept 'average calving rate' more or less useless. I.e. 'average calving rate' will depend on measurement time and always have fluctuaions in the range of 100% more or less independent of the averaging time.
First Principles Investigation of Hydrogen Physical Adsorption on Graphynes' layers
Bartolomei, Massimiliano; Giorgi, Giacomo
2015-01-01
Graphynes are 2D porous structures deriving from graphene featuring triangular and regularly distributed subnanometer pores, which may be exploited to host small gaseous species. First principles adsorption energies of molecular hydrogen (H2) on graphene, graphdiyne and graphtriyne molecular prototypes are obtained at the MP2C level of theory. First, a single layer is investigated and it is found that graphynes are more suited than graphene for H2 physical adsorption since they provide larger binding energies at equilibrium distances much closer to the 2D plane. In particular, for graphtriyne a flat minimum located right in the geometric center of the pore is identified. A novel graphite composed of graphtriyne stacked sheets is then proposed and an estimation of its 3D arrangement is obtained at the DFT level of theory. In contrast to pristine graphite this new carbon material allow both H2 intercalation and out-of-plane diffusion by exploiting the larger volume provided by its nanopores. Related H2 binding ...
First-principles investigations of the physical properties of binary uranium silicide alloys
NASA Astrophysics Data System (ADS)
Yang, Jin; Long, Jianping; Yang, Lijun; Li, Dongmei
2013-11-01
The structural, elastic properties and the Debye temperature of binary Uranium Silicide (U-Si) alloys are investigated by using the first-principles plane-wave pseudopotential density function theory within the generalized gradient approximation (GGA). The ground states properties are found to agree with the available experimental data. The mechanical properties like shear modulus, Young's modulus, Poisson's ratio ? and ratio B/G are also calculated. Finally, The averaged sound velocity (vm), the longitudinal sound velocity (vl), transverse sound velocity (vt) and the Debye temperature (?D) are obtained. However, the theoretical values are slightly different from few existed experiment data because the latter was obtained at room temperature while the former one at 0 K.
First-principles study of FeSe epitaxial films on SrTiO3
NASA Astrophysics Data System (ADS)
Liu, Kai; Gao, Miao; Lu, Zhong-Yi; Xiang, Tao
2015-11-01
The discovery of high temperature superconductivity in FeSe films on SrTiO3 substrate has inspired great experimental and theoretical interests. First-principles density functional theory calculations, which have played an important role in the study of bulk iron-based superconductors, also participate in the investigation of interfacial superconductivity. In this article, we review the calculation results on the electronic and magnetic structures of FeSe epitaxial films, emphasizing on the interplay between different degrees of freedom, such as charge, spin, and lattice vibrations. Furthermore, the comparison between FeSe monolayer and bilayer films on SrTiO3 is discussed. Project supported by the National Natural Science Foundation of China (Grant Nos. 11190024 and 11404383), the National Basic Research Program of China (Grant No. 2011CBA00112), the Fundamental Research Funds for the Central Universities, China, and the Research Funds of Renmin University of China (Grant No. 14XNLQ03).
NASA Astrophysics Data System (ADS)
Li, Yang; Lian, Fang; Chen, Ning; Hao, Zhen-jia; Chou, Kuo-chih
2015-05-01
A first-principles method is applied to comparatively study the stability of lithium metal oxides with layered or spinel structures to predict the most energetically favorable structure for different compositions. The binding and reaction energies of the real or virtual layered LiMO2 and spinel LiM2O4 (M = Sc-Cu, Y-Ag, Mg-Sr, and Al-In) are calculated. The effect of element M on the structural stability, especially in the case of multiple-cation compounds, is discussed herein. The calculation results indicate that the phase stability depends on both the binding and reaction energies. The oxidation state of element M also plays a role in determining the dominant structure, i.e., layered or spinel phase. Moreover, calculation-based theoretical predictions of the phase stability of the doped materials agree with the previously reported experimental data.
First-principles study on phase transition and ferroelectricity in lithium niobate and tantalate
NASA Astrophysics Data System (ADS)
Toyoura, Kazuaki; Ohta, Masataka; Nakamura, Atsutomo; Matsunaga, Katsuyuki
2015-08-01
The phase transitions and ferroelectricity of LiNbO3 and LiTaO3 have been investigated theoretically from first principles. The phonon analyses and the molecular dynamics simulations revealed that the ferroelectric phase transition is not conventional displacive type but order-disorder type with strong correlation between cation displacements. According to the evaluated potential energy surfaces around the paraelectric structures, the large difference in ferroelectricity between the two oxides results from the little difference in short-range interionic interaction between Nb-O and Ta-O. As the results of the crystal orbital overlap population analyses, the different short-range interaction originates from the difference in covalency between Nb4d-O2p and Ta5d-O2p orbitals, particularly dxz-px/dyz-py orbitals (? orbitals), from the electronic point of view.
Formation and annealing behaviors of qubit centers in 4H-SiC from first principles
Wang, Xiaopeng; Zhao, Mingwen Bu, Hongxia; He, Xiujie; Wang, Aizhu; Zhang, Hongyu
2013-11-21
Inspired by finding that the nitrogen-vacancy center in diamond is a qubit candidate, similar defects in silicon carbide (SiC) have drawn considerable interest. However, the generation and annealing behaviors of these defects remain unclear. Using first-principles calculations, we describe the equilibrium concentrations and annealing mechanisms based on the diffusion of silicon vacancies. The formation energies and energy barriers along different migration paths, which are responsible for the formation rates, stability, and concentrations of these defects, are investigated. The effects on these processes of charge states, annealing temperature, and crystal orientation are also discussed. These theoretical results are expected to be useful in achieving controllable generation of these defects in experiments.
Ultrathin Carbon Nanotubes for Efficient Energy Storage: A First-Principles Study
NASA Astrophysics Data System (ADS)
Wang, Xue-Qing; Wang, Yu-Sheng; Wang, Yu-Cang; Wang, Fei; Sun, Qiang; Jia, Yu
2014-02-01
On the basis of first-principles density functional calculations, the present study sheds theoretical insight on ultrathin carbon nanotube (UCNT) and hydrogenated ultrathin carbon nanotube (HUCNT) for use as potential materials not only for Li-ion battery anode but also for high-capacity hydrogen storage. The highest Li storage capacities in UCNT and HUCNT can be of LiC4 and LiC4H2, respectively, which are higher than that in graphite and LiC6. Binding between Li (Ca) atoms and these materials are found to be enhanced considerably. Each Li (Ca) atom may bind multi-hydrogen molecules, and the adsorption energies are ideally suited for storing hydrogen under ambient conditions, and the predicted weight percentage of molecular hydrogen are in the range of 6.4-12 wt% exceeding the target set by the United States Department of Energy.
Desnavi, Sameerah; Chakraborty, Brahmananda; Ramaniah, Lavanya M.
2014-04-24
The electronic structure and hydrogen storage capability of Yttrium-doped grapheme has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site of the hexagonal ring with a binding energy of 1.40 eV. Doping by Y makes the system metallic and magnetic with a magnetic moment of 2.11 ?{sub B}. Y decorated graphene can adsorb up to four hydrogen molecules with an average binding energy of 0.415 eV. All the hydrogen atoms are physisorbed with an average desorption temperature of 530.44 K. The Y atoms can be placed only in alternate hexagons, which imply a wt% of 6.17, close to the DoE criterion for hydrogen storage materials. Thus, this system is potential hydrogen storage medium with 100% recycling capability.
Supercapacitors composed of graphene and boron nitride layers: A first-principles study
Özçelik, V Ongun; Ciraci, S
2012-01-01
We propose a model for nanoscale supercapacitor consisting of two-dimensional insulating BN layers placed between two commensurate and metallic graphene layers. First-principles Density Functional calculations of structure optimized total energy and self-consistent field potential performed on these nanoscale capacitors for different levels of charging and different number of BN layers mark the values of capacitance per unit mass, which are larger than those measured values for the supercapacitors made from other carbon based materials. Our theoretical study also compares results obtained for the present nanoscale capacitor with those of classical Helmholtz model and reveals crucial differences. Our model allows the fabrication of series/parallel mixed combinations consisting of epitaxially grown, sequential and multiple graphene/BN sheets.
Discharge Reaction Mechanisms in Na/FeS2 Batteries: First-Principles Calculations
NASA Astrophysics Data System (ADS)
Momida, Hiroyoshi; Kitajou, Ayuko; Okada, Shigeto; Yamashita, Tomoki; Oguchi, Tamio
2015-12-01
We have studied microscopic discharge reaction mechanisms in Na/FeS2 batteries by first-principles calculations. The calculated Na-Fe-S phase diagram shows that the discharge reactions can proceed by converting 4Na and FeS2 into 2Na2S and Fe as a fully discharged state. As an intermediate discharge reaction, we find that NaxFeS2 (x ˜ 1.5) intermediate products can be generated in the cathode, giving two major plateaus in voltage-capacity curves. The calculated voltage-capacity characteristics and X-ray absorption spectra at S and Fe K-edges of Na-discharged FeS2 cathode materials are compared with experimental results, showing that theoretically determined reaction formulas can account for the experimental discharge reactions.
Thermoelectric properties of AgSbTe? from first-principles calculations
Rezaei, Nafiseh; Akbarzadeh, Hadi; Hashemifar, S. Javad
2014-09-14
The structural, electronic, and transport properties of AgSbTe? are studied by using full-relativistic first-principles electronic structure calculation and semiclassical description of transport parameters. The results indicate that, within various exchange-correlation functionals, the cubic Fd3?m and trigonal R3?m structures of AgSbTe? are more stable than two other considered structures. The computed Seebeck coefficients at different values of the band gap and carrier concentration are accurately compared with the available experimental data to speculate a band gap of about 0.1–0.35 eV for AgSbTe? compound, in agreement with our calculated electronic structure within the hybrid HSE (Heyd-Scuseria-Ernzerhof) functional. By calculating the semiclassical Seebeck coefficient, electrical conductivity, and electronic part of thermal conductivity, we present the theoretical upper limit of the thermoelectric figure of merit of AgSbTe? as a function of temperature and carrier concentration.
Stability of the hcp Ruthenium at high pressures from first principles
Lugovskoy, A. V. Belov, M. P.; Vekilov, Yu. Kh; Krasilnikov, O. M.
2014-09-14
The method of calculation of the elastic constants up to third order from the energy-strain relation under pressure for the hcp crystals is given and described in details. The method is applied to the hcp phase of Ruthenium. Elastic constants, lattice dynamics, and electronic structure are investigated in the pressure interval of 0–600 GPa by means of first principles calculations. The obtained parameters are in very good agreement with available experimental and theoretical data. No preconditions for phase transformation driven by mechanical or dynamical instabilities for hcp Ru were found in the investigated pressure range. The reason of stability at such high pressures is explained in the context of electronic structure peculiarities.
Experimental and first principle studies on electronic structure of BaTiO{sub 3}
Sagdeo, Archna Ghosh, Haranath Chakrabarti, Aparna Kamal, C. Ganguli, Tapas Deb, S. K.; Phase, D. M.
2014-04-24
We have carried out photoemission experiments to obtain valence band spectra of various crystallographic symmetries of BaTiO{sub 3} system which arise as a function of temperature. We also present results of a detailed first principle study of these symmetries of BaTiO{sub 3} using generalized gradient approximation for the exchange-correlation potential. Here we present theoretical results of density of states obtained from DFT based simulations to compare with the experimental valence band spectra. Further, we also perform calculations using post density functional approaches like GGA + U method as well as non-local hybrid exchange-correlation potentials like PBE0, B3LYP, HSE in order to understand the extent of effect of correlation on band gaps of different available crystallographic symmetries (5 in number) of BaTiO{sub 3}.
Risk reduction and the privatization option: First principles
Bjornstad, D.J.; Jones, D.W.; Russell, M.; Cummings, R.C.; Valdez, G.; Duemmer, C.L.
1997-06-25
The Department of Energy`s Office of Environmental Restoration and Waste Management (EM) faces a challenging mission. To increase efficiency, EM is undertaking a number of highly innovative initiatives--two of which are of particular importance to the present study. One is the 2006 Plan, a planning and budgeting process that seeks to convert the clean-up program from a temporally and fiscally open-ended endeavor to a strictly bounded one, with firm commitments over a decade-long horizon. The second is a major overhauling of the management and contracting practices that define the relationship between the Department and the private sector, aimed at cost reduction by increasing firms` responsibilities and profit opportunities and reducing DOE`s direct participation in management practices and decisions. The goal of this paper is to provide an independent perspective on how EM should create new management practices to deal with private sector partners that are motivated by financial incentives. It seeks to ground this perspective in real world concerns--the background of the clean-up effort, the very difficult technical challenges it faces, the very real threats to environment, health and safety that have now been juxtaposed with financial drivers, and the constraints imposed by government`s unique business practices and public responsibilities. The approach is to raise issues through application of first principles. The paper is targeted at the EM policy officer who must implement the joint visions of the 2006 plan and privatization within the context of the tradeoff between terminal risk reduction and interim risk management.
Monolayer II-VI semiconductors: A first-principles prediction
NASA Astrophysics Data System (ADS)
Zheng, Hui; Li, Xian-Bin; Chen, Nian-Ke; Xie, Sheng-Yi; Tian, Wei Quan; Chen, Yuanping; Xia, Hong; Zhang, S. B.; Sun, Hong-Bo
2015-09-01
A systematic study of 32 honeycomb monolayer II-VI semiconductors is carried out by first-principles methods. While none of the two-dimensional (2D) structures can be energetically stable, it appears that BeO, MgO, CaO, ZnO, CdO, CaS, SrS, SrSe, BaTe, and HgTe honeycomb monolayers have a good dynamic stability. The stability of the five oxides is consistent with the work published by Zhuang et al. [Appl. Phys. Lett. 103, 212102 (2013), 10.1063/1.4831972]. The rest of the compounds in the form of honeycomb are dynamically unstable, revealed by phonon calculations. In addition, according to the molecular dynamic (MD) simulation evolution from these unstable candidates, we also find two extra monolayers dynamically stable, which are tetragonal BaS [P 4 /n m m (129 ) ] and orthorhombic HgS [P 21/m (11 ) ] . The honeycomb monolayers exist in the form of either a planar perfect honeycomb or a low-buckled 2D layer, all of which possess a band gap and most of them are in the ultraviolet region. Interestingly, the dynamically stable SrSe has a gap near visible light, and displays exotic electronic properties with a flat top of the valence band, and hence has a strong spin polarization upon hole doping. The honeycomb HgTe has recently been reported to achieve a topological nontrivial phase under appropriate in-plane tensile strain and spin-orbital coupling (SOC) [J. Li et al., arXiv:1412.2528]. Some II-VI partners with less than 5 % lattice mismatch may be used to design novel 2D heterojunction devices. If synthesized, potential applications of these 2D II-VI families could include optoelectronics, spintronics, and strong correlated electronics.
First-principles investigation of hydrous post-perovskite
NASA Astrophysics Data System (ADS)
Townsend, Joshua P.; Tsuchiya, Jun; Bina, Craig R.; Jacobsen, Steven D.
2015-07-01
A stable, hydrogen-defect structure of post-perovskite (hy-ppv, Mg1-xSiH2xO3) has been determined by first-principles calculations of the vibrational and elastic properties up to 150 GPa. Among three potential hy-ppv structures analyzed, one was found to be stable at pressures relevant to the lower-mantle D? region. Hydrogen has a pronounced effect on the elastic properties of post-perovskite due to magnesium defects associated with hydration, including a reduction of the zero-pressure bulk (K0) and shear (G0) moduli by 5% and 8%, respectively, for a structure containing ?1 wt.% H2O. However, with increasing pressure the moduli of hy-ppv increase significantly relative to ppv, resulting in a structure that is only 1% slower in bulk compressional velocity and 2.5% slower in shear-wave velocity than ppv at 120 GPa. In contrast, the reduction of certain anisotropic elastic constants (Cij) in hy-ppv increases with pressure (notably, C55, C66, and C23), indicating that hydration generally increases elastic anisotropy in hy-ppv at D? pressures. Calculated infrared absorption spectra show two O-H stretching bands at ?3500 cm-1 that shift with pressure to lower wavenumber by about 2 cm-1/GPa. At 120 GPa the hydrogen bonds in hy-ppv are still asymmetric. The stability of a hy-ppv structure containing 1-2 wt.% H2O at D? pressures implies that post-perovskite may be a host for recycled or primordial hydrogen near the Earth's core-mantle boundary.
A digitally reconstructed radiograph algorithm calculated from first principles
Staub, David; Murphy, Martin J.
2013-01-15
Purpose: To develop an algorithm for computing realistic digitally reconstructed radiographs (DRRs) that match real cone-beam CT (CBCT) projections with no artificial adjustments. Methods: The authors used measured attenuation data from cone-beam CT projection radiographs of different materials to obtain a function to convert CT number to linear attenuation coefficient (LAC). The effects of scatter, beam hardening, and veiling glare were first removed from the attenuation data. Using this conversion function the authors calculated the line integral of LAC through a CT along rays connecting the radiation source and detector pixels with a ray-tracing algorithm, producing raw DRRs. The effects of scatter, beam hardening, and veiling glare were then included in the DRRs through postprocessing. Results: The authors compared actual CBCT projections to DRRs produced with all corrections (scatter, beam hardening, and veiling glare) and to uncorrected DRRs. Algorithm accuracy was assessed through visual comparison of projections and DRRs, pixel intensity comparisons, intensity histogram comparisons, and correlation plots of DRR-to-projection pixel intensities. In general, the fully corrected algorithm provided a small but nontrivial improvement in accuracy over the uncorrected algorithm. The authors also investigated both measurement- and computation-based methods for determining the beam hardening correction, and found the computation-based method to be superior, as it accounted for nonuniform bowtie filter thickness. The authors benchmarked the algorithm for speed and found that it produced DRRs in about 0.35 s for full detector and CT resolution at a ray step-size of 0.5 mm. Conclusions: The authors have demonstrated a DRR algorithm calculated from first principles that accounts for scatter, beam hardening, and veiling glare in order to produce accurate DRRs. The algorithm is computationally efficient, making it a good candidate for iterative CT reconstruction techniques that require a data fidelity term based on the matching of DRRs and projections.
First-principles studies of Ni-Ta intermetallic compounds
Zhou Yi; Wen Bin; Ma Yunqing; Melnik, Roderick; Liu Xingjun
2012-03-15
The structural properties, heats of formation, elastic properties, and electronic structures of Ni-Ta intermetallic compounds are investigated in detail based on density functional theory. Our results indicate that all Ni-Ta intermetallic compounds calculated here are mechanically stable except for P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2}. Furthermore, we found that Pmmn-Ni{sub 3}Ta is the ground state stable phase of Ni{sub 3}Ta polymorphs. The polycrystalline elastic modulus has been deduced by using the Voigt-Reuss-Hill approximation. All Ni-Ta intermetallic compounds in our study, except for NiTa, are ductile materials by corresponding G/K values and poisson's ratio. The calculated heats of formation demonstrated that Ni{sub 2}Ta are thermodynamically unstable. Our results also indicated that all Ni-Ta intermetallic compounds analyzed here are conductors. The density of state demonstrated the structure stability increases with the Ta concentration. - Graphical abstract: Mechanical properties and formation heats of Ni-Ta intermetallic compounds are discussed in detail in this paper. Highlights: Black-Right-Pointing-Pointer Ni-Ta intermetallic compounds are investigated by first principle calculations. Black-Right-Pointing-Pointer P21/m-Ni{sub 3}Ta and hc-NiTa{sub 2} are mechanically unstable phases. Black-Right-Pointing-Pointer Pmmn-Ni{sub 3}Ta is ground stable phase of Ni{sub 3}Ta polymorphs. Black-Right-Pointing-Pointer All Ni-Ta intermetallic compounds are conducting materials.
First-principles study of codoping in lanthanum bromide
NASA Astrophysics Data System (ADS)
Erhart, Paul; Sadigh, Babak; Schleife, André; Åberg, Daniel
2015-04-01
Codoping of Ce-doped LaBr3 with Ba, Ca, or Sr improves the energy resolution that can be achieved by radiation detectors based on these materials. Here, we present a mechanism that rationalizes this enhancement on the basis of first-principles electronic structure calculations and point defect thermodynamics. It is shown that incorporation of Sr creates neutral VBr-SrLa complexes that can temporarily trap electrons. As a result, Auger quenching of free carriers is reduced, allowing for a more linear, albeit slower, scintillation light yield response. Experimental Stokes shifts can be related to different CeLa-SrLa-VBr triple complex configurations. Codoping with other alkaline as well as alkaline-earth metals is considered as well. Alkaline elements are found to have extremely small solubilities on the order of 0.1 ppm and below at 1000 K. Among the alkaline-earth metals the lighter dopant atoms prefer interstitial-like positions and create strong scattering centers, which has a detrimental impact on carrier mobilities. Only the heavier alkaline-earth elements (Ca, Sr, Ba) combine matching ionic radii with sufficiently high solubilities. This provides a rationale for the experimental finding that improved scintillator performance is exclusively achieved using Sr, Ca, or Ba. The present mechanism demonstrates that codoping of wide-gap materials can provide an efficient means for managing charge carrier populations under out-of-equilibrium conditions. In the present case dopants are introduced that manipulate not only the concentrations but also the electronic properties of intrinsic defects without introducing additional gap levels. This leads to the availability of shallow electron traps that can temporarily localize charge carriers, effectively deactivating carrier-carrier recombination channels. The principles of this mechanism are therefore not specific to the material considered here but can be adapted for controlling charge carrier populations and recombination in other wide-gap materials.
Vibrational spectra of vitreous germania from first-principles
NASA Astrophysics Data System (ADS)
Giacomazzi, Luigi; Umari, P.; Pasquarello, Alfredo
2006-10-01
We report on a first-principles investigation of the structural and vibrational properties of vitreous germania (v-GeO2) . Our work focuses on a periodic model structure of 168 atoms, but three smaller models are also studied for comparison. We first carry out a detailed structural analysis both in real and reciprocal spaces. Our study comprises the partial pair correlation functions, the angular distributions, the total neutron correlation function, the neutron and x -ray total structure factors, and the Faber-Ziman and Bhatia-Thornthon partial structure factors. We find overall good agreement with available experimental data. We then obtain the vibrational frequencies and eigenmodes. We analyze the vibrational density of states in terms of Ge and O motions, and further in terms of rocking, bending, and stretching contributions. The inelastic neutron spectrum is found to differ only marginally from the vibrational density of states. Using a methodology based on the application of finite electric fields, we derive dynamical Born charge tensors and Raman coupling tensors. For the infrared spectra, we calculate the real and imaginary parts of the dielectric function, including the high-frequency and static dielectric constants. The Raman spectra are shown to be sensitive to the medium-range structure and support an average Ge-O-Ge angle of 135°. We identify the shoulder X2 as a signature of breathing O vibrations in three-membered rings. Four-membered rings are found to contribute to the main Raman peak. We advance an interpretation for the shoulder X1 in terms of delocalized bond-bending modes. We derive bond polarizability parameters from the calculated Raman coupling tensors and demonstrate their level of reliability in reproducing the spectra. The calculated vibrational spectra all show good agreement with the respective experimental spectra.
Zhang, Jian; Yang, Ping; Sun, Zhenrong; Wang, Xue B.
2014-09-18
Molecular species with electron affinities (EAs) larger than that of the chlorine atom (3.6131 eV) are superhalogens. The corresponding negative ions, namely, superhalogen anions, are intrinsically very stable with high electron binding energies (EBEs), and widely exist as building blocks of bulk materials and ionic liquids. The most common superhalogen anions proposed and confirmed to date are either ionic salts or compact inorganic species. Herein we report a new class of superhalogen species, a series of tetracoordinated organoboron anions [BL4]– (L = phenyl (1), 4-fluorophenyl (2), 1-imidazolyl (3), L4 = H(pyrazolyl)3 (4)) with bulky organic ligands covalently bound to the central B atom. Negative ion photoelectron spectroscopy (NIPES) reveals all of these anions possessing EBEs higher than that of Cl- with the adiabatic / vertical detachment energy (ADE / VDE) of 4.44/4.8 (1), 4.78/5.2 (2), 5.08/5.4 (3), and 4.59/4.9 eV (4), respectively. First-principles calculations confirmed high EBEs of [BL4]– and predicted that these anions are thermodynamically stable against fragmentation. The unraveled superhalogen nature of these species provides a molecular basis to explain the wide-range applications of tetraphenylborate (TPB) (1) and trispyrazolylborate (Tp) (4) in many areas spanning from industrial waste treatment to soft material synthesis and organometallic chemistry
Antirelaxation coatings in coherent spectroscopy: Theoretical investigation and experimental test
NASA Astrophysics Data System (ADS)
Nasyrov, K.; Gozzini, S.; Lucchesini, A.; Marinelli, C.; Gateva, S.; Cartaleva, S.; Marmugi, L.
2015-10-01
We describe a theoretical model, based on a density matrix and the Liouville equation, for the investigation of magneto-optical resonances in alkali-metal atomic vapor, in particular in the case of the electromagnetically induced transparency (EIT) in the presence of antirelaxation coatings. The influence of the coating is parametrized with an empirical coefficient describing its efficiency; the calculations are extended to a broad range of coating quality, contrary to previous works, and to uncoated cells. The model takes into account also different configurations for the EIT formation and different efficiency of optical pumping, as determined by the coating characteristics and the atomic energy structure. The model is validated by investigating the EIT with degenerate Zeeman levels in 39K D1 and Cs D2 lines, which exhibit respectively an almost negligible and a relevant impact of hyperfine optical pumping. The results are compared to experimental data, exhibiting good agreement; in particular, for the 39K D1 line, recent findings are shown here in the case of degenerate and nondegenerate EIT with amplitude-modulated light. Our results demonstrate an effective approach for the investigation of antirelaxation coatings and their contribution in the formation of magneto-optical resonances in alkali-metal atoms, in different regimes and with largely different efficiencies. This sheds new light on well-known but not yet entirely clarified phenomena and their behavior as a function of experimental parameters.
Simulations of silicate glasses under pressure with first principles approach
NASA Astrophysics Data System (ADS)
Ghosh, D. B.; Karki, B. B.
2011-12-01
Silicate glasses have long been studied because they are considered as analog of geologically relevant silicate melts. Experimental studies have suggested that silicate glasses undergo significant structural changes including irreversibility under compression. Here, we perform first-principles molecular dynamics simulations to explore the pressure-induced structural changes in two silicate glasses, MgSiO3 and CaAl2Si2O8, at 300 K over relevant mantle pressures. Our simulations show that at ambient conditions Si atoms remain mainly in tetrahedral arrangement (> 95 % four-fold coordination) with a mean coordination of slightly greater than 4. Al-O coordination environment consists of both tetrahedral and pentahedral species in large amounts. In contrary to a complete tetrahedral network in pure SiO2 glass, the linkage is partial (via bridging oxygens) in these Mg- and Ca-bearing systems. Upon compression, five-coordinated Si's appear initially in increasing abundance and they gradually turn into six-fold state and even 6+ coordinated states appear at very high pressure. In case of Ca and Mg, where ambient pressure coordination is a mixture of four-fold to seven-fold species, pressure induces gradual increase in coordination (seven- to nine-fold). In a similar fashion, O-Si and O-Al coordinations increase at the expense of free and non-bridging oxygens on compression. Appearance of oxygen tri-clusters (O atoms coordinated with 3 Si/Al atoms) at the compressed volumes is consistent with the experimental findings. Our prediction of various odd coordination species is supported by experimental studies of silicate glasses. We find that glass densification is rather rapid initially and becomes more gradual at pressures above 20 GPa. This behavior can be associated with the way the glass structure changes in terms of bond distances, bond angles and coordination environments as pressure increases. On decompression, the system fails to revert back to its initial structural state, consistent with the experimental observations, and this irreversibility can be attributed to the memory effects, i.e., to continuing existence of high coordination species (pentahedra and octahedra) to larger volumes.
First Principles Modeling of Bimolecular Reactions with Diffusion
NASA Astrophysics Data System (ADS)
Hansen, S. K.; Scher, H.; Berkowitz, B.
2013-12-01
We consider three approaches to modeling A + B ? C irreversible reactions in natural media: 1) a discretized diffusion-reaction equation (DRE), 2) a particle tracking (PT) scheme in which reaction occurs if and only if an A and B particle pair are within a fixed distance, r (the "reaction radius"), and 3) a PT scheme using an alternative to the fixed reaction radius: a collocation probability distribution derived directly from first principles. Each approach has advantages. In some cases a discretized DRE may be the most computationally efficient method. For PT simulations, robust codes exist based on use of a fixed reaction radius. And finally, collocation probabilities may be derived directly from the Fick's Law constant, D, which is a well-established property for most species. In each approach, a single parameter governs the 'promiscuity' of the reaction (i.e. the thermodynamic favorability of reaction, predicated on the particles being locally well mixed). For the DRE, fixed-reaction-radius PT, and collocation-based PT, these parameters are, respectively: a second-order decay rate, r, and D. We established a number of new results enhancing these approaches and relating them to each other (and to nature). In particular, a thought experiment concerning a simple system in which the predictions of each approach can be computed analytically was used to derive formulas establishing a universal one-to-one correspondence among each of the governing parameters. We thus showed the conditions for equivalence of the three approaches, and grounded both the DRE approach and the fixed-radius PT approach in the Fick's Law D. We further showed that the existing collocation-based PT theory is based on a probability distribution that is only correct for infinitesimally small times, but which can be modified to be accurate for larger times by means of continuous time random walk analysis and first-passage probability distributions. Finally, we employed a novel mathematical approach to adapt this into a workable collocation-based particle tracking technique.
First-principles theory, coarse-grained models, and simulations of ferroelectrics.
Waghmare, Umesh V
2014-11-18
CONSPECTUS: A ferroelectric crystal exhibits macroscopic electric dipole or polarization arising from spontaneous ordering of its atomic-scale dipoles that breaks inversion symmetry. Changes in applied pressure or electric field generate changes in electric polarization in a ferroelectric, defining its piezoelectric and dielectric properties, respectively, which make it useful as an electromechanical sensor and actuator in a number of applications. In addition, a characteristic of a ferroelectric is the presence of domains or states with different symmetry equivalent orientations of spontaneous polarization that are switchable with large enough applied electric field, a nonlinear property that makes it useful for applications in nonvolatile memory devices. Central to these properties of a ferroelectric are the phase transitions it undergoes as a function of temperature that involve lowering of the symmetry of its high temperature centrosymmetric paraelectric phase. Ferroelectricity arises from a delicate balance between short and long-range interatomic interactions, and hence the resulting properties are quite sensitive to chemistry, strains, and electric charges associated with its interface with substrate and electrodes. First-principles density functional theoretical (DFT) calculations have been very effective in capturing this and predicting material and environment specific properties of ferroelectrics, leading to fundamental insights into origins of ferroelectricity in oxides and chalcogenides uncovering a precise picture of electronic hybridization, topology, and mechanisms. However, use of DFT in molecular dynamics for detailed prediction of ferroelectric phase transitions and associated temperature dependent properties has been limited due to large length and time scales of the processes involved. To this end, it is quite appealing to start with input from DFT calculations and construct material-specific models that are realistic yet simple for use in large-scale simulations while capturing the relevant microscopic interactions quantitatively. In this Account, we first summarize the insights obtained into chemical mechanisms of ferroelectricity using first-principles DFT calculations. We then discuss the principles of construction of first-principles model Hamiltonians for ferroelectric phase transitions in perovskite oxides, which involve coarse-graining in time domain by integrating out high frequency phonons. Molecular dynamics simulations of the resulting model are shown to give quantitative predictions of material-specific ferroelectric transition behavior in bulk as well as nanoscale ferroelectric structures. A free energy landscape obtained through coarse-graining in real-space provides deeper understanding of ferroelectric transitions, domains, and states with inhomogeneous order and points out the key role of microscopic coupling between phonons and strain. We conclude with a discussion of the multiscale modeling strategy elucidated here and its application to other materials such as shape memory alloys. PMID:25361389
Kim, Sunhee; Sorescu, Dan C; Byl, Oleg; Yates, John T
2006-03-16
The coadsorption of CO and triethylenediamine (TEDA) (also called 1,4-diazabicyclo[2.2.2]octane, DABCO) on a high-area gamma-Al2O3 surface has been investigated with use of transmission FTIR spectroscopy. It has been found that TEDA binds more strongly to both Lewis acid sites and to Brønsted Al-OH sites than does CO. Competition experiments indicate that TEDA displaces CO to less strong binding sites. Evidence for weak CO...TEDA interactions is found in which small nu(CO) redshifts are produced. Comparison between different amines such as triethylenemonoamine (TEMA) (also called 1-azabicyclo[2.2.2]octane, ABCO), trimethylamine (TMA), and ammonia indicates that the nu(CO) redshift increases with increasing amine polarizability, indicating that the redshift is mainly due to dipole image damping effects on the CO oscillator frequency. The direct bonding between the exposed N lone pair electrons of the TEDA molecule and CO does not occur. First principles theoretical studies have characterized the bonding of CO with gamma-Al2O3 Lewis acid sites of various types as well as TEDA bonding to both Lewis acid sites and to Al-OH groups. The theoretical studies also indicate that strong bonding of adsorbed CO with TEDA molecules does not occur, and that the observed decrease in the binding energy of CO when coadsorbed with TEDA on gamma-Al2O3 is expected. PMID:16526710
Photoexcitation and Photochemical Stability of Organic Photovoltaic Materials from First Principles
NASA Astrophysics Data System (ADS)
Sai, Na; Leung, Kevin
2013-03-01
The development of high efficiency organic photovoltaics (OPV) has recently become enabled by the synthesis of new conjugated polymers with low band gap that allow light absorption over a broader range of the spectrum. Stability of these new polymers, a key requirement for commercialization, has not yet received sufficient attention. Here, we report first-principles theoretical modeling of photo-induced degradation of OPV polymers carried out using ab-initio density functional theory (DFT). We report photooxidation routes and reaction products for reactive species including superoxide oxygen anions and hydroxyl groups interacting with the standard workhorse OPV polymer, poly(3-hexyl-thiophene) (P3HT). We discuss theoretical issues and challenges affecting the modeling such reactions in OPV polymers. We also discuss the application of theoretical methods to low-band-gap polymers, and in particular, the effect of the chemical substitution on the photoexcitation properties of these new polymers. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Deparment of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000. This work is supported by the Energy Frontier Research Center funded by the U.S. DOE Office of Basic Energy Sciences under Award number DE-SC0001091.
First principles calculations of interlayer exchange coupling in bcc Fe/Cu/Fe structures
Kowalewski, M.; Heninrich, B.; Schulthess, T.C.; Butler, W.H.
1998-01-01
The authors report on theoretical calculations of interlayer exchange coupling between two Fe layers separated by a modified Cu spacer. These calculations were motivated by experimental investigations of similar structures by the SFU group. The multilayer structures of interest have the general form: Fe/Cu(k)/Fe and Fe/Cu(m)/X(1)/Cu(n)/Fe where X indicates one AL (atomic layer) of foreign atoms X (Cr, Ag, or Fe) and k, m, n represent the number of atomic layers of Cu. The purpose of the experimental and theoretical work was to determine the effect of modifying the pure Cu spacer by replacing the central Cu atomic layer with the atomic layer of foreign atoms X. The first principles calculation were performed using the Layer Korringa-Kohn-Rostoker (LKKR) method. The theoretical thickness dependence of the exchange coupling between two semi-infinite Fe layers was calculated for pure Cu spacer thicknesses in the range of 0 < k < 16. The effect of the foreign atoms X on the exchange coupling was investigated using the structure with 9 AL Cu spacer as a reference sample. The calculated changes in the exchange coupling are in qualitative agreement with experiment.
Shock Hugoniot of osmium up to 800 GPa from first principles calculations.
Joshi, K D; Gupta, Satish C; Banerjee, S
2009-10-14
First principles total energy calculations on hcp, ? (a three atom simple hexagonal), ? (bcc) and fcc phases of osmium have been performed as a function of hydrostatic compression employing the FP-LAPW method. The comparison of total energies of these phases up to a maximum compression V/V(0) = 0.58 (pressure?700 GPa) shows that the hcp structure remains stable up to this compression. The 300 K isotherm is determined after adding finite temperature thermal contributions to the total energy calculated as a function of volume at 0 K. From the theoretically determined isotherm, we have derived the shock Hugoniot of this metal and determined the shock parameters C(0) and s to be 4.48 km s(-1) and 1.32, respectively. Employing the theoretically calculated Gruneisen parameter in the differential form of the Lindemann melting rule, we have determined the variation of melting point of the osmium with pressure. The theoretically derived melting curve and the temperature rise along the Hugoniot predict the shock melting of osmium at ?447 GPa with a corresponding temperature of ?9203 K. PMID:21693986
Kumar, Ravhi S; Svane, Axel; Vaitheeswaran, Ganapathy; Kanchana, Venkatakrishnan; Antonio, Daniel; Cornelius, Andrew L; Bauer, Eric D; Xiao, Yuming; Chow, Paul
2015-11-01
The crystal structure and the Yb valence of the YbFe2Ge2 heavy fermion compound was measured at room temperature and under high pressures using high-pressure powder X-ray diffraction and X-ray absorption spectroscopy via both partial fluorescence yield and resonant inelastic X-ray emission techniques. The measurements are complemented by first-principles density functional theoretical calculations using the self-interaction corrected local spin density approximation investigating in particular the magnetic structure and the Yb valence. While the ThCr2Si2-type tetragonal (I4/mmm) structure is stable up to 53 GPa, the X-ray emission results show an increase of the Yb valence from v = 2.72(2) at ambient pressure to v = 2.93(3) at ?9 GPa, where at low temperature a pressure-induced quantum critical state was reported. PMID:26479903
Kumar, Ravhi S.; Svane, Axel; Vaitheeswaran, Ganapathy; Kanchana, Venkatakrishnan; Antonio, Daniel; Cornelius, Andrew L.; Bauer, Eric D.; Xiao, Yuming; Chow, Paul
2015-10-19
The crystal structure and the Yb valence of the YbFe_{2}Ge_{2} heavy fermion compound was measured at room temperature and under high pressures using high-pressure powder X-ray diffraction and X-ray absorption spectroscopy via both partial fluorescence yield and resonant inelastic X-ray emission techniques. Furthermore, the measurements are complemented by first-principles density functional theoretical calculations using the self-interaction corrected local spin density approximation investigating in particular the magnetic structure and the Yb valence. While the ThCr_{2}Si_{2}-type tetragonal (I4/mmm) structure is stable up to 53 GPa, the X-ray emission results show an increase of the Yb valence from v = 2.72(2) at ambient pressure to v = 2.93(3) at ~9 GPa, where at low temperature a pressure-induced quantum critical state was reported.
Strain sensitivity and superconducting properties of Nb3Sn from first principles calculations.
De Marzi, G; Morici, L; Muzzi, L; della Corte, A; Nardelli, M Buongiorno
2013-04-01
Using calculations from first principles based on density-functional theory we have studied the strain sensitivity of the A15 superconductor Nb3Sn. The Nb3Sn lattice cell was deformed in the same way as observed experimentally on multifilamentary, technological wires subject to loads applied along their axes. The phonon dispersion curves and electronic band structures along different high-symmetry directions in the Brillouin zone were calculated, at different levels of applied strain, ?, on both the compressive and the tensile side. Starting from the calculated averaged phonon frequencies and electron-phonon coupling, the superconducting characteristic critical temperature of the material, T(c), has been calculated by means of the Allen-Dynes modification of the McMillan formula. As a result, the characteristic bell-shaped T(c) versus ? curve, with a maximum at zero intrinsic strain, and with a slight asymmetry between the tensile and compressive sides, has been obtained. These first-principle calculations thus show that the strain sensitivity of Nb3Sn has a microscopic and intrinsic origin, originating from shifts in the Nb3Sn critical surface. In addition, our computations show that variations of the superconducting properties of this compound are correlated to stress-induced changes in both the phononic and electronic properties. Finally, the strain function describing the strain sensitivity of Nb3Sn has been extracted from the computed T(c)(?) curve, and compared to experimental data from multifilamentary, composite wires. Both curves show the expected bell-shaped behavior, but the strain sensitivity of the wire is enhanced with respect to the theoretical predictions for bulk, perfectly binary and stoichiometric Nb3Sn. An understanding of the origin of this difference might open potential pathways towards improvement of the strain tolerance in such systems. PMID:23478497
First principle optoelectronic studies of visible light sensitive CZT
NASA Astrophysics Data System (ADS)
Khan, Imad; Aliabad, H. A. Rahnamaye; Ahmad, Waqar; Ali, Zahid; Ahmad, Iftikhar
2013-11-01
The most attractive optical material in solar cells applications, CdZnTe (CZT), has been extensively studied both, experimentally and theoretically. The results obtained by various theoretical models are way too far from the experiments and hence, they fail to demonstrate the true theoretical picture of the compound. In the present study the electronic band gap, band gap bowing and optical properties of Cd1-xZnxTe (0 ? x ? 1) are revisited with an effective theoretical model to provide accurate theoretical foundations to the experimental results. The calculations are performed with the full potential linearized augmented plane wave (FPLAPW) method with the generalized gradient approximation + modified Becke-Johnson (GGAmBJ) potential. The calculated results are in agreement with the experimental results. The band gap increases non-lineally with the concentration. The optical properties of the compound like absorption coefficient, refractive index, reflectivity, energy loss function and oscillator strength are also calculated. The number of effective electrons in optical excitations decreases with the increase in concentration of Zn.
The flexoelectricity of barium and strontium titanates from first principles.
Hong, Jiawang; Catalan, G; Scott, J F; Artacho, E
2010-03-24
We present ab initio calculations of the longitudinal flexoelectricity for BaTiO(3) and SrTiO(3) using a direct approach. The calculated value for SrTiO(3) agrees with recently reported measurements. For BaTiO(3), however, the theoretical values are smaller than the measured ones; possible reasons for the discrepancy are discussed. PMID:21389458
First-principles elastic properties of (alpha)-Pu
Soderlind, P; Klepeis, J E
2008-11-04
Density-functional electronic structure calculations have been used to investigate the ambient pressure and low temperature elastic properties of the ground-state {alpha} phase of plutonium metal. The electronic structure and correlation effects are modeled within a fully relativistic anti-ferromagnetic treatment with a generalized gradient approximation for the electron exchange and correlation functionals. The 13 independent elastic constants, for the monoclinic {alpha}-Pu system, are calculated for the observed geometry. A comparison of the results with measured data from resonant ultrasound spectroscopy for a cast sample is made.
First principles effective electronic couplings for hole transfer in natural and size-expanded DNA
Migliore, Agostino; Corni, Stefano; Varsano, Daniele; Klein, Michael L.; Di Felice, Rosa
2009-01-01
Hole transfer processes between base pairs in natural DNA and size-expanded DNA (xDNA) are studied and compared, by means of an accurate first principles evaluation of the effective electronic couplings (also known as transfer integrals), in order to assess the effect of the base augmentation on the efficiency of charge transport through double-stranded DNA. According to our results, the size expansion increases the average electronic coupling, and thus the CT rate, with potential implications in molecular biology and in the implementation of molecular nanoelectronics. Our analysis shows that the effect of the nucleobase expansion on the charge-transfer (CT) rate is sensitive to the sequence of base pairs. Furthermore, we find that conformational variability is an important factor for the modulation of the CT rate. From a theoretical point of view, this work offers a contribution to the CT chemistry in ?-stacked arrays. Indeed, we compare our methodology against other standard computational frameworks that have been adopted to tackle the problem of CT in DNA, and unravel basic principles that should be accounted for in selecting an appropriate theoretical level. PMID:19537767
First-principle study of thermoelectric properties of impurity-doped magnesium silicide Mg2Si
NASA Astrophysics Data System (ADS)
Funashima, Hiroki
2014-03-01
The electronic structure and the thermoelectric properties of Mg2Si doped with several dopants, Al, Bi, Sb, and Zn, are theoretically examined using a first-principles calculation method. Mg2Si is a promising thermoelectric material that is functional in the temperature range from 500 to 800 K. Therefore, it is expected to be useful for recovering waste heat from exhaust gas in automotive applications, incinerators, and boilers. Moreover, this material has several desirable attributes with respect to cost and environmental protection: it is cheap, nontoxic, and composed of elements abundant on Earth. These advantages are important for practical usage in thermoelectric applications. Impurity doping is a well-established way to improve the thermoelectric performance of Mg2Si. Undoped Mg2Si crystals have n-type conductivity, but they can be doped with both n- and p-type impurities. A fundamental understanding of the relationship between impurity doping and the thermoelectric properties of Mg2Si will allow us to provide theoretical guidelines for further development of this material. As an effort toward this goal, we present here the band structure of Mg2Si using the full-potential linearized augmented plane-wave (FLAPW) method based on LDA/DFT and the conductivity.
A first principles method to simulate electron mobilities in 2D materials
NASA Astrophysics Data System (ADS)
Restrepo, Oscar D.; Krymowski, Kevin E.; Goldberger, Joshua; Windl, Wolfgang
2014-10-01
We examine the predictive capabilities of first-principles theoretical methods to calculate the phonon- and impurity-limited electron mobilities for a number of technologically relevant two-dimensional materials in comparison to experiment. The studied systems include perfect graphene, graphane, germanane and MoS2, as well as graphene with vacancies, and hydrogen, gold, and platinum adsorbates. We find good agreement with experiments for the mobilities of graphene (? = 2 × 105 cm2 V-1s-1) and graphane (? = 166 cm2 V-1s-1) at room temperature. For monolayer MoS2 we obtain ? = 225 cm2 V-1s-1. This value is higher than what is observed experimentally (0.5-200 cm2 V-1s-1) but is on the same order of magnitude as other recent theoretical results. For bulk MoS2 we obtain ? = 48 cm2 V-1s-1. We obtain a very high mobility of 18 200 cm2 V-1s-1 for single-layer germanane. The calculated reduction in mobility from the different impurities compares well to measurements where experimental data are available, demonstrating that the proposed method has good predictive capabilities and can be very useful for validation and materials design.
First-Principles Theory of Quantum Well Resonance in Double Barrier Magnetic Tunnel Junctions
Wang, Wei Hua
First-Principles Theory of Quantum Well Resonance in Double Barrier Magnetic Tunnel Junctions Yan) Quantum well (QW) resonances in Fe001=MgO=Fe=MgO=Fe double barrier magnetic tunnel junctions are calculated from first principles. By including the Coulomb blockade energy due to the finite size islands
Design and Characterization of Photoelectrodes from First Principles
Ogitsu, T; Wood, B; Choi, W; Huda, M; Wei, S
2012-05-11
Although significant performance improvements have been realized since the first demonstration of sunlight-driven water splitting in 1972, mainstream adoption of photoelectrochemical (PEC) cells remains limited by an absence of cost-effective electrodes that show simultaneously high conversion efficiency and good durability. Here we outline current and future efforts to use advanced theoretical techniques to guide the development of a durable, high-performance PEC electrode material. Working in close collaboration with experimental synthesis and characterization teams, we use a twofold approach focusing on: (1) rational design of novel high-performance electrode materials; and (2) characterization and optimization of the electrode-electrolyte interface.
NASA Astrophysics Data System (ADS)
Mary, J. Arul; Vijaya, J. Judith; Bououdina, M.; Kennedy, L. John; Dai, J. H.; Song, Y.
2015-02-01
Ce, Cu co-doped ZnO (Zn1-2xCexCuxO: x=0.00, 0.01, 0.02, 0.03, 0.04 and 0.05) nanocrystals were synthesized by a microwave combustion method. These nanocrystals were investigated by using X-ray diffraction (XRD), UV-visible diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), and vibrating sample magnetometer (VSM). The stability and magnetic properties of Ce and Cu co-doped ZnO were probed by first principle calculations. XRD results revealed that all the compositions are single crystalline. hexagonal wurtzite structure. The optical band gap of pure ZnO was found to be 3.22 eV, and it decreased from 3.15 to 3.10 eV with an increase in the concentration of Cu and Ce content. The morphologies of Ce and Cu co-doped ZnO samples confirmed the formation of nanocrystals with an average grain size ranging from 70 to 150 nm. The magnetization measurement results affirmed the antiferro and ferromagnetic state for Ce and Cu co-doped ZnO samples and this is in agreement with the first principles theoretical calculations.
Rohlfing, Michael; Tiago, M.L.; Louie, Steven G.
2000-03-20
Experimental and theoretical studies have shown that excitonic effects play an important role in the optical properties of conjugated polymers. The optical absorption spectrum of trans-polyacetylene, for example, can be understood as completely dominated by the formation of exciton bound states. We review a recently developed first-principles method for computing the excitonic effects and optical spectrum, with no adjustable parameters. This theory is used to study the absorption spectrum of two conjugated polymers: trans-polyacetylene and poly-phenylene-vinylene(PPV).
Gavrilenko, V. I.; Wu, R. Q.; Downer, M. C.; Ekerdt, J. G.; Lim, D.; Parkinson, P.
2001-04-15
We present calculated second-harmonic-generation (SHG) spectra of the Si(001) surface based on a first-principles description of eigenvalues and eigenvectors using ab initio pseudopotentials. We also present SHG spectra for Ge-covered Si(001). The theoretical results explain all essential features of recent experimental SHG spectra of the Si(001)-(2x1) surface with low coverages of hydrogen and/or germanium, which alter the E{sub 1} resonance in contrasting ways. The strong adatom specificity of the spectra results from redistribution of the adatom-related electronic states on the surface.
Kanagaprabha, S.; Rajeswarapalanichamy, R. Sudhapriyanga, G. Murugan, A. Santhosh, M.; Iyakutti, K.
2014-04-24
The electronic, structural and mechanical properties of ZrH and ZrH{sub 2} are investigated by means of first principles calculation based on density functional theory as implemented in VASP code with generalized gradient approximation. The calculated ground state properties are in good agreement with previous experimental and other theoretical results. Among the six crystallographic structures considered for ZrH, ZB phase is found to be the most stable phase, whereas ZrH{sub 2} is energetically stable in tetragonal structure at ambient condition. A structural phase transition from ZB?NaCl at a pressure 10 GPa is predicted for ZrH.
Theoretical background of optical emission spectroscopy for analysis of atmospheric pressure plasmas
NASA Astrophysics Data System (ADS)
Belmonte, Thierry; Noël, Cédric; Gries, Thomas; Martin, Julien; Henrion, Gérard
2015-12-01
This review contains a theoretical background of optical emission spectroscopy and some selected examples of issues in the field of atmospheric plasmas. It includes elements like line broadening, emission of continua and molecules, radiation models, etc. Modernized expressions figuring the terms hidden in global constants where cgs units prevail are given together with restrictions of use. Easy-to-use formulas are provided to give access to essential plasma parameters.
First-Principles Study of Casimir Repulsion in Metamaterials
Yannopapas, Vassilios; Vitanov, Nikolay V.
2009-09-18
We examine theoretically the Casimir effect between a metallic plate and several types of magnetic metamaterials in pursuit of Casimir repulsion, by employing a rigorous multiple-scattering theory for the Casimir effect. We first examine metamaterials in the form of two-dimensional lattices of inherently nonmagnetic spheres such as spheres made from materials possessing phonon-polariton and exciton-polariton resonances. Although such systems are magnetically active in infrared and optical regimes, the force between finite slabs of these materials and metallic slabs is plainly attractive since the effective electric permittivity is larger than the magnetic permeability for the studied spectrum. When lattices of magnetic spheres made from superparamagnetic composites are employed, we achieve not only Casimir repulsion but almost total suppression of the Casimir effect itself in the micrometer scale.
NASA Astrophysics Data System (ADS)
Groh, Sébastien; Alam, Masud
2015-06-01
An approach to derive, from first-principles data, accurate and reliable potentials in the modified embedded-atom method in view of modeling the mechanical behavior of metals is presented in this work and applied to the optimization of a potential representative of lithium (Li). Although the theoretical background of the modified embedded-atom method was considered in this work, the proposed method is general and it can be applied to any other functional form. The main feature of the method is to introduce several path transformations in the material database that are critical for plastic and failure behavior. As part of the potential validation, path transformations different from the ones used for the parameterization procedure are considered. Applied in the case of Li, the material database was enriched with the generalized stacking fault energy curve along the??<1?1?1>??-direction on the {1?1?0}-plane, and with the traction-separation behavior of a {1?0?0}-surface. The path transformations used to enrich the material database were initially derived from first-principles calculations. For validation, the generalized stacking fault energy curves along the??<1?1?1>??-direction on the {1?1?2}- and {1?2?3}-planes were considered for plasticity, while traction-separation behavior of {1?1?0} and {1?1?1}-planes were considered for failure behavior. As part of the validation procedure, the predictions made in the MEAM framework were validated by first-principles data. The final potential accurately reproduced basic equilibrium properties, elastic constants, surface energies in agreement with first-principles predictions, and transition energy between different crystal structures. Furthermore, generalized stacking fault energy curves along the??<1?1?1>??-direction on the {1?1?0}, {1?1?2}, and {1?2?3}-planes, and tensile cohesive stress, characteristic length of fracture, and work of separation of a {1?0?0}, {1?1?0}, and {1?1?1} surfaces obtained in the MEAM framework compared well with first-principles predictions. It also predicts good elastic constants for a crystal structure different than the one used for the fitting of the potential and the other four path transformations. The potential was tested for failure behavior using a full atomistic setup, and in addition of being qualitatively correct, the stress intensity factor for different crack orientations was found to be in agreement with the theory of Rice (1992 J. Mech. Phys. Solids 40 239-71) within an error of 10%. Finally, the optimized Li-MEAM potential is expected to be transferable to different local environments encountered in atomistic simulations of lattice defects.
First-principles studies of Al-Ni intermetallic compounds
Shi Dongmin; Wen Bin; Melnik, Roderick; Yao Shan; Li Tingju
2009-10-15
The structural properties, heats of formation, elastic properties, and electronic structures of Al-Ni intermetallic compounds are analyzed here in detail by using density functional theory. Higher calculated absolute values of heats of formation indicate a very strong chemical interaction between Al and Ni for all Al-Ni intermetallic compounds. According to the computational single crystal elastic constants, all the Al-Ni intermetallic compounds considered here are mechanically stable. The polycrystalline elastic modulus and Poisson's ratio have been deduced by using Voigt, Reuss, and Hill (VRH) approximations, and the calculated ratio of shear modulus to bulk modulus indicated that AlNi, Al{sub 3}Ni, AlNi{sub 3} and Al{sub 3}Ni{sub 5} compounds are ductile materials, but Al{sub 4}Ni{sub 3} and Al{sub 3}Ni{sub 2} are brittle materials. With increasing Ni concentration, the bulk modulus of Al-Ni intermetallic compounds increases in a linear manner. The electronic energy band structures confirm that all Al-Ni intermetallic compounds are conductors. - Graphical abstract: Calculated bulk modulus compared to experimental and other theoretical values for the Al-Ni intermetallic compounds.
Thermal transport properties of complex oxides from first principles
NASA Astrophysics Data System (ADS)
Bhatti, Aqyan; Jain, Ankit; McGaughey, Alan; Benedek, Nicole
2015-03-01
Thermal transport properties of materials are key parameters in the design of many engineering devices. For this reason, it is highly desirable to be able to control or tailor the thermal properties of materials for specific applications. Complex oxides are attractive in this regard, due to their low and potentially highly tunable thermal conductivity. However, the theoretical description of the thermal transport properties of oxides presents a number of challenges compared to conventional semiconductors. For example, oxides tend to have complex crystal structures and the atoms interact through long-range electrostatic forces. In this talk, we use the example of PbTiO3 to discuss some of the challenges and opportunities associated with thermal transport predictions in complex oxides. For example, many oxides contain very low-lying optical branches, which may provide important acoustic-optical scattering channels. In addition, it is often possible to tune the frequencies of such optical modes with epitaxial strain. We also link the observed negative thermal expansion behavior of PbTiO3 to two zone-boundary modes with large, negative Grüneisen parameters and comment on the consequences of this finding for the thermal transport properties of this material.
First Principles Equations of State of LLM-105
NASA Astrophysics Data System (ADS)
Manaa, Riad
2015-06-01
Equations of states (EOS) of unreacted energetic materials extending to high-pressure and temperatures regimes are provide fundamental information about the associated thermodynamic properties of these materials at extreme conditions. Using dispersion-corrected density functional theoretical calculations, we performed large-scale constant-volume, constant-pressure and temperature molecular dynamics simulations on crystal 2,6-diamino-3, 5-dinitropyrazine-1-oxide (LLM-105) for pressures ranging from ambient to 35 GPa, and temperatures ranging from 300 K to 1400 K. These calculations allowed us to construct an unreacted P-V-T EOS and obtain bulk modulus for each P-V isotherm. We also obtained the thermal expansion coefficient of LLM-105 in the temperature range of this study. Finally, we conducted a quantum-based molecular dynamics study at the C-J point to characterize the decomposition products of reacting LLM-105 at complete reactivity condition. This work performed under the auspices of the U.S. Department of Energy Lawrence Livermore National Laboratory under Contract DE-AC52-07NA27344.
First-principles study of two-dimensional electride: Yttrium carbide
NASA Astrophysics Data System (ADS)
Nandadasa, Chandani; Kim, Sungho; Kim, Seong-Gon; Lee, Young; Kim, Sung
2015-03-01
Electrides are an exclusive class of ionic compounds in which electrons serve as anions. We have performed first-principles density functional theory (DFT) calculations to investigate the structural, electronic and magnetic properties of two-dimensional layered-structure yttrium carbide (Y2C). Generalized gradient approximation (GGA) with Projector Augmented Potentials (PAW) was used to obtain optimized lattice parameters, energy band structure, charge density and density of states (DOS) plots for Y2C. The theoretically predicted structure of Y2C is in good agreement with the experimental results. The band crossing the Fermi energy level proved that Y2C has metallic properties. Additionally projected electronic density of states profiles were obtained to identify the electronic contribution from Y, C and non-atomic orbital located in interstitial site. The results of these calculations indicate that the presence of trapped electrons within the Y2C interlayers. Furthermore, surface energies of Y-Y and Y-C were calculated and charge densities were plotted with these surfaces. Magnetization density plots were used to obtain magnetic properties.
Lithium Intercalation in Graphene/MoS2 Composites: First-Principles Insights
Shao, Xiji; Pang, Rui; Shi, Xingqiang
2015-01-01
As a storage material for Li-ion batteries, graphene/molybdenum disulfide (Gr/MoS2) composites have been intensively studied in experiments. But the relevant theoretical works from first-principles are lacking. In the current work, van-der-Waals-corrected density functional theory calculations are performed to investigate the interaction of Li in Gr/MoS2 composites. Three interesting features are revealed for the intercalated Gr/Li(n)/MoS2 composites (n = 1 to 9). One is the reason for large Li storage capacity of Gr/MoS2: due to the binding energies per Li atom increase with the increasing number of intercalated Li atoms. Secondly, the band gap opening of Gr is found, and the band gap is enlarged with the increasing number of intercalated Li atoms, up to 160 meV with nine Li; hence these results suggest an efficient way to tune the band gap of graphene. Thirdly, the Dirac cone of Gr always preserve for different number of ionic bonded Li atoms.
First-principles calculation on ?-SiC(111)/?-WC(0001) interface
Jin, Na; Yang, Yanqing E-mail: jinna319@163.com; Li, Jian; Luo, Xian; Huang, Bin; Sun, Qing; Guo, Pengfei
2014-06-14
The ?-WC(0001) surface and ?-SiC(111)/?-WC(0001) interface were studied by first-principles calculation based on density functional theory. It is demonstrated that the ?-WC(0001) surface models with more than nine atom-layers exhibit bulk-like interior, wherein the surface relaxations localized within the top three layers are well converged. Twenty-four specific geometry models of SiC/WC interface structures with different terminations and stacking sites were chosen. The calculated work of adhesion and interface energy suggest that the most stable interface structure has the C-C bonding across the interface, yielding the largest work of adhesion and the lowest interface energy. Moreover, the top-site stacking sequence is preferable for the C/C-terminated interface. The effects of the interface on the electronic structures of the C/C-terminated interfaces are mainly localized within the first and second layers of the interface. Calculations of the work of adhesion and interface energy provide theoretical evidence that the mechanical failure may initiate at the interface or in SiC but not in WC.
Analyzing Variability in Short-Channel Quantum Transport from Atomistic First Principles
NASA Astrophysics Data System (ADS)
Shi, Qing; Guo, Hong; Zhu, Yu; Liu, Lei
2015-06-01
Effects of disorder scattering critically influence quantum-transport properties of nanostructures both fundamentally and practically. In this work, we report a theoretical analysis of the important issue of device-to-device quantum-transport variability (DDV) induced by random configurations of discrete dopants. Instead of calculating many impurity configurations by brute force, which is practically impossible to accomplish from first principles, here we use a state-of-the-art atomistic technique where the configurational average is carried out analytically, thereby, DDV can be predicted for any impurity concentration. The DDV we quantitatively analyze is the off-state tunnel conductance variability in Si nanosized field-effect transistor channels with channel lengths ranging from 6.5 to 15.2 nm doped with different concentrations of boron impurity atoms. The variability is predicted by varying the doping concentration, channel length, and the doping positions. We find that doping away from the source or drain contacts of the channel very significantly reduces variability, and doping close to the source or drain produces a nonintuitive outcome of increasing variability. The physics is understood by analyzing the microscopic details of the potential profile in the tunnel barrier. Finally, we organize the ab initio data by a Wentzel-Kramers-Brillouin model.
A first-principles study of He, Xe, Kr and O incorporation in thorium carbide
NASA Astrophysics Data System (ADS)
Pérez Daroca, D.; Llois, A. M.; Mosca, H. O.
2015-05-01
Thorium-based materials are currently being investigated in relation with their potential utilization in Generation-IV reactors as nuclear fuels. Understanding the incorporation of fission products and oxygen is very important to predict the behavior of nuclear fuels. A first approach to this goal is the study of the incorporation energies and stability of these elements in the material. By means of first-principles calculations within the framework of density functional theory, we calculate the incorporation energies of He, Xe, Kr and O atoms in Th and C vacancy sites, in tetrahedral interstitials and in Schottky defects along the <1 1 1> and <1 0 0> directions. We also analyze atomic displacements, volume modifications and Bader charges. This kind of results for ThC, to the best authors' knowledge, have not been obtained previously, neither experimentally, nor theoretically. This should deal as a starting point towards the study of the complex behavior of fission products in irradiated ThC.
Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.
2014-11-21
Structural, elastic, and lattice dynamical stability of YSe has been investigated as a function of pressure through first principles electronic band structure calculations. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of pressure suggests that the B1 phase will transform to B2 structure at ?32 (30?GPa at 300?K obtained from comparison of Gibbs free energy at 300?K). The transition is identified to be of first order in nature with a volume discontinuity of ?6.2% at the transition pressure. Furthermore, the theoretically determined equation of state has been utilized to derive various physical quantities, such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus. The single crystal elastic constants have been predicted at various pressures for both the B1 and B2 structures using the energy strain method. The activation barrier between B1 and B2 phases calculated at transition point is ?19.7mRy/formula unit. Our lattice dynamic calculations show that both the B1 as well as B2 structures are lattice dynamically stable not only at ambient pressure but also at transition pressure. The B1 phase becomes lattice dynamically unstable at ?112 GPa, i.e., much beyond the transition pressure. The effect of temperature on volume and bulk modulus of the YSe in B1 phase has also been examined.
Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.
2014-03-28
First principles calculations have been carried out to analyze structural, elastic, and dynamic stability of yttrium sulphide (YS) under hydrostatic compression. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of compression suggests the B1 ? B2 transition at ?49?GPa (the same transition occurs at ?48?GPa at 300?K). Various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus have been derived from the theoretically determined equation of state. The single crystal elastic constants derived from the energy strain method agree well with the experimental values. The activation barrier between B1 and B2 phases calculated at transition point is ?17/mRy/f.u. Our lattice dynamic calculations show that at ambient condition, the B1 phase is lattice dynamically stable, and frequencies of phonon modes in different high symmetry directions of Brillouin zone agrees well with experimental values. The B2 phase also is dynamical stable at ambient condition as well as at ?49?GPa, supporting our static lattice calculation. The effect of temperature on volume and bulk modulus of the YS in B1 phase has also been examined. The superconducting temperature of ?2.78?K determine at zero pressure agrees well with experimental data. The effect of pressure is found to suppress the superconducting nature of this material.
Pressure-induced novel compounds in the Hf-O system from first-principles calculations
NASA Astrophysics Data System (ADS)
Zhang, Jin; Oganov, Artem R.; Li, Xinfeng; Xue, Kan-Hao; Wang, Zhenhai; Dong, Huafeng
2015-11-01
Using first-principles evolutionary simulations, we have systematically investigated phase stability in the Hf-O system at pressure up to 120 GPa. New compounds Hf5O2,Hf3O2 , HfO, and HfO3 are discovered to be thermodynamically stable at certain pressure ranges. Two new high-pressure phases are found for Hf2O : one with space group Pnnm and anti-CaCl2-type structure, another with space group I 41/amd. Pnnm-HfO3 shows interesting structure, simultaneously containing oxide O2 - and peroxide [O-O]2 - anions. Remarkably, it is P 6 ¯2 m -HfO rather than OII-HfO2 that exhibits the highest mechanical characteristics among Hf-O compounds. Pnnm-Hf2O , Imm2-Hf5O2 ,P 3 ¯1 m -Hf2O , and P 4 ¯m 2 -Hf2O3 phases also show superior mechanical properties; theoretically these phases become metastable phases to ambient pressure and their properties can be exploited.
Gao, Chao; Wang, Zhenhui; Liang, Xingbo; Tian, Daxi; Liu, Hongyan; Ma, Xiangyang; Yang, Deren
2012-12-12
The effect of heavy phosphorus (P) doping on oxygen diffusion in Czochralski (Cz) silicon has been experimentally and theoretically investigated. It is experimentally found that the oxygen diffusion in heavily P-doped Cz silicon is retarded, with a diffusion activation energy which is ?0.12 eV larger than that of its lightly P-doped counterpart. First-principles calculations suggest that the P-O complexes in the -P-Si-O-Si- configuration can form in heavily P-doped Cz silicon, leading to the trapping of interstitial oxygen (O(i)) atoms at the twelve equivalent second-nearest neighbors of the P atoms. Furthermore, the calculated increase of the oxygen diffusion activation energy, taking account of the trapping effect of such P-O complexes, is in accordance with the experimental result. This indicates that the retarded oxygen diffusion in the heavily P-doped Cz silicon can be ascribed to the trapping of O(i) atoms associated with the formation of the aforementioned P-O complexes. PMID:23160172
NASA Astrophysics Data System (ADS)
Jang, Woosun; Yoo, Su-Hyun; Soon, Aloysius
2015-03-01
Owing to its unique and exotic physical and chemical properties, there has been a lot of effort undertaken to explore and study ultrathin low-dimensional nanostructures (e.g. graphene and MoS2). Of late, two-dimensional (2D) nanomembranes of silicon - a well-known prototypical bulk semiconductor - have attracted much attention, and has found its potential in niche nanodevice applications e.g. field effect transistors (FET) and secondary battery anodes. In this work, after considering various nanomembranes of Si with varying thicknesses, we study geometric and electronic structures using first-principles density-functional theory calculations (and beyond). Here, we consider both bulk-terminated pristine Si nanomembranes as well as surface-reconstructed ones, as motivated by available experimental and theoretical reports. To understand the influence of growth conditions on these Si nanomembranes, we have also studied the role of surface-passivation (e.g. with O, H, and OH) on their electronic and optical properties. Namely, we carefully investigate their thickness-dependent electronic band structure (i.e. both their fundamental and optical band gap energies), so as to elucidate their intrinsic structure-property relations for designing future technologically important nanodevices.
Thermodynamic ground state of MgB{sub 6} predicted from first principles structure search methods
Wang, Hui; Department of Physics and Engineering Physics, University of Saskatchewan, Saskatoon, Saskatchewan S7N 5E2 ; LeBlanc, K. A.; Gao, Bo; Yao, Yansun; Canadian Light Source, Saskatoon, Saskatchewan S7N 0X4
2014-01-28
Crystalline structures of magnesium hexaboride, MgB{sub 6}, were investigated using unbiased structure searching methods combined with first principles density functional calculations. An orthorhombic Cmcm structure was predicted as the thermodynamic ground state of MgB{sub 6}. The energy of the Cmcm structure is significantly lower than the theoretical MgB{sub 6} models previously considered based on a primitive cubic arrangement of boron octahedra. The Cmcm structure is stable against the decomposition to elemental magnesium and boron solids at atmospheric pressure and high pressures up to 18.3 GPa. A unique feature of the predicted Cmcm structure is that the boron atoms are clustered into two forms: localized B{sub 6} octahedra and extended B{sub ?} ribbons. Within the boron ribbons, the electrons are delocalized and this leads to a metallic ground state with vanished electric dipoles. The present prediction is in contrast to the previous proposal that the crystalline MgB{sub 6} maintains a semiconducting state with permanent dipole moments. MgB{sub 6} is estimated to have much weaker electron-phonon coupling compared with that of MgB{sub 2}, and therefore it is not expected to be able to sustain superconductivity at high temperatures.
First principles DFT study of dye-sensitized CdS quantum dots
Jain, Kalpna; Singh, Kh. S.; Kishor, Shyam; Josefesson, Ida; Odelius, Michael; Ramaniah, Lavanya M.
2014-04-24
Dye-sensitized quantum dots (QDs) are considered promising candidates for dye-sensitized solar cells. In order to maximize their efficiency, detailed theoretical studies are important. Here, we report a first principles density functional theory (DFT) investigation of experimentally realized dye - sensitized QD / ligand systems, viz., Cd{sub 16}S{sub 16}, capped with acetate molecules and a coumarin dye. The hybrid B3LYP functional and a 6?311+G(d,p)/LANL2dz basis set are used to study the geometric, energetic and electronic properties of these clusters. There is significant structural rearrangement in all the clusters studied - on the surface for the bare QD, and in the positions of the acetate / dye ligands for the ligated QDs. The density of states (DOS) of the bare QD shows states in the band gap, which disappear on surface passivation with the acetate molecules. Interestingly, in the dye-sensitised QD, the HOMO is found to be localized mainly on the dye molecule, while the LUMO is on the QD, as required for photo-induced electron injection from the dye to the QD.
Electrical contacts to monolayer black phosphorus: A first-principles investigation
NASA Astrophysics Data System (ADS)
Gong, Kui; Zhang, Lei; Ji, Wei; Guo, Hong
2014-09-01
We report first-principles theoretical investigations of possible metal contacts to monolayer black phosphorus (BP). By analyzing lattice geometry, five metal surfaces are found to have minimal lattice mismatch with BP: Cu(111), Zn(0001), In(110), Ta(110), and Nb(110). Further studies indicate Ta and Nb bond strongly with monolayer BP causing substantial bond distortions, but the combined Ta-BP and Nb-BP form good metal surfaces to contact a second layer BP. By analyzing the geometry, bonding, electronic structure, charge transfer, potential, and band bending, it is concluded that Cu(111) is the best candidate to form excellent Ohmic contact to monolayer BP. The other four metal surfaces or combined surfaces also provide viable structures to form metal/BP contacts, but they have Schottky character. Finally, the band bending property in the current-in-plane (CIP) structure where metal/BP is connected to a freestanding monolayer BP, is investigated. By both work function estimates and direct calculations of the two-probe CIP structure, we find that the freestanding BP channel is n type.
First-principles investigation of boron defects in nickel ferrite spinel
NASA Astrophysics Data System (ADS)
Rák, Zs.; O'Brien, C. J.; Brenner, D. W.
2014-09-01
The accumulation of boron within the porous nickel ferrite (NiFe2O4, NFO) deposited on nuclear reactor fuel rods is a major technological problem with important safety and economical implications. In this work, the electronic structure of nickel ferrite spinel has been investigated using first-principles methods, and the theoretical results have been combined with experimental data to analyze B incorporation into the spinel structure of NFO. Under thermodynamic solid-solid equilibrium between NFO and atomic reservoirs of Ni and Fe, our calculations predict that the incorporation of B into the NFO structure is unfavorable. The main factors that limit B incorporation are the narrow stability domain of NFO and the precipitation of B2O3, Fe3BO5, and Ni3B2O6 compounds as secondary phases. The B incorporation energies depend sensitively on the electron chemical potential (EF) and the charge state of the defect. In n-type NFO, the most stable defect is the Ni vacancy VNi2- while in p-type material lowest the formation energy belongs to the interstitial B occupying a tetrahedrally coordinated site BT2+. Because of these limiting conditions it is more thermodynamically favorable for B to form secondary phases with Fe, Ni and O (e.g. B2O3, Fe3BO5, and Ni3B2O6) than it is to form point defects in NFO.
Ordered structures in rhenium binary alloys from first-principles calculations.
Levy, Ohad; Jahnátek, Michal; Chepulskii, Roman V; Hart, Gus L W; Curtarolo, Stefano
2011-01-12
Rhenium is an important alloying agent in catalytic materials and superalloys, but the experimental and computational data on its binary alloys are sparse. Only 6 out of 28 Re transition-metal systems are reported as compound-forming. Fifteen are reported as phase-separating, and seven have high-temperature disordered ? or ? phases. Comprehensive high-throughput first-principles calculations predict stable ordered structures in 20 of those 28 systems. In the known compound-forming systems, they reproduce all the known compounds and predict a few unreported ones. These results indicate the need for an extensive revision of our current understanding of Re alloys through a combination of theoretical predictions and experimental validations. The following systems are investigated: AgRe(?), AuRe(?), CdRe(?), CoRe, CrRe(?), CuRe(?), FeRe, HfRe, HgRe(?), IrRe, MnRe, MoRe, NbRe, NiRe, OsRe, PdRe, PtRe, ReRh, ReRu, ReSc, ReTa, ReTc, ReTi, ReV, ReW(?), ReY, ReZn(?), and ReZr ((?) = systems in which the ab initio method predicts that no compounds are stable). PMID:21142072
First principle study of elastic and thermodynamic properties of FeB4 under high pressure
NASA Astrophysics Data System (ADS)
Zhang, Xinyu; Qin, Jiaqian; Ning, Jinliang; Sun, Xiaowei; Li, Xinting; Ma, Mingzhen; Liu, Riping
2013-11-01
The elastic properties, elastic anisotropy, and thermodynamic properties of the lately synthesized orthorhombic FeB4 at high pressures are investigated using first-principles density functional calculations. The calculated equilibrium parameters are in good agreement with the available experimental and theoretical data. The obtained normalized volume dependence of high pressure is consistent with the previous experimental data investigated using high-pressure synchrotron x-ray diffraction. The complete elastic tensors and crystal anisotropies of the FeB4 are also determined in the pressure range of 0-100 GPa. By the elastic stability criteria and vibrational frequencies, it is predicted that the orthorhombic FeB4 is stable up to 100 GPa. In addition, the calculated B/G ratio reveals that FeB4 possesses brittle nature in the range of pressure from 0 to 100 GPa. The calculated elastic anisotropic factors suggest that FeB4 is elastically anisotropic. By using quasi-harmonic Debye model, the compressibility, bulk modulus, the coefficient of thermal expansion, the heat capacity, and the Grüneisen parameter of FeB4 are successfully obtained in the present work.
NASA Astrophysics Data System (ADS)
Hanagud, Sathya
2005-07-01
?-Fe2O3 (Hematite) is of special interest in the design of multifunctional structural energetic materials (SEM), based on a thermite mixture of metal and metal oxide. In this paper, from first-principles, we obtained the thermodynamically complete EOS P = P(?,T) for hematite for pressures up to 50GPa and temperatures up to 1000K. There are only a few theoretical works on hematite. The difficulty of techniques traces back to the complication of the description of highly correlated d-electrons induced localization of valence states in Fe, and the mixing of the O 2p states and the Fe 3d states. In this paper, we implemented the ground state calculations in the framework of DFT, using sGGA and projector augmented wave approach. Particularly, the Hubbard-U method is used to describe the on-site Coulomb interactions of strongly correlated d-electrons in Fe atoms. The lattice thermal contributions are obtained by populating the phonon modes, according to the Boltzmann statistics. In comparison to the previous studies, the thermal contributions to EOS from lattice vibrations are included. In addition, we investigate the magnetic phase transitions at pressures and temperatures of interest. In the applications of SEMs, pressures are lower than 50 GPa which exclude the HP phases. The phonon dispersion curves with Hubbard-U are compared with those without Hubbard-U.
Thermoelectric transport properties of warm dense molybdenum from first-principles simulations
NASA Astrophysics Data System (ADS)
French, Martin; Haill, Thomas; Desjarlais, Michael; Mattsson, Thomas
2013-10-01
Molybdenum, with its high melting point, significant electrical conductivity, and high material strength, is a technologically important material in general and has in particular recently been proposed as a driver material in high-pressure strength experiments on Sandia's Z-machine. To simulate and understand the processes in these experiments with magneto-hydrodynamic simulations, accurate models for the electrical and thermal conductivity are needed for a wide range of thermodynamic parameters. Here, we present novel results for the electrical and thermal conductivity of molybdenum in various states ranging from the solid to the dense plasma phase. The results were obtained with first-principles simulation techniques that combine density functional theory with molecular dynamics and linear response theory. We find good agreement between our theoretical results and available experimental data. Sandia National Laboratories is a multiprogram laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the US Department of Energy's National Nuclear Security Administration under Contract No. DE-AC04-94AL85000.
Susan, S.
1993-04-30
Theoretical electronic structure techniques are used to analyze widely different systems from Si clusters to transition metal solids and surfaces. For the Si clusters, first principles density functional methods are used to investigate Si{sub N} for N=2-8. Goal is to understand the different types of bonding that can occur in such small clusters where the atomic coordination differs substantially from tetrahedral bonding; such uncoordinated structures can test approximate models of Si surfaces. For the transition metal systems, non-self-consistent electronic structure methods are used to understand the driving force for surface relaxations. In-depth analysis of results is presented and physical basis of surface relaxation within the theory is discussed. Limitations inherent in calculations of metal surface relaxation are addressed. Finally, in an effort to understand approximate methods, a novel non-self- consistent density functional electronic structure method is developed that is about 1000 times faster than more sophisticated methods; this method is tested for various systems including diatomics, mixed clusters, surfaces, and bulk lattices.
High pressure phase transformation in yttrium sulfide(YS): A first principle study
Sahoo, B. D. Joshi, K. D. Gupta, Satish C.
2014-04-24
First principles calculations have been carried out to analyze structural, elastic and dynamic stability, of YS under hydrostatic compression. The comparison of enthalpies of rocksalt type (B1) and CsCl type cubic (B2) structures determined as a function of compression suggests the B1?B2 transition at ? 49 GPa. Various physical quantities such as zero pressure equilibrium volume, bulk modulus, and pressure derivative of bulk modulus have been derived from the theoretically determined equation of state. The single crystal elastic constants derived from the energy strain method agree well with the experimental values. The activation barrier between B1 and B2 phases calculated at transition point is ? 17/mRy/formula unit. Our lattice dynamic calculations show that at ambient condition, the B1 phase is lattice dynamically stable and frequencies of phonon modes in different high symmetry directions of Brillouin zone agrees well with experimental values. The B2 phase also is dynamical stable at ambient condition as well as at ? 49 GPa, supporting our static lattice calculation.
Water solubility in calcium aluminosilicate glasses investigated by first principles techniques
Bouyer, Frederic; Geneste, Gregory; Ispas, Simona; Kob, Walter; Ganster, Patrick
2010-12-15
First-principles techniques have been employed to study the reactivity of water into a calcium aluminosilicate glass. In addition to the well known hydrolysis reactions Si-O-Si+H{sub 2}O{yields}Si-OH+Si-OH and Si-O-Al+H{sub 2}O{yields}Si-OH+Al-OH, a peculiar mechanism is found, leading to the formation of an AlO{sub 3}-H{sub 2}O entity and the breaking of Al-O-Si bond. In the glass bulk, most of the hydrolysis reactions are endothermic. Only a few regular sites are found reactive (i.e. in association with an exothermic reaction), and in that case, the hydrolysis reaction leads to a decrease of the local disorder in the amorphous vitreous network. Afterwards, we suggest that ionic charge compensators transform into network modifiers when hydrolysis occurs, according to a global process firstly suggested by Burnham in 1975. Our theoretical computations provide a more general model of the first hydrolysis steps that could help to understand experimental data and water speciation in glasses. -- Graphical Abstract: Reactivity within glass bulk: structures obtained after hydrolyses reactions (endothermic and exothermic processes) and mechanisms involving Si-OH, Al-OH, Si-OH-Al groups within aluminosilicates glasses (through ab initio molecular dynamics): formation of the Si-OH-Al entity coupled with an H exchange-Frederic Bouyer and Gregory Geneste. Display Omitted
Water confined in nanotubes and between graphene sheets: A first principle study
Cicero, G; Grossman, J C; Schwegler, E; Gygi, F; Galli, G
2008-10-17
Water confined at the nanoscale has been the focus of numerous experimental and theoretical investigations in recent years, y yet there is no consensus on such basic properties et as diffusion and the nature of hydrogen bonding (HB) under confinement. Unraveling these properties is important to understand fluid flow and transport at the nanoscale, and to shed light on the solvation of biomolecules. Here we report on a first principle, computational study focusing on water confined between prototypical non polar substrate, i.e. , single wall carbon nanotubes and graphene sheets, 1 to 2.5 nm apart. The results of our molecular dynamics simulations show the presence of a thin, interfacial liquid layer ({approx} 5 Angstroms) whose microscopic structure and thickness are independent of the distance between confining layers. The prop properties of the hydrogen bonded network are very similar to those of the bulk outside the interfacial region, even in the case of strong confinement , confinement. Our findings indicate that the perturbation induced by the presence of confining media is extremely local in liquid water, and we propose that many of the effects attributed to novel phases under confinement are determined by subtle electronic structure rearrangements occurring at the interface with the confining medium.
Characteristics of Co islets on Cu(111) from first principles calculations
NASA Astrophysics Data System (ADS)
Le, Duy; Raman, Talat
2009-03-01
Through first principles electronic calculations, based on the spin-polarized density functional theory using the generalized gradient approximation and the ultrasoft pseudopotential method in the plane wave representation, we have examined the structure and magnetic properties of Co monomer, dimer and several n-mers on Cu(111). We find that the monomer has slight preference for the fcc site as compared to the hcp (about 0.02eV) while there is no such preference in the case of the Co dimer. The dimer bond length is found to be about 2.15?. For the 6 atoms cluster, we find that it prefers to be antiferromagnetic and absolute magnetic moment of each Co atom is about 0.07-0.08?B. The monomer is non-magnetic while a high magnetic moment of 1.94?B per Co atom is found in the case of dimer. We discuss our results in the context of recent experimental and theoretical findings [1,2] [3pt] [1] S. Borisova et al, Phys. Rev. B 78, 075428 (2008) [0pt] [2] O. Mironets et al, Phys. Rev. Lett. 100, 096103 (2008)
Goddard III, William A.
Isotopic fractionations associated with phosphoric acid digestion of carbonate minerals: Insights 27 May 2009; available online 23 June 2009 Abstract Phosphoric acid digestion has been used with phosphoric acid digestion of carbonates at 25 °C are 10.72&, 0.220&, 0.137&, 0.593& for, respectively, 18 O
First-Principles Study on Graphene/Hexagonal Boron Nitride Heterostructures
NASA Astrophysics Data System (ADS)
Sakai, Yuki; Saito, Susumu; Cohen, Marvin L.
2015-12-01
This article reviews recent progresses in first-principles studies on graphene/hexagonal boron nitride (h-BN) heterostructures. The experimental demonstration of the usefulness of hexagonal boron nitride as a substrate for graphene devices has attracted considerable interest of graphene/h-BN heterostructure systems. More complicated graphene/h-BN heterostructures have also been fabricated in recent years. In parallel with the experimental progress, first-principles studies have also revealed interesting properties of these heterostructures. The structural and electronic properties of the graphene/h-BN heterostructures are discussed here based on the recent first-principles results.
First-principles study of the covalently functionalized graphene
NASA Astrophysics Data System (ADS)
Jha, Sanjiv Kumar
Theoretical investigations of nanoscale systems, such as functionalized graphene, present major challenges to conventional computational methods employed in quantum chemistry and solid state physics. The properties of graphene can be affected by chemical functionalization. The surface functionalization of graphene offers a promising way to increase the solubility and reactivity of graphene for use in nanocomposites and chemical sensors. Covalent functionalization is an efficient way to open band-gap in graphene for applications in nanoelectronics. We apply ab initio computational methods based on density functional theory to study the covalent functionalization of graphene with benzyne (C6H4), tetracyanoethylene oxide (TCNEO), and carboxyl (COOH) groups. Our calculations are carried out using the SIESTA and Quantum-ESPRESSO electronic structure codes combined with the generalized gradient (GGA) and local density approximations (LDA) for the exchange correlation functionals and norm-conserving Troullier-Martins pseudopotentials. Calculated binding energies, densities of states (DOS), band structures, and vibrational spectra of functionalized graphene are analyzed in comparison with the available experimental data. Our calculations show that the reactions of [2 + 2] and [2 + 4] cycloaddition of C6H4 to the surface of pristine graphene are exothermic, with binding energies of --0.73 eV and --0.58 eV, respectively. Calculated band structures indicate that the [2 + 2] and [2 + 4] attachments of benzyne results in opening small band gap in graphene. The study of graphene--TCNEO interactions suggests that the reaction of cycloaddition of TCNEO to the surface of pristine graphene is endothermic. On the other hand, the reaction of cycloaddition of TCNEO is found to be exothermic for the edge of an H-terminated graphene sheet. Simulated Raman and infrared spectra of graphene functionalized with TCNEO are consistent with experimental results. The Raman (non-resonant) and infrared (IR) spectra of graphene functionalized with carboxyl (COON) groups are studied in graphene with no surface defects, di-vacancies (DV), and Stone-Wales (SW) defects. Simulated Raman and IR spectra of carboxylated graphene are consistent with available experimental results. Computed vibrational spectra of carboxylated graphene show that the presence of point defects near the functionalization site affect the Raman and IR spectroscopic signatures of the functionalized graphene.
Deiss, E.; Wokaun, A.; Barras, J.L.; Daul, C.; Dufek, P.
1997-11-01
The theoretical average voltage, energy density (energy per volume), and specific energy (energy per mass) based on the active electrode material have been calculated from first principles for two types of rechargeable lithium-ion batteries. In the charged state the two batteries consist of LiC{sub 6} and Mo{sub 2} electrodes (M = Mo and Ni). The calculation was performed using the linearized augmented plane wave crystal code WIEN95 based on density functional theory (DFT). The structure was calculated by varying the unit cell volume of the experimentally known crystallographic data with respect to the total energy. The calculated results are compared with measured values. The temperature dependence of the average voltage, energy density, and specific energy was demonstrated to be of minor importance. In the case of the LiC{sub 6}/NiO{sub 2} battery this was done by calculating the vibrational energy contribution to the enthalpy change using the cluster approximation and the Amsterdam density functional (ADF) molecular code based on DFT. The agreement between theoretical and experimental values opens up the use of first principles quantum chemistry in battery technology.
Ceder, Gerbrand
The idea of first-principles methods is to determine the properties of materials by solving the basic equations of quantum mechanics and statistical mechanics. With such an approach, one can, in principle, predict the ...
First principles high throughput screening of oxynitrides for water-splitting photocatalysts
Wu, Yabi
2013-01-01
In this paper, we present a first principles high throughput screening system to search for new water-splitting photocatalysts. We use the approach to screen through nitrides and oxynitrides. Most of the known photocatalytic ...
Lin, Xi, 1973-
2003-01-01
In this thesis, the chemistry of sulfur oxides on transition metals is studied extensively via first-principles density functional theory (DFT) computations, focusing on the chemical reactivity and selectivity in sulfur ...
First-principles investigation of Li intercalation kinetics in phospho-olivines
Malik, Rahul
2013-01-01
This thesis focuses broadly on characterizing and understanding the Li intercalation mechanism in phospho-olivines, namely LiFePO? and Li(Fe,Mn)PO?, using first-principles calculations. Currently Li-ion battery technology ...
Prediction of semiconductor band edge positions in aqueous environments from first principles
Wu, Yabi
The ability to predict a semiconductor's band edge positions in solution is important for the design of water-splitting photocatalyst materials. In this paper, we introduce a first-principles method to compute the ...
Kim, Sejoong
We present a first-principles approach for inelastic quantum transport calculations based on maximally localized Wannier functions. Electronic-structure properties are obtained from density-functional theory in a plane-wave ...
Aqueous systems from first-principles : structure, dynamics and electron-transfer reactions
Sit, Patrick Hoi Land
2006-01-01
In this thesis, we show for the first time how it is possible to calculated fully from first-principles the diabatic free-energy surfaces of electron-transfer reactions. The excitation energy corresponding to the transfer ...
Thermal conductivity from first-principles in bulk, disordered, and nanostructured materials
Garg, Jivtesh
2011-01-01
Thermal conductivity is an important transport property that plays a vital role in applications such as high efficiency thermoelectric devices as well as in thermal management of electronics. We present a first-principles ...
Luo, Tengfei
In this paper, thermal conductivity of crystalline GaAs is calculated using first-principles lattice dynamics. The harmonic and cubic force constants are obtained by fitting them to the force-displacement data from density ...
Lattice thermal conductivity of Bi, Sb, and Bi-Sb alloy from first principles
Lee, Sangyeop
Using first principles, we calculate the lattice thermal conductivity of Bi, Sb, and Bi-Sb alloys, which are of great importance for thermoelectric and thermomagnetic cooling applications. Our calculation reveals that the ...
First principles Raman study of boron and nitrogen doped planar T-graphene clusters
NASA Astrophysics Data System (ADS)
Bandyopadhyay, Arka; Pal, Parthasarathi; Chowdhury, Suman; Jana, Debnarayan
2015-09-01
Tetragonal graphene (TG) is one of the theoretically proposed dynamically stable graphene allotropes. In this study, the Raman spectra, IR spectra and some electronic properties of pristine and doped (single boron (B) and nitrogen (N)) TG have been investigated by first-principles based density functional theory (DFT) at the B3LYP/6-31G(d) level. Formation energy computation indicates that for the pristine structures, stability increases with increasing cluster size. In addition, for a particular cluster size, single B doping introduces some distortion in the system while single N doping increases the stability of it. The Raman spectrum of the N doped system is dominated by a single peak but for the B doped system several intense lines are found. For all the structures low intensity similar breathing-like modes have been observed. Besides, relatively low (high) intensity Raman lines are found for single B (N) doping compared to those of the pristine one. The vibrational study also reveals the existence of a prominent phonon Raman line for pristine clusters which hardly changes its position and nature of vibration with varying cluster size. So this mode can be used for identification of pristine TG structures. Unlike pristine TG, the doped structures possess non-zero finite dipole moments due to asymmetry in charge distribution. Large values of the HOMO-LUMO gap as well as the absence of DOS at the Fermi level lead to the semiconducting nature of all the structures. All these theoretical predictions from DFT calculations may shed light on experimental observations involving TG systems.
First-principles investigation of vanadium isotope fractionation in solution and during adsorption
NASA Astrophysics Data System (ADS)
Wu, Fei; Qin, Tian; Li, Xuefang; Liu, Yun; Huang, Jen-How; Wu, Zhongqing; Huang, Fang
2015-09-01
Equilibrium fractionation factors of vanadium (V) isotopes among tri- (V(III)), tetra- (V(IV)) and penta-valent (V(V)) inorganic V species in aqueous system and during adsorption of V(V) to goethite are estimated using first-principles calculation. Our results highlight the dependence of V isotope fractionation on valence states and the chemical binding environment. The heavy V isotope (51V) is enriched in the main V species following a sequence of V(III) < V(IV) < V(V). According to our calculations, at 25 °C, the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V4+O(H2O)5]2+ (ln ?? V (V)- V (IV)) is 3.9‰, and the equilibrium isotope fractionation factor between [V5+O2(OH)2]- and [V3+(OH)3(H2O)3] (ln ?? V (V)- V (III)) is 6.4‰. In addition, isotope fractionation between +5 valence species [V5+O2(OH)2]- and [V5+O2(H2O)4]+ is 1.5‰ at 25 °C, which is caused by their different bond lengths and coordination numbers (CN). Theoretical calculations also show that light V isotope (50V) is preferentially adsorbed on the surface of goethite. Our work reveals that V isotopes can be significantly fractionated in the Earth's surface environments due to redox reaction and mineral adsorption, indicating that V isotope data can be used to monitor toxic V(V) attenuation processes through reduction or adsorption in natural water systems. In addition, a simple mass balance model suggests that V isotope composition of seawater might vary with change of ambient oxygen levels. Thus our theoretical investigations imply a promising future for V isotopes as a potential new paleo-redox tracer.
NASA Astrophysics Data System (ADS)
Lemal, Sébastien; Nguyen, Ngoc; de Boor, Johannes; Ghosez, Philippe; Varignon, Julien; Klobes, Benedikt; Hermann, Raphaël P.; Verstraete, Matthieu J.
2015-11-01
Using a combination of first-principles calculations and experimental transport measurements, we study the electronic and magnetic structure of the unfilled skutterudite FeSb3. We employ the hybrid functional approach for exchange correlation. The ground state is determined to be antiferromagnetic with an atomic magnetic moment of 1.6 ?B/Fe . The Néel temperature TN is estimated at 6 K, in agreement with experiments which found a paramagnetic state down to 10 K. The ground state is semiconducting, with a small electronic gap of 33 meV , also consistent with previous experiments on films. Charge carrier concentrations are estimated from Hall resistance measurements. The Seebeck coefficient is measured and mapped using a scanning probe at room temperature that yields an average value of 38.6 ? V K-1 , slightly lower than the theoretical result. The theoretical conductivity is analyzed as a function of temperature and concentration of charge carriers.
NASA Astrophysics Data System (ADS)
Parreiras, D. E.; Soares, E. A.; Abreu, G. J. P.; Bueno, T. E. P.; Fernandes, W. P.; de Carvalho, V. E.; Carara, S. S.; Chacham, H.; Paniago, R.
2014-10-01
The structural properties of graphene/Ni(111) are investigated by a combination of low-energy electron diffraction (LEED), x-ray photoelectron spectroscopy (XPS), angle-scanned photoelectron diffraction (PED), and first-principles calculations. XPS data indicate that graphene interacts strongly with the topmost Ni layer. Diffraction data show that graphene is deposited commensurably with the underlying Ni surface atoms. Twelve different graphene preparations were analyzed by LEED and one by PED. Considering the relative position between the carbon and Ni atoms, five experimental sets indicate a top-fcc structure, three show a bridge-top structure, and four have a mixed structure. The analysis of the PED experiment suggests the top-fcc termination. Our first-principles calculations show that the total energies of the top-fcc and bridge-top structures are nearly degenerate, which corroborates the observed bistability of those phases. Moreover, by comparing the structural parameters obtained by the three methods (LEED, PED, and ab initio calculations), excellent agreement is achieved.
Singh, Vijay; Kosa, Monica; Majhi, Koushik; Major, Dan Thomas
2015-01-13
First-principles density functional theory (DFT) and a many-body Green's function method have been employed to elucidate the electronic, magnetic, and photonic properties of a spinel compound, Co3O4. Co3O4 is an antiferromagnetic semiconductor composed of cobalt ions in the Co(2+) and Co(3+) oxidation states. Co3O4 is believed to be a strongly correlated material, where the on-site Coulomb interaction (U) on Co d orbitals is presumably important, although this view has recently been contested. The suggested optical band gap for this material ranges from 0.8 to 2.0 eV, depending on the type of experiments and theoretical treatment. Thus, the correlated nature of the Co d orbitals in Co3O4 and the extent of the band gap are still under debate, raising questions regarding the ability of DFT to correctly treat the electronic structure in this material. To resolve the above controversies, we have employed a range of theoretical methods, including pure DFT, DFT+U, and a range-separated exchange-correlation functional (HSE06) as well as many-body Green's function theory (i.e., the GW method). We compare the electronic structure and band gap of Co3O4 with available photoemission spectroscopy and optical band gap data and confirm a direct band gap of ca. 0.8 eV. Furthermore, we have also studied the optical properties of Co3O4 by calculating the imaginary part of the dielectric function (Im(?)), facilitating direct comparison with the measured optical absorption spectra. Finally, we have calculated the nearest-neighbor interaction (J1) between Co(2+) ions to understand the complex magnetic structure of Co3O4. PMID:26574204
ERIC Educational Resources Information Center
Cappelletti, John
1989-01-01
Details the following thoughts on directing for the theater: select the play, read the play, read the play again, ask questions, discover the spine, form a concept, cast the play, listen to the actors, make it move, make it spontaneous, make it real, look for obstacles, make it relevant, and make it important. (PRA)
Bondi, Robert J. Desjarlais, Michael P.; Thompson, Aidan P.; Brennecka, Geoff L.; Marinella, Matthew J.
2013-11-28
We apply first-principles density-functional theory (DFT) calculations, ab-initio molecular dynamics, and the Kubo-Greenwood formula to predict electrical conductivity in Ta{sub 2}O{sub x} (0???x???5) as a function of composition, phase, and temperature, where additional focus is given to various oxidation states of the O monovacancy (V{sub O}{sup n}; n?=?0,1+,2+). In the crystalline phase, our DFT calculations suggest that V{sub O}{sup 0} prefers equatorial O sites, while V{sub O}{sup 1+} and V{sub O}{sup 2+} are energetically preferred in the O cap sites of TaO{sub 7} polyhedra. Our calculations of DC conductivity at 300?K agree well with experimental measurements taken on Ta{sub 2}O{sub x} thin films (0.18???x???4.72) and bulk Ta{sub 2}O{sub 5} powder-sintered pellets, although simulation accuracy can be improved for the most insulating, stoichiometric compositions. Our conductivity calculations and further interrogation of the O-deficient Ta{sub 2}O{sub 5} electronic structure provide further theoretical basis to substantiate V{sub O}{sup 0} as a donor dopant in Ta{sub 2}O{sub 5}. Furthermore, this dopant-like behavior is specific to the neutral case and not observed in either the 1+ or 2+ oxidation states, which suggests that reduction and oxidation reactions may effectively act as donor activation and deactivation mechanisms, respectively, for V{sub O}{sup n} in Ta{sub 2}O{sub 5}.
Jaramillo-Botero, Andres; Nielsen, Robert; Abrol, Ravi; Su, Julius; Pascal, Tod; Mueller, Jonathan; Goddard, William A
2012-01-01
We expect that systematic and seamless computational upscaling and downscaling for modeling, predicting, or optimizing material and system properties and behavior with atomistic resolution will eventually be sufficiently accurate and practical that it will transform the mode of development in the materials, chemical, catalysis, and Pharma industries. However, despite truly dramatic progress in methods, software, and hardware, this goal remains elusive, particularly for systems that exhibit inherently complex chemistry under normal or extreme conditions of temperature, pressure, radiation, and others. We describe here some of the significant progress towards solving these problems via a general multiscale, multiparadigm strategy based on first-principles quantum mechanics (QM), and the development of breakthrough methods for treating reaction processes, excited electronic states, and weak bonding effects on the conformational dynamics of large-scale molecular systems. These methods have resulted directly from filling in the physical and chemical gaps in existing theoretical and computational models, within the multiscale, multiparadigm strategy. To illustrate the procedure we demonstrate the application and transferability of such methods on an ample set of challenging problems that span multiple fields, system length- and timescales, and that lay beyond the realm of existing computational or, in some case, experimental approaches, including understanding the solvation effects on the reactivity of organic and organometallic structures, predicting transmembrane protein structures, understanding carbon nanotube nucleation and growth, understanding the effects of electronic excitations in materials subjected to extreme conditions of temperature and pressure, following the dynamics and energetics of long-term conformational evolution of DNA macromolecules, and predicting the long-term mechanisms involved in enhancing the mechanical response of polymer-based hydrogels. PMID:21243466
Prediction of new high pressure structural sequence in thorium carbide: A first principles study
Sahoo, B. D. Joshi, K. D.; Gupta, Satish C.
2015-05-14
In the present work, we report the detailed electronic band structure calculations on thorium monocarbide. The comparison of enthalpies, derived for various phases using evolutionary structure search method in conjunction with first principles total energy calculations at several hydrostatic compressions, yielded a high pressure structural sequence of NaCl type (B1) ? Pnma ? Cmcm ? CsCl type (B2) at hydrostatic pressures of ?19?GPa, 36?GPa, and 200?GPa, respectively. However, the two high pressure experimental studies by Gerward et al. [J. Appl. Crystallogr. 19, 308 (1986); J. Less-Common Met. 161, L11 (1990)] one up to 36?GPa and other up to 50?GPa, on substoichiometric thorium carbide samples with carbon deficiency of ?20%, do not report any structural transition. The discrepancy between theory and experiment could be due to the non-stoichiometry of thorium carbide samples used in the experiment. Further, in order to substantiate the results of our static lattice calculations, we have determined the phonon dispersion relations for these structures from lattice dynamic calculations. The theoretically calculated phonon spectrum reveal that the B1 phase fails dynamically at ?33.8?GPa whereas the Pnma phase appears as dynamically stable structure around the B1 to Pnma transition pressure. Similarly, the Cmcm structure also displays dynamic stability in the regime of its structural stability. The B2 phase becomes dynamically stable much below the Cmcm to B2 transition pressure. Additionally, we have derived various thermophysical properties such as zero pressure equilibrium volume, bulk modulus, its pressure derivative, Debye temperature, thermal expansion coefficient and Gruneisen parameter at 300?K and compared these with available experimental data. Further, the behavior of zero pressure bulk modulus, heat capacity and Helmholtz free energy has been examined as a function temperature and compared with the experimental data of Danan [J. Nucl. Mater. 57, 280 (1975)].
NASA Astrophysics Data System (ADS)
Takahashi, Masae; Ishikawa, Yoichi; Ito, Hiromasa
2013-03-01
A weak hydrogen bond (WHB) such as CH-O is very important for the structure, function, and dynamics in a chemical and biological system WHB stretching vibration is in a terahertz (THz) frequency region Very recently, the reasonable performance of dispersion-corrected first-principles to WHB has been proven. In this lecture, we report dispersion-corrected first-principles calculation of the vibrational absorption of some organic crystals, and low-temperature THz spectral measurement, in order to clarify WHB stretching vibration. The THz frequency calculation of a WHB crystal has extremely improved by dispersion correction. Moreover, the discrepancy in frequency between an experiment and calculation and is 10 1/cm or less. Dispersion correction is especially effective for intermolecular mode. The very sharp peak appearing at 4 K is assigned to the intermolecular translational mode that corresponds to WHB stretching vibration. It is difficult to detect and control the WHB formation in a crystal because the binding energy is very small. With the help of the latest intense development of experimental and theoretical technique and its careful use, we reveal solid-state WHB stretching vibration as evidence for the WHB formation that differs in respective WHB networks The research was supported by the Ministry of Education, Culture, Sports, Science and Technology of Japan (Grant No. 22550003).
Combined Raman spectroscopy and first-principles calculation for essential oil of Lemongrass
NASA Astrophysics Data System (ADS)
Faria, Rozilaine A. P. G.; Picanço, Nágela F. M.; Campo, Gladís S. D. L.; Faria, Jorge L. B.; Instituto de Física/UFMT Collaboration; Instituto Federal de Mato Grosso/IFMT Team
2014-03-01
The essential oils have increased food's industry interest by the presence of antioxidant and antimicrobial. Many of them have antimicrobial and antioxidant, antibacterial and antifungal activities. But, due to the concentrations required to be added in the food matrix, the sensory quality of the food is changed. The production and composition of essential oil extracted from plants depend on the plant-environment interactions, the harvest season, phenophase and physiological state of the vegetal. Cymbopogom citratus (Lemongrass) has a good yield in essential oil with neral (citral A), geranial (citral B) and myrcene, reaching 90% of the oil composition. In our experimental work, the essential oil of lemongrass was obtained by hydrodistillation in Clevenger apparatus for 4 hours. The compound was further analyzed by Raman scattering in a spectrometer HR 800, with excitation at 633nm, in the range 80-3400 cm-1. The spectrum obtained was compared with DFT calculations of molecules of the oil components. Our results show the vibrational signatures of the main functional groups and suggest a simple, but very useful, methodology to quantify the proportions of these components in the oil composition, showing good agreement with Raman data. CNPq/Capes/Fapemat.
Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; Heine, Nadja; Yacovitch, Tara I.; Wende, Torsten; Asmis, Knut R.; Neumark, Daniel M.; Liu, Zhi -Feng
2015-06-05
We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H_{2}PO_{4}^{-}(H_{2}O)_{n} anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogen bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H_{2}PO_{4}^{-}(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H_{2}PO_{4}^{-}, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.
NASA Astrophysics Data System (ADS)
Kumar, Kishor; Bhatt, Samir; Jani, A. R.; Ahuja, B. L.
2015-12-01
We present the first-ever experimental Compton profiles (CPs) of ZrSSe2 and ZrS1.5Se1.5 using 100 mCi 241Am Compton spectrometer. To analyze the experimental momentum densities, we have computed for the first-time the CPs, energy bands and density of states using linear combination of atomic orbitals (LCAO) method. To model the exchange and correlation effects within LCAO approach, we have considered Hartree-Fock (HF), density functional theory (DFT) with revised functional of Perdew-Becke-Ernzerhof (PBEsol) and hybridization of HF and DFT. Going beyond computation of electronic properties using LCAO method, we have also derived electronic and optical properties using the modified Becke-Johnson (mBJ) potential within full potential linearized augmented plane wave (FP-LAPW) method. There is notable decrease in the energy band gap on replacing S by Se atoms in ZrSSe2 to obtain ZrS1.5Se1.5 composition, which is mainly attributed to readjustment of Zr-4d, S-3p and Se-4p states. It is seen that the CPs based on hybridization of HF and DFT show a better agreement with the experimental profiles than those based on individual HF and DFT-GGA-PBEsol schemes. The optical properties computed using FP-LAPW-mBJ method unambiguously depict feasibility of using both the sulphoselenides in photovoltaics and also utility of ZrS1.5Se1.5 in the field of non-linear optics.
Sun, Shou -Tian; Jiang, Ling; Liu, J. W.; Heine, Nadja; Yacovitch, Tara I.; Wende, Torsten; Asmis, Knut R.; Neumark, Daniel M.; Liu, Zhi -Feng
2015-06-05
We report infrared multiple photon dissociation (IRMPD) spectra of cryogenically-cooled H2PO4-(H2O)n anions (n = 2–12) in the spectral range of the stretching and bending modes of the solute anion (600–1800 cm-1). The spectra cannot be fully understood using the standard technique of comparison to harmonic spectra of minimum-energy structures; a satisfactory assignment requires considering anharmonic effects as well as entropy-driven hydrogen bond network fluctuations. Aided by finite temperature ab initio molecular dynamics simulations, the observed changes in the position, width and intensity of the IRMPD bands with cluster size are related to the sequence of microsolvation. Due to stronger hydrogenmore »bonding to the two terminal P=O groups, these are hydrated before the two P–OH groups. By n = 6, all four end groups are involved in the hydrogen bond network and by n = 12, the cluster spectra show similarities to the condensed phase spectrum of H2PO4-(aq). Our results reveal some of the microscopic details concerning the formation of the aqueous solvation environment around H2PO4-, provide ample testing grounds for the design of model solvation potentials for this biologically relevant anion, and support a new paradigm for the interpretation of IRMPD spectra of microhydrated ions.« less
Xiang, Huimin; Feng, Zhihai; Li, Zhongping; Zhou, Yanchun E-mail: yczhou714@gmail.com
2015-06-14
High temperature mechanical and thermodynamic properties of TiB{sub 2} are important to its applications as ultrahigh temperature ceramic, which were not well understood. In this study, the thermodynamic and mechanical properties of TiB{sub 2} were investigated by the combination of first principle and phonon dispersion calculations. The thermal expansion of TiB{sub 2} was anisotropic, ?{sub c}/?{sub a} is nearly constant (1.46) from 300?K to 1500?K, theoretically. The origination of this anisotropy is the anisotropic compressibility. The heat capacity at constant pressure was estimated from the theoretical entropy and fitted the experimental result quite well when higher-order anharmonic effects were considered. Theoretical isentropic elastic constants and mechanical properties were calculated and their temperature dependence agreed with the existed experiments. From room temperature to 1500?K, the theoretical slope is ?0.0211 GPa·K{sup ?1}, ?0.0155 GPa·K{sup ?1}, and ?0.0384 GPa·K{sup ?1} for B, G, and E, respectively. Our theoretical results highlight the suitability of this method in predicting temperature dependent properties of ultrahigh temperature ceramics and show ability in selecting and designing of novel ultrahigh temperature ceramics.
NASA Astrophysics Data System (ADS)
Qiu, Bo; Tian, Zhiting; Vallabhaneni, Ajit; Liao, Bolin; Mendoza, Jonathan M.; Restrepo, Oscar D.; Ruan, Xiulin; Chen, Gang
2015-03-01
The mean free paths (MFPs) of energy carriers are of critical importance to the nano-engineering of better thermoelectric materials. Despite significant progress in the first-principles-based understanding of the spectral distribution of phonon MFPs in recent years, the spectral distribution of electron MFPs remains unclear. In this work, we compute the energy-dependent electron scatterings and MFPs in silicon from first principles. The electrical conductivity accumulation with respect to electron MFPs is compared to that of the phonon thermal conductivity accumulation to illustrate the quantitative impact of nanostructuring on electron and phonon transport. By combining all electron and phonon transport properties from first principles, we predict the thermoelectric properties of the bulk and nanostructured silicon, and find that silicon with 20 nm nanograins can result in a higher than five times enhancement in their thermoelectric figure of merit as the grain boundaries scatter phonons more significantly than that of electrons due to their disparate MFP distributions.
NASA Astrophysics Data System (ADS)
Paul, Sujata
In the course of my PhD I have worked on a broad range of problems using simulations from first principles: from catalysis and chemical reactions at surfaces and on nanostructures, characterization of carbon-based systems and devices, and surface and interface physics. My research activities focused on the application of ab-initio electronic structure techniques to the theoretical study of important aspects of the physics and chemistry of materials for energy and environmental applications and nano-electronic devices. A common theme of my research is the computational study of chemical reactions of environmentally important molecules (CO, CO2) using high performance simulations. In particular, my principal aim was to design novel nano-structured functional catalytic surfaces and interfaces for environmentally relevant remediation and recycling reactions, with particular attention to the management of carbon dioxide. We have studied the carbon-mediated partial sequestration and selective oxidation of carbon monoxide (CO), both in the presence and absence of hydrogen, on graphitic edges. Using first-principles calculations we have studied several reactions of CO with carbon nanostructures, where the active sites can be regenerated by the deposition of carbon decomposed from the reactant (CO) to make the reactions self-sustained. Using statistical mechanics, we have also studied the conditions under which the conversion of CO to graphene and carbon dioxide is thermodynamically favorable, both in the presence and in the absence of hydrogen. These results are a first step toward the development of processes for the carbon-mediated partial sequestration and selective oxidation of CO in a hydrogen atmosphere. We have elucidated the atomic scale mechanisms of activation and reduction of carbon dioxide on specifically designed catalytic surfaces via the rational manipulation of the surface properties that can be achieved by combining transition metal thin films on oxide substrates. We have analyzed the mechanisms of the molecular reactions on the class of catalytic surfaces so designed in an effort to optimize materials parameters in the search of optimal catalytic materials. All these studies are likely to bring new perspectives and substantial advancement in the field of high-performance simulations in catalysis and the characterization of nanostructures for energy and environmental applications. Moving to novel materials for electronics applications, I have studied the structural and vibrational properties of mono and bi-layer graphene. I have characterized the lattice thermal conductivity of ideal monolayer and bi-layer graphene, demonstrating that their behavior is similar to that observed in graphite and indicating that the intra-layer coupling does not affect significantly the thermal conductance. I have also calculated the electron-phonon interaction in monolayer graphene and obtained electron scattering rates associated with all phonon modes and the intrinsic resistivity/mobility of monolayer graphene is estimated as a function of temperature. On another project, I have worked on ab initio molecular dynamic studies of novel Phase Change Materials (PCM) for memory and 3D-integration. We characterized high-temperature, sodium | nickel chloride, rechargeable batteries. These batteries are under consideration for hybrid drive systems in transportation applications. As part of our activities to improve performance and reliability of these batteries, we developed an engineering transport model of the component electrochemical cell. To support that model, we have proposed a reaction kinetics expression for the REDOX (reduction-oxidation) reaction at the porous positive electrode. We validate the kinetics expression with electrochemical measurements. A methodology based on the transistor body effect is used to estimate inversion oxide thicknesses (Tinv) in high-kappa/metal gate, undoped, ultra-thin body SOI FINFETs. The extracted Tinvs are compared to independent capacitance voltage (CV) measurements.
Point defects in ZnO: an approach from first principles
NASA Astrophysics Data System (ADS)
Oba, Fumiyasu; Choi, Minseok; Togo, Atsushi; Tanaka, Isao
2011-06-01
Recent first-principles studies of point defects in ZnO are reviewed with a focus on native defects. Key properties of defects, such as formation energies, donor and acceptor levels, optical transition energies, migration energies and atomic and electronic structure, have been evaluated using various approaches including the local density approximation (LDA) and generalized gradient approximation (GGA) to DFT, LDA+U/GGA+U, hybrid Hartree-Fock density functionals, sX and GW approximation. Results significantly depend on the approximation to exchange correlation, the simulation models for defects and the post-processes to correct shortcomings of the approximation and models. The choice of a proper approach is, therefore, crucial for reliable theoretical predictions. First-principles studies have provided an insight into the energetics and atomic and electronic structures of native point defects and impurities and defect-induced properties of ZnO. Native defects that are relevant to the n-type conductivity and the non-stoichiometry toward the O-deficient side in reduced ZnO have been debated. It is suggested that the O vacancy is responsible for the non-stoichiometry because of its low formation energy under O-poor chemical potential conditions. However, the O vacancy is a very deep donor and cannot be a major source of carrier electrons. The Zn interstitial and anti-site are shallow donors, but these defects are unlikely to form at a high concentration in n-type ZnO under thermal equilibrium. Therefore, the n-type conductivity is attributed to other sources such as residual impurities including H impurities with several atomic configurations, a metastable shallow donor state of the O vacancy, and defect complexes involving the Zn interstitial. Among the native acceptor-type defects, the Zn vacancy is dominant. It is a deep acceptor and cannot produce a high concentration of holes. The O interstitial and anti-site are high in formation energy and/or are electrically inactive and, hence, are unlikely to play essential roles in electrical properties. Overall defect energetics suggests a preference for the native donor-type defects over acceptor-type defects in ZnO. The O vacancy, Zn interstitial and Zn anti-site have very low formation energies when the Fermi level is low. Therefore, these defects are expected to be sources of a strong hole compensation in p-type ZnO. For the n-type doping, the compensation of carrier electrons by the native acceptor-type defects can be mostly suppressed when O-poor chemical potential conditions, i.e. low O partial pressure conditions, are chosen during crystal growth and/or doping.
Data set for diffusion coefficients of alloying elements in dilute Mg alloys from first-principles
Zhou, Bi-Cheng; Shang, Shun-Li; Wang, Yi; Liu, Zi-Kui
2015-01-01
Diffusion coefficients of alloying elements in Mg are critical for the development of new Mg alloys for lightweight applications. Here we present the data set of the temperature-dependent dilute tracer diffusion coefficients for 47 substitutional alloying elements in hexagonal closed packed (hcp) Mg calculated from first-principles calculations based on density functional theory (DFT) by combining transition state theory and an 8-frequency model. Benchmark for the DFT calculations and systematic comparison with experimental diffusion data are also presented. The data set refers to “Diffusion coefficients of alloying elements in dilute Mg alloys: A comprehensive first-principles study” by Zhou et al. [1]. PMID:26702419
Buck, D.R.
2000-09-12
Theoretical simulations and ultrafast pump-probe laser spectroscopy experiments were used to study photosynthetic pigment-protein complexes and antennae found in green sulfur bacteria such as Prosthecochloris aestuarii, Chloroflexus aurantiacus, and Chlorobium tepidum. The work focused on understanding structure-function relationships in energy transfer processes in these complexes through experiments and trying to model that data as we tested our theoretical assumptions with calculations. Theoretical exciton calculations on tubular pigment aggregates yield electronic absorption spectra that are superimpositions of linear J-aggregate spectra. The electronic spectroscopy of BChl c/d/e antennae in light harvesting chlorosomes from Chloroflexus aurantiacus differs considerably from J-aggregate spectra. Strong symmetry breaking is needed if we hope to simulate the absorption spectra of the BChl c antenna. The theory for simulating absorption difference spectra in strongly coupled photosynthetic antenna is described, first for a relatively simple heterodimer, then for the general N-pigment system. The theory is applied to the Fenna-Matthews-Olson (FMO) BChl a protein trimers from Prosthecochloris aestuarii and then compared with experimental low-temperature absorption difference spectra of FMO trimers from Chlorobium tepidum. Circular dichroism spectra of the FMO trimer are unusually sensitive to diagonal energy disorder. Substantial differences occur between CD spectra in exciton simulations performed with and without realistic inhomogeneous distribution functions for the input pigment diagonal energies. Anisotropic absorption difference spectroscopy measurements are less consistent with 21-pigment trimer simulations than 7-pigment monomer simulations which assume that the laser-prepared states are localized within a subunit of the trimer. Experimental anisotropies from real samples likely arise from statistical averaging over states with diagonal energies shifted by in homogeneous broadening and as such, are quite sensitive to diagonal energy disorder. The experimental anisotropies exhibit strong oscillations with {approximately}220 fs period for certain wavelengths in one-color absorption difference experiments. The oscillations only appear when the laser pulse spectrum overlaps both of the lowest-energy groups of exciton levels clustered near 815 and 825 nm. Results suggest that the oscillations stem from quantum beating between exciton levels, rather than from coherent nuclear motion.
NASA Astrophysics Data System (ADS)
Gouda, Mohammed K.; Nakamura, Koichi; A. H. Gepreel, Mohamed
2015-06-01
Theoretical deformation response of hypothetical ?-titanium alloys was investigated using first-principles calculation technique under periodic boundary conditions. Simulation was carried out on hypothetical 54-atom supercell of Ti-X (X = Cr, Mn, Fe, Zr, Nb, Mo, Al, and Sn) binary alloys. The results showed that the strength of Ti increases by alloying, except for Cr. The most effective alloying elements are Nb, Zr, and Mo in the current simulation. The mechanism of bond breaking was revealed by studying the local structure around the alloying element atom with respect to volume change. Moreover, the effect of alloying elements on bulk modulus and admissible strain was investigated. It was found that Zr, Nb, and Mo have a significant effect to enhance the admissible strain of Ti without change in bulk modulus.
NASA Astrophysics Data System (ADS)
Jain, Richa Naja; Chakraborty, Brahmananda; Ramaniah, Lavanya M.
2015-06-01
The electronic structure and hydrogen storage capability of Yttrium-doped BNNTs has been theoretically investigated using first principles density functional theory (DFT). Yttrium atom prefers the hollow site in the center of the hexagonal ring with a binding energy of 0.8048eV. Decorating by Y makes the system half-metallic and magnetic with a magnetic moment of 1.0µB. Y decorated Boron-Nitride (8,0) nanotube can adsorb up to five hydrogen molecules whose average binding energy is computed as 0.5044eV. All the hydrogen molecules are adsorbed with an average desorption temperature of 644.708 K. Taking that the Y atoms can be placed only in alternate hexagons, the implied wt% comes out to be 5.31%, a relatively acceptable value for hydrogen storage materials. Thus, this system can serve as potential hydrogen storage medium.
Gouda, Mohammed K. Gepreel, Mohamed A. H.; Nakamura, Koichi
2015-06-07
Theoretical deformation response of hypothetical ?-titanium alloys was investigated using first-principles calculation technique under periodic boundary conditions. Simulation was carried out on hypothetical 54-atom supercell of Ti–X (X?=?Cr, Mn, Fe, Zr, Nb, Mo, Al, and Sn) binary alloys. The results showed that the strength of Ti increases by alloying, except for Cr. The most effective alloying elements are Nb, Zr, and Mo in the current simulation. The mechanism of bond breaking was revealed by studying the local structure around the alloying element atom with respect to volume change. Moreover, the effect of alloying elements on bulk modulus and admissible strain was investigated. It was found that Zr, Nb, and Mo have a significant effect to enhance the admissible strain of Ti without change in bulk modulus.
NASA Astrophysics Data System (ADS)
Mayfield, Cedric; Huda, Muhammad
2015-03-01
Transition metal inclusion has enhanced photocatalytic activity of bismuth titanate (Bi2Ti2O7) up to an impurity threshold concentration. Beyond the threshold, spectral absorbance is continually red shifted but increased photocurrent is not reciprocated. We investigated, from first principles, the origin of decreased photocurrent in modified Bi2Ti2O7 (BTO) by calculating the electronic structures of a representative set of doping configurations and by performing a phase stability analysis of the doping. We report our theoretical/computational strategy of analyzing free energy space and show an explicit dependence of pure phase synthesis on changes in free energy. Also, we present a probability distribution of the doping configurations based on formation enthalpy to better understand the nature of doping in BTO. We found that transition metal substitutions are favorable at the A-sites due to unchanging coordination with O ions. This work is supported by National Science Foundation, Award No. 1133672.
NASA Astrophysics Data System (ADS)
Zhao, Y. N.; Han, H. L.; Yu, Y.; Xue, W. H.; Gao, T.
2009-02-01
We study the electronic band structure, dielectric, and lattice dynamical properties of FeSi, RuSi and OsSi from first principles using density functional theory. We performed the band structure calculations for these compounds to confirm they are indirect band-gap semiconductors. Density functional perturbation theory is employed to evaluate the Born effective charge tensors, the dielectric permittivity tensors, the phonon frequencies at the ?-point, and the phonon dispersion curves as well as the corresponding density of states. These calculated results are in reasonable agreement with the experimental data and theoretical values available. From the present calculation we also predict that there exist longitudinal-transverse optical (LO-TO) splittings by 2-32 cm- 1 for these three compounds, which were not observed in previous experiments.
First-principles Study of Structural Properties of MgxZn1-xO ternary alloys
NASA Astrophysics Data System (ADS)
Gao, J.; Zhao, G. J.; Liang, X. X.; Song, T. L.
2015-01-01
First-principles calculations have been carried out to investigate the structural and electronic properties of MgxZn1-xO ternary alloys. The calculations are performed using the full potential linearized augmented plane wave (FP-LAPW) method within the density functional theory(DFT). We conclude that the structural properties of these materials, in particular the composition dependence on the lattice constant and the band gap is found to be linear. The a-axis length in the lattice gradually increases, while the c-axis length decreases with the increase in Mg doping concentration, and be corresponded with the Vegard's law linear rule. The lattice parameters of the MgxZn1-xO ternary alloys are consistent with experimental data and other theoretical results. We found in the conduction band portion, the Mg 2p 2s states are moved to high energy region as the Mg content increases, so the band gap increases.
Lakel, S.; Okbi, F.; Ibrir, M.; Almi, K.
2015-03-30
We have performed first-principles calculations to investigate the behavior under hydrostatic pressure of the structural, elastic and lattice dynamics properties of aluminum phosphide crystal (AlP), in both zinc-blende (B3) and nickel arsenide (B8) phases. Our calculated structural and electronic properties are in good agreement with previous theoretical and experimental results. The elastic constants, bulk modulus (B), shear modulus (G), and Young's modulus (E), Born effective charge and static dielectric constant ?{sub 0}, were calculated with the generalized gradient approximations and the density functional perturbation theory (DFPT). Our results in the pressure behavior of the elastic and dielectric properties of both phases are compared and contrasted with the common III–V materials. The Born effective charge ZB decreases linearly with pressure increasing, while the static dielectric constant decreases quadratically with the increase of pressure.
NASA Astrophysics Data System (ADS)
Yadav, Vivek K.; Karmakar, Anwesa; Choudhuri, Jyoti Roy; Chandra, Amalendu
2012-10-01
We present a first principles theoretical study of vibrational spectral diffusion and hydrogen bond dynamics in liquid methanol at room temperature. The dynamics of spectral diffusion of OD modes of deuterated methanol reveals two times scales: a short time scale of about 120 fs and a longer time scale of about 3.2 ps. A damped oscillation is also found at around 120-180 fs. Calculations of power spectrum of relative velocities and hydrogen bond correlation functions reveal that the short time dynamics originates from intermolecular motion of hydrogen bonded methanol pairs while the long time relaxation corresponds to the breaking dynamics of hydrogen bonds. The quantitative details of the time constants are found to depend on the frequency of tagged OD bonds.
NASA Astrophysics Data System (ADS)
Hellman, Anders; Iandolo, Beniamino; Wickman, Björn; Grönbeck, Henrik; Baltrusaitis, Jonas
2015-10-01
The oxygen evolution reaction on hydroxyl- and oxygen-terminated hematite was investigated using first-principle calculations within a theoretical electrochemical framework. Both pristine hematite and hematite containing oxygen vacancies were considered. The onset potential was determined to be 1.79 V and 2.09 V vs. the reversible hydrogen electrode (RHE) for the pristine hydroxyl- and oxygen-terminated hematite, respectively. The presence of oxygen vacancies in the hematite surface resulted in pronounced shifts of the onset potential to 3.09 V and 1.83 V, respectively. Electrochemical oxidation measurements conducted on thin-film hematite anodes, resulted in a measured onset potential of 1.66 V vs. RHE. Furthermore, the threshold potential between the hydroxyl- and oxygen-terminated hematite was determined as a function of pH. The results indicate that electrochemical water oxidation on hematite occurs on the oxygen-terminated hematite, containing oxygen vacancies.
NASA Astrophysics Data System (ADS)
Deng, Zun-Yi; Zhang, Jian-Min; Xu, Ke-Wei
2015-08-01
To exploit the potential application of nitride nanotube (BNNT), the adsorption of sulfur dioxide (SO2) on pristine and Mn-doped BNNT was theoretically studied using first-principles approach based on density functional theory (DFT). The most stable adsorption geometry, adsorption energy, magnetic moment, charge transfer and density of states of these systems are discussed. SO2 molecule is weakly adsorbed on the pristine BNNT. The Mn-doped BNNT show high reactivity toward SO2 regardless of the MnB site or MnN site adsorption. The larger formation energies and analysis of density of states show the SO2 molecules are chemically bonded to Mn-doped BNNT and the covalent interaction between the SO2 molecule and Mn atom can be formed. Therefore, the Mn-doped BNNT can be used as SO2 gas sensor manufacturing raw materials, and it may be a potential material for nanodevice applications.
NASA Astrophysics Data System (ADS)
Wan, L. F.; Nishimatsu, T.; Beckman, S. P.
2012-05-01
The elastic and dielectric properties of the four experimentally known phases of KNbO3 (KNO) are investigated by first-principles methods. The atomic structure is reported along with the Born effective charge tensor to reveal the relation between Nb-O bonds hybridization and ferroelectric structural distortion. The dielectric, elastic, and piezoelectric properties of each phase are presented and compared to results in the literature. The computed structures are found to match experiment to an accuracy of approximately 2%. Although there have been very few experimental studies of single crystal KNO, it is found that the elastic parameters computed for orthorhombic KNO agree with the measured values to better than 25%, which is within the anticipated exchange-correlation error; however, the computed piezoelectric coefficient differ from the experimental values by as much as 50%, which suggests that the disagreement may not be solely due to the theoretical approximations.
NASA Astrophysics Data System (ADS)
Brik, M. G.; Ogasawara, K.
2007-11-01
Systematic analysis of the energy level scheme and ground state absorption of the Cr4+ ion in Li2CaSiO4 crystal was performed using the exchange charge model of the crystal field [B.Z. Malkin, in: A.A. Kaplyanskii, B.M. Macfarlane (Eds.), Spectroscopy of Solids Containing Rare-earth Ions, North-Holland, Amsterdam, 1987, pp. 33-50] and recently developed first-principles approach to the analysis of the absorption spectra of impurity ions in crystals based on the discrete variational multielectron (DVME) method [K. Ogasawara, T. Iwata, Y. Koyama, T. Ishii, I. Tanaka, H. Adachi, Phys. Rev. B 64 (2001) 115413]. Using the former method, the values of parameters of crystal field acting on the Cr4+ ion valence electrons were calculated using the Li2CaSiO4 crystal structure data. Energy levels of the Cr4+ ion obtained after diagonalizing the crystal field Hamiltonian are in good agreement with those obtained from the experimental spectra. The latter method is based on the numerical solution of the Dirac equation; therefore, all relativistic effects are automatically considered. As a result, energy level scheme of Cr4+ and its absorption spectra in both polarizations were calculated, assigned and compared with experimental data; energy of the lowest charge transfer transition was evaluated and compared with theoretical predictions for the CrO44- complex available in the literature. The main features of the experimental spectra shape are reproduced well by the calculations. By performing analysis of the molecular orbitals (MO) population, it was shown that the covalent effects play an important role in formation of the spectral properties of Cr4+ ion in the considered crystal.
FT-Raman, surface-enhanced Raman spectroscopy and theoretical investigations of diclofenac sodium
NASA Astrophysics Data System (ADS)
Iliescu, T.; Baia, M.; Kiefer, W.
2004-03-01
Raman and surface-enhanced Raman (SER) spectroscopies have been applied to the vibrational characterization of diclofenac sodium (DCF-Na). Theoretical calculations (DFT and ab initio) of two DCF-Na conformers have been performed to find the optimized structure and computed vibrational wavenumbers of the most stable one. SER spectra in silver colloid at different pH values have been also recorded and analyzed. Good SER spectra have been obtained in acidic and neutral environments, proving the chemisorption of the DCF-Na molecule on the silver surface. In the investigated pH range the carboxylate anion has been bonded to the silver surface through the lone pair oxygen electrons. The phenyl rings' orientation with respect to the silver surface changed on passing from acidic to neutral pH from a tilted close to flat to a more perpendicular one.
Predicting Raman Spectra of Aqueous Silica and Alumina Species in Solution From First Principles
NASA Astrophysics Data System (ADS)
Hunt, J. D.; Schauble, E. A.; Manning, C. E.
2006-12-01
Dissolved silica and alumina play an important role in lithospheric fluid chemistry. Silica concentrations in aqueous fluids vary over the range of crustal temperatures and pressures enough to allow for significant mass transport of silica via fluid-rock interaction. The polymerization of silica, and the possible incorporation of alumina into the polymer structure, could afford crystal-like or melt-like sites to otherwise insoluble elements such as titanium, leading to enhanced mobility. Raman spectroscopy in a hydrothermal diamond anvil cell (HDAC) has been used to study silica polymerization at elevated pressure and temperature [Ref. 1, 2], but Raman spectra of expected solutes are not fully understood. We calculated Raman spectra of H4SiO4 monomers, H6Si2O7 dimers, and H6SiAlO_7^- dimers, from first principles using hybrid density functional theory (B3LYP). These spectra take into account the variation in bridging angle (Si-O-Si and Si-O-Al angles) that the dimers will have at a given temperature by calculating a potential energy surface of the dimer as the bridging angle varies, and using a Boltzmann distribution at that temperature to determine relative populations at each geometry. Solution effects can be incorporated by using a polarizable continuum model (PCM), and a potential energy surface has been constructed for the silica dimer using a PCM. The bridging angle variation explains the broadness of the 630 cm^-^1 silica dimer peak observed in HDAC experiments [Ref. 1, 2] at high temperatures. The silica-alumina dimer bridging angle is shown to be stiffer than the silica dimer bridging angle, which results in a much narrower main peak. The synthetic spectrum obtained for the silica-alumina dimer suggests that there may be a higher ratio of complexed alumina to free alumina in solution at highly basic pH than previously estimated [Ref. 3]. References: 1. Zotov, N. and H. Keppler, Chemical Geology, 2002. 184: p. 71-82. 2. Zotov, N. and H. Keppler, American Mineralogist, 2000. 85: p. 600-603. 3. Gout, R., et al., Journal of Solution Chemistry, 2000. 29: p. 1173-1186.
Super hard cubic phases of period VI transition metal nitrides: First principles investigation
Khare, Sanjay V.
Super hard cubic phases of period VI transition metal nitrides: First principles investigation S July 2008 Keywords: Coatings Elastic properties Hardness Nitrides We report a systematic studyN in rocksalt phase has a bulk modulus of 380 GPa making them candidates for super hardness. Based on the bulk
Militzer, Burkhard
FPEOS: A First-Principles Equation of State Table of Deuterium for Inertial Confinement Fusion) Understanding and designing inertial confinement fusion (ICF) implosions through radiation- hydrodynamics. To minimize the drive energy for ignition, the imploding shell of DT- fuel needs to be kept as cold
First-principles, quantum-mechanical simulations of electron solvation by a water cluster
Herbert, John
mechanics, with forces computed on the fly by solving the quantum-mechanical all-electron problem at eachFirst-principles, quantum-mechanical simulations of electron solvation by a water cluster John M initio molecular dynamics scheme, balancing accuracy against feasibility, to simu- late vibrational
First principles thermodynamical modeling of the binodal and spinodal curves in lead chalcogenides
Curtarolo, Stefano
First principles thermodynamical modeling of the binodal and spinodal curves in lead chalcogenides decompositions features in the pseudo-binary lead chalcogenides PbSe-PbTe, PbS-PbTe, and PbS-PbSe. While our For decades, the physical properties of lead chalco- genides have generated substantial interest in a number
Learning Biped Locomotion from First Principles on a Simulated Humanoid Robot
Fernandez, Thomas
://www.frt.fy.chalmers.se/cs/index.html Abstract. We describe the first instance of an approach for control programming of humanoid robots, based in this concept is to evolve control pro- grams from first principles on a simulated robot, transfer the resulting state tournament algorithm. Evolution created controller programs that made the simulated robot produce
The New Face of Rhodium Alloys: Revealing Ordered Structures from First Principles
Hart, Gus
The New Face of Rhodium Alloys: Revealing Ordered Structures from First Principles Ohad Levy-mail: stefano@duke.edu Abstract: The experimental and computational data on rhodium binary alloys is sparse, and platinum), rhodium has a high catalytic potential for a variety of chemical reactions.1,2 It is used
Schmidt, Wolf Gero
Lithium niobate-tantalate mixed crystals electronic and optical properties calculated from first lithium niobatetantalate has been calculated from first principles. Based on density functional theory we, LiTaO3, birefringence, BSE, GWA I. INTRODUCTION Lithium niobate (LN) and lithium tantalate (LN
Amorphous structures of Cu, Ag, and Au nanoclusters from first principles calculations
NASA Astrophysics Data System (ADS)
Oviedo, J.; Palmer, R. E.
2002-12-01
We have carried out first-principles density functional calculations for clusters of the coinage metals containing thirteen atoms (M13, where M=Cu, Ag, or Au). We find that for this geometric "magic number" the low energy isomers are actually disordered, forming almost a continuous distribution as a function of energy.
Emergence of rigidity at the structural glass transition: a first principle computation
Hajime Yoshino; Marc Mezard
2012-01-12
We compute the shear modulus of structural glasses from a first principle approach based on the cloned liquid theory. We find that the intra-state shear-modulus, which corresponds to the plateau modulus measured in linear visco-elastic measurements, strongly depends on temperature and vanishes continuously when the temperature is increased beyond the glass temperature.
Metalloboranes from first-principles calculations: A candidate for high-density hydrogen storage
Akbarzadeh, A R; Tymczak, C J
2015-01-01
Using first principles calculations, we show the high hydrogen storage capacity of a new class of compounds, metalloboranes. Metalloboranes are transition metal (TM) and borane compounds that obey a novel-bonding scheme. We have found that the transition metal atoms can bind up to 10 H2 molecules.
Magneto-elastic effects in compressed cobalt from first-principles Gerd Steinle-Neumann*
Steinle-Neumann, Gerd
Magneto-elastic effects in compressed cobalt from first-principles Gerd Steinle of the close-packed phases of cobalt are computed as a function of compression using the linearized augmented, a lot of effort has focused on the metal adjacent to iron in the Periodic Table: cobalt. The study
ERIC Educational Resources Information Center
Bowen, J. Philip; Sorensen, Jennifer B.; Kirschner, Karl N.
2007-01-01
The analysis explains the basis set superposition error (BSSE) and fragment relaxation involved in calculating the interaction energies using various first principle theories. Interacting the correlated fragment and increasing the size of the basis set can help in decreasing the BSSE to a great extent.
Melnik, Roderick
Temperature dependent elastic constants for crystals with arbitrary symmetry: Combined first principles and continuum elasticity theory Tianjiao Shao, Bin Wen, Roderick Melnik, Shan Yao, Yoshiyuki by the American Institute of Physics. Related Articles High-pressure elastic properties of a fluorinated copolymer
Ordered magnesium-lithium alloys: First-principles predictions Richard H. Taylor
Hart, Gus
Ordered magnesium-lithium alloys: First-principles predictions Richard H. Taylor Department 2010 Magnesium-lithium Mg-Li alloys are among the lightest structural materials. Although considerable Emerging technologies increasingly depend on the pro- duction of ultralight-weight materials. Magnesium
FIRST PRINCIPLES SIMULATION OF IRON-BASED INTERMETALLIC ALLOYS Michael Widom1
Widom, Michael
. In a many-component alloy, phase segregation needed to grow thermodynamically stable intermetallic compoundsFIRST PRINCIPLES SIMULATION OF IRON-BASED INTERMETALLIC ALLOYS Michael Widom1 , Libo Xie1 is on glass-forming compounds including up to six different metal and metalloid elements, and calculations
First-principles studies of NiTa intermetallic compounds , Bin Wen b,n
Melnik, Roderick
First-principles studies of NiTa intermetallic compounds Yi Zhou a , Bin Wen b,n , Yunqing Ma properties, and electronic structures of NiTa intermetallic compounds are investigated in detail based on density functional theory. Our results indicate that all NiTa intermetallic compounds calculated here
First principles study of CrH and CrM2H
NASA Astrophysics Data System (ADS)
Kanagaprabha, S.; Santhosh, M.; Rajeswarapalanichamy, R.; Iyakutti, K.
2013-06-01
First principles calculation were performed using Tight-binding LMTO method with Local density approximation (LDA) and Atomic sphere approximation (ASA) to understand the electronic properties of CrH. A pressure induced structural phase transition from cubic to hexagonal structure of CrH is predicted. The stability of CrM2H is analyzed.
Electron-hole excitations and optical spectra from first principles Michael Rohlfing
Wu, Zhigang
Electron-hole excitations and optical spectra from first principles Michael Rohlfing Institut fu April 2000 We present a recently developed approach to calculate electron-hole excitations of the electronic system by the corresponding one- and two-particle Green's function. The method combines three
Bennett, Joseph W.; Rabe, Karin M.
2012-11-15
In this concept paper, the development of strategies for the integration of first-principles methods with crystallographic database mining for the discovery and design of novel ferroelectric materials is discussed, drawing on the results and experience derived from exploratory investigations on three different systems: (1) the double perovskite Sr(Sb{sub 1/2}Mn{sub 1/2})O{sub 3} as a candidate semiconducting ferroelectric; (2) polar derivatives of schafarzikite MSb{sub 2}O{sub 4}; and (3) ferroelectric semiconductors with formula M{sub 2}P{sub 2}(S,Se){sub 6}. A variety of avenues for further research and investigation are suggested, including automated structure type classification, low-symmetry improper ferroelectrics, and high-throughput first-principles searches for additional representatives of structural families with desirable functional properties. - Graphical abstract: Integration of first-principles methods with crystallographic database mining, for the discovery and design of novel ferroelectric materials, could potentially lead to new classes of multifunctional materials. Highlights: Black-Right-Pointing-Pointer Integration of first-principles methods and database mining. Black-Right-Pointing-Pointer Minor structural families with desirable functional properties. Black-Right-Pointing-Pointer Survey of polar entries in the Inorganic Crystal Structural Database.
Pressure dependent phase stability transformations of GaS: A first principles study
Melnik, Roderick
Pressure dependent phase stability transformations of GaS: A first principles study Bin Wen a principle calculations are used to determine the pressure dependent phase stability transformations for GaS polytypes at pressures up to 1000 GPa. Our results indicate that the relative stability sequence changes
Thermal Conductivity of Periclase (MgO) from First Principles Stephen Stackhouse*
Stixrude, Lars
Thermal Conductivity of Periclase (MgO) from First Principles Stephen Stackhouse* Department thermal conductivity k of periclase (MgO) up to conditions representative of the Earth's core, 83.10.Rs Thermal conductivity is central to our understanding of planetary evolution as it sets
Ordered Structures in Rhenium Binary Alloys from First-Principles Calculations
Hart, Gus
Ordered Structures in Rhenium Binary Alloys from First-Principles Calculations Ohad Levy,, Michal-mail: stefano@duke.edu Abstract: Rhenium is an important alloying agent in catalytic materials and superalloys to a comprehensive screening of rhenium intermetallic binary alloys. This choice is motivated by the wide array
Nuclear Quantum Effects in Ice Phases and Water from First Principles Calculations
NASA Astrophysics Data System (ADS)
Pamuk, Betul
Despite the simplicity of the molecule, condensed phases of water show many physical anomalies, some of which are still unexplained to date. This thesis focuses on one striking anomaly that has been largely neglected and never explained. When hydrogen (1H) is replaced by deuterium (2 D), zero point fluctuations of the heavy isotope causes ice to expand, whereas in normal isotope effect, heavy isotope causes volume contraction. Furthermore, in a normal isotope effect, the shift in volume should decrease with increasing temperature, while, in ice, the volume shift increases with increasing temperature and persists up to the melting temperature and also exists in liquid water. In this dissertation, nuclear quantum effects on structural and cohesive properties of different ice polymorphs are investigated. We show that the anomalous isotope effect is well described by first principles density functional theory with van der Waals (vdW-DF) functionals within the quasi-harmonic approximation. Our theoretical modeling explains how the competition between the intra- and inter-molecular bonding of ice leads to an anomalous isotope effect in the volume and bulk modulus of ice. In addition, we predict a normal isotope effect when 16O is replaced by 18O, which is experimentally confirmed. Furthermore, the transition from proton disordered hexagonal phase, ice Ih to proton ordered hexagonal phase, ice XI occurs with a temperature difference between 1H and 2D of 6K, in good agreement with experimental value of 4K. We explain, for first time for that this temperature difference is entirely due to the zero point energy. In the second half of this thesis, we expand our study to the other ice phases: ice Ic, ice IX, ice II, ice VIII, clathrate hydrates, and low and high density amorphous ices. We employ the methodology that we have developed to investigate the isotope effect in structures with different configurations. We show that there is a transition from anomalous isotope effect to normal isotope effect in these structures as the density increases. We analyse the bonding mechanism of these structures and make links to the most important anomalies of liquid water.
Solution-based thermodynamic modeling of the Ni-Al-Mo system using first-principles calculations
Zhou, S H; Wang, Y; Chen, L -Q; Liu, Z -K; Napolitano, R E
2014-09-01
A solution-based thermodynamic description of the ternary Ni–Al–Mo system is developed here, incorporating first-principles calculations and reported modeling of the binary Ni–Al, Ni–Mo and Al–Mo systems. To search for the configurations with the lowest energies of the N phase, the Alloy Theoretic Automated Toolkit (ATAT) was employed and combined with VASP. The liquid, bcc and ?-fcc phases are modeled as random atomic solutions, and the ??-Ni3Al phase is modeled by describing the ordering within the fcc structure using two sublattices, summarized as (Al,Mo,Ni)0.75(Al,Mo,Ni)0.25. Thus, ?-fcc and ??-Ni3Al are modeled with a single Gibbs free energy function with appropriate treatment of the chemical ordering contribution. In addition, notable improvements are the following: first, the ternary effects of Mo and Al in the B2-NiAl and D0a-Ni3Mo phases, respectively, are considered; second, the N-NiAl8Mo3 phase is described as a solid solution using a three-sublattice model; third, the X-Ni14Al75Mo11 phase is treated as a stoichiometric compound. Model parameters are evaluated using first-principles calculations of zero-Kelvin formation enthalpies and reported experimental data. In comparison with the enthalpies of formation for the compounds ?-AlMo, ?-Al8Mo3 and B2-NiAl, the first-principles results indicate that the N-NiAl8Mo3 phase, which is stable at high temperatures, decomposes into other phases at low temperature. Resulting phase equilibria are summarized in the form of isothermal sections and liquidus projections. To clearly identify the relationship between the ?-fcc and ??-Ni3Al phases in the ternary Ni–Al–Mo system, the specific ?-fcc and ??-Ni3Al phase fields are plotted in x(Al)–x(Mo)–T space for a temperature range 1200–1800 K.
Cysewski, Piotr; Jeli?ski, Tomasz
2013-10-01
The electronic spectrum of four different anthraquinones (1,2-dihydroxyanthraquinone, 1-aminoanthraquinone, 2-aminoanthraquinone and 1-amino-2-methylanthraquinone) in methanol solution was measured and used as reference data for theoretical color prediction. The visible part of the spectrum was modeled according to TD-DFT framework with a broad range of DFT functionals. The convoluted theoretical spectra were validated against experimental data by a direct color comparison in terms of CIE XYZ and CIE Lab tristimulus model color. It was found, that the 6-31G** basis set provides the most accurate color prediction and there is no need to extend the basis set since it does not improve the prediction of color. Although different functionals were found to give the most accurate color prediction for different anthraquinones, it is possible to apply the same DFT approach for the whole set of analyzed dyes. Especially three functionals seem to be valuable, namely mPW1LYP, B1LYP and PBE0 due to very similar spectra predictions. The major source of discrepancies between theoretical and experimental spectra comes from L values, representing the lightness, and the a parameter, depicting the position on green?magenta axis. Fortunately, the agreement between computed and observed blue?yellow axis (parameter b) is very precise in the case of studied anthraquinone dyes in methanol solution. Despite discussed shortcomings, color prediction from first principle quantum chemistry computations can lead to quite satisfactory results, expressed in terms of color space parameters. PMID:23250806
First principles versus spherical ion models of the B1 and B2 phases of NaCl
NASA Astrophysics Data System (ADS)
Bukowinski, M. S. T.; Aidun, John
1985-02-01
The electron density-functional formalism is used to compute first-principles equations of state and charge distributions for the B1 and B2 phases of NaCl. The B1 equation of state is in excellent agreement with available static, acoustic, and shock wave data. The theoretical B2 equation of state differs significantly from available diamond anvil data but agrees well with shock wave data. Analysis of the theoretical and experimental isotherms suggest that the former may be a little low in pressure, while the latter is almost certainly too stiff. The computed charge distribution and valence band energies indicate that Cl-Cl interaction may dominate the energetics of the B2 phase and that, consequently, the Cl ions are significantly distorted. The theoretical zero pressure Cl radius is smaller than the classical crystallographical radius, is sensitive to coordination, and expands significantly across the B1-B2 transformation. In contrast, the Na ion is insensitive to coordination and seems to retain classical ionic properties (+1 charge, spherical charge distribution) up to the highest pressures investigated (˜70 GPa). These properties are largely responsible for the failure of Born-Mayer-type structure independent pair potentials to account accurately for the changes in elastic properties of NaCl across the B1-B2 transformation.
A First Principles Molecular Dynamics Study Of Calcium Ion In Water
Lightstone, F; Schwegler, E; Allesch, M; Gygi, F; Galli, G
2005-01-28
In this work we report on Car-Parrinello simulations of the divalent calcium ion in water, aimed at understanding the structure of the hydration shell and at comparing theoretical results with a series of recent experiments. Our paper shows some of the progress in the investigation of aqueous solutions brought about by the advent of ab initio molecular dynamics and highlights the importance of accessing subtle details of ion-water interactions from first-principles. Calcium plays a vital role in many biological systems, including signal transduction, blood clotting and cell division. In particular, calcium ions are known to interact strongly with proteins as they tend to bind well to both negatively charged (e.g. in aspartate and glutamate) and uncharged oxygens (e.g. in main-chain carbonyls). The ability of calcium to coordinate multiple ligands (from 6 to 8 oxygen atoms) with an asymmetric coordination shell enables it to cross-link different segments of a protein and induce large conformational changes. The great biochemical importance of the calcium ion has led to a number of studies to determine its hydration shell and its preferred coordination number in water. Experimental studies have used a variety of techniques, including XRD, EXAFS, and neutron diffraction to elucidate the coordination of Ca{sup 2+} in water. The range of coordination numbers (n{sub C}) inferred by X-ray diffraction studies varies from 6 to 8, and is consistent with that reported in EXAFS experiments (8 and 7.2). A wider range of values (6 to 10) was found in early neutron diffraction studies, depending on concentration, while a more recent measurement by Badyal, et al. reports a value close to 7. In addition to experimental measurements, many theoretical studies have been carried out to investigate the solvation of Ca{sup 2+} in water and have also reported a wide range of coordination numbers. Most of the classical molecular dynamics (MD) and QM/MM simulations report n{sub C} in the range of 8 to 10; in general, n{sub C} appears to be highly sensitive to the choice of the ion-water potential used in the calculations. Even ab initio MD simulations have so far obtained conflicting values for n{sub C}. For the structure of the first salvation shell Naor, et al. found n{sub C} = 7 to 8 and a Ca{sup 2+} - oxygen average distance (r{sub Ca-O}) of 2.64 {angstrom}, while Bako, et al. found n{sub C} = 6 and r{sub Ca-O} = 2.45 {angstrom}. In view of the existing controversies, we have carried out extensive Car-Parrinello simulations of Ca{sup 2+} solvation in water, using both a rigid and a flexible water model, up to time scales of 40 ps. Our simulations show variations of coordination numbers from 6, 7 and 8 occurring over intervals of {approx} 0.3/0.4 exchanges/ps, and yielding average coordination numbers of 6.2 and 7 for flexible and rigid water models, respectively. These results are consistent with those reported in recent EXAFS and neutron diffraction experiments. In addition, our calculations show an asymmetric coordination of Ca{sup 2+} to oxygen, similar to the case of Mg{sup 2+}.
New Stable Phases in the Re-B System: A First-principles Study
NASA Astrophysics Data System (ADS)
Zhao, Xin; Nguyen, Manh Cuong; Wang, Cai-Zhuang; Ho, Kai-Ming; Iowa State University Team
2014-03-01
We studied rhenium borides using genetic algorithm in combination with first-principles calculations and revealed several new stable phases in the Re-B system. The structures obtained from our genetic algorithm search are energetically much superior to those proposed in the literature. Two new phases of Re2B were found to be thermodynamically stable at different pressures, which possibly explains the recent experimental observations (Solid State Sciences 25 85-92 (2013)). ReB is stable against decomposition reactions below 10 GPa and ReB3 is stable above 22 GPa. A C2/m structure was discovered for ReB4 to have lower energy than the R-3m structure reported earlier (J. Alloys Compd. 573 20-26 (2013)). Elastic properties from first-principles calculations indicate that the structures we report in this work are mechanically stable and promising targets as new ultra-hard materials.
Zhou, Fei; Nielson, Weston; Xia, Yi; Ozoli?š, Vidvuds
2014-10-01
First-principles prediction of lattice thermal conductivity ?_{L} of strongly anharmonic crystals is a long-standing challenge in solid-state physics. Making use of recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics. Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Nonintuitively, high accuracy is achieved when the model is trained on first-principles forces in quasirandom atomic configurations. The method is demonstrated for Si, NaCl, and Cu_{12}Sb_{4}S_{13}, an earth-abundant thermoelectric with strong phonon-phonon interactions that limit the room-temperature ?_{L} to values near the amorphous limit.
First principles study of the Young's modulus of Si <001> nanowires
Lee, B; Rudd, R E
2006-07-03
We report the results of first-principles calculations of the Young's modulus and other mechanical properties of hydrogen-passivated Si <001> nanowires. The nanowires are taken to have predominantly {l_brace}100{r_brace} surfaces, with small {l_brace}110{r_brace} facets according to the Wulff shape. The Young's modulus, the equilibrium length and the constrained residual stress of a series of prismatic beams of differing sizes is found to have a size dependence that scales like the surface area to volume ratio for all but the smallest beam. The results are compared with two different models (and the results of classical atomistic calculations based on an empirical potential). We discuss the physics of the hydrogen interactions on the surface and the charge density variations within the beam that may account for the discrepancies of the models and the first principles results.
Redox condition in molten salts and solute behavior: A first-principles molecular dynamics study
NASA Astrophysics Data System (ADS)
Nam, Hyo On; Morgan, Dane
2015-10-01
Molten salts technology is of significant interest for nuclear, solar, and other energy systems. In this work, first-principles molecular dynamics (FPMD) was used to model the solute behavior in eutectic LiCl-KCl and FLiBe (Li2BeF4) melts at 773 K and 973 K, respectively. The thermo-kinetic properties for solute systems such as the redox potential, solute diffusion coefficients and structural information surrounding the solute were predicted from FPMD modeling and the calculated properties are generally in agreement with the experiments. In particular, we formulate an approach to model redox energetics vs. chlorine (or fluorine) potential from first-principles approaches. This study develops approaches for, and demonstrates the capabilities of, FPMD to model solute properties in molten salts.
Zhou, Fei; Nielson, Weston; Xia, Yi; Ozoli?š, Vidvuds
2014-10-31
First-principles prediction of lattice thermal conductivity ?(L) of strongly anharmonic crystals is a long-standing challenge in solid-state physics. Making use of recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics. Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Nonintuitively, high accuracy is achieved when the model is trained on first-principles forces in quasirandom atomic configurations. The method is demonstrated for Si, NaCl, and Cu(12)Sb(4)S(13), an earth-abundant thermoelectric with strong phonon-phonon interactions that limit the room-temperature ?(L) to values near the amorphous limit. PMID:25396378
NASA Astrophysics Data System (ADS)
Zhou, Fei; Nielson, Weston; Xia, Yi; Ozoli?š, Vidvuds
2014-10-01
First-principles prediction of lattice thermal conductivity ?L of strongly anharmonic crystals is a long-standing challenge in solid-state physics. Making use of recent advances in information science, we propose a systematic and rigorous approach to this problem, compressive sensing lattice dynamics. Compressive sensing is used to select the physically important terms in the lattice dynamics model and determine their values in one shot. Nonintuitively, high accuracy is achieved when the model is trained on first-principles forces in quasirandom atomic configurations. The method is demonstrated for Si, NaCl, and Cu12Sb4S13 , an earth-abundant thermoelectric with strong phonon-phonon interactions that limit the room-temperature ?L to values near the amorphous limit.
A Massive Core in Jupiter Predicted From First-Principles Simulations
B. Militzer; W. B. Hubbard; J. Vorberger; I. Tamblyn; S. A. Bonev
2008-07-26
Hydrogen-helium mixtures at conditions of Jupiter's interior are studied with first-principles computer simulations. The resulting equation of state (EOS) implies that Jupiter possesses a central core of 14-18 Earth masses of heavier elements, a result that supports core accretion as standard model for the formation of hydrogen-rich giant planets. Our nominal model has about 2 Earth masses of planetary ices in the H-He-rich mantle, a result that is, within modeling errors, consistent with abundances measured by the 1995 Galileo Entry Probe mission (equivalent to about 5 Earth masses of planetary ices when extrapolated to the mantle), suggesting that the composition found by the probe may be representative of the entire planet. Interior models derived from this first-principles EOS do not give a match to Jupiter's gravity moment J4 unless one invokes interior differential rotation, implying that jovian interior dynamics has an observable effect on the measured gravity field.
NASA Astrophysics Data System (ADS)
Johnston, Karen; Nieminen, Risto M.
2007-03-01
The adhesion of plastics to ceramics is important for many industrial and technological appliations. It is therefore essential to understand the underlying structure and bonding of the polymer and the surface. The aim of this research is to improve plastic adhesion using a multiscale approach. The first step involves the use of density functional calculations to understand the atomic-scale structure and bonding of polymers on surfaces. The plastic of interest is mainly composed of the polymer bisphenol-A-polycarbonate (BPA-PC). The BPA-PC monomer consists of two phenol groups, one propane group and a carbonic acid group. First-principles calculations of the adsorption of these molecules onto the Si(001)-(2x1) dimer surface will be presented. Finally, the incorporation of first-principles data into a coarse-graining method will be discussed.
First-principles investigation of the band gap evolution in (Pb,Sn)Te
NASA Astrophysics Data System (ADS)
Gao, Xing; Daw, Murray
2007-03-01
The electronic structure of Sn-doped PbTe is interesting because of the so-called band inversion in its two end members, PbTe and SnTe [1,2]. Although, the electronic structure of these two compounds have been extensively studied by first-principles calculations, to our best knowledge, there are no direct first-principles calculations of the band gap evolution through the full range of alloying. We report a study of the electronic structure of this material through the full range of alloy content, combining SQS [3] and LDA. Our results show that disorder plays an important role in the electronic structure of this alloy. [1] Dimmock, Melngailis, and Strauss, Phys. Rev. Lett. 16, 1193 (1966). [2] Tung, and Cohen, Phys. Rev. 180, 823 (1969). [3] Wei and Zunger, Phys. Rev. B 55, 13605 (1997).
First-principles insights into f magnetism: A case study on some magnetic pyrochlores
NASA Astrophysics Data System (ADS)
Deilynazar, Najmeh; Khorasani, Elham; Alaei, Mojtaba; Javad Hashemifar, S.
2015-11-01
First-principles calculations are performed to investigate f magnetism in A2Ti2O7 (A=Eu, Gd, Tb, Dy, Ho, Er, Yb) magnetic pyrochlore oxides. The Hubbard U parameter and the relativistic spin orbit correction are applied for a more accurate description of the electronic structure of the systems. It is argued that the main obstacle for the first-principles study of these systems is the multi-minima solutions of their electronic configuration. Among the studied pyrochlores, Gd2Ti2O7 shows the least multi-minima problem. The crystal electric field theory is applied for phenomenological comparison of the calculated spin and orbital moments with the experimental data.
Structure of the (111) surface of bismuth: LEED analysis and first-principles calculations
Moenig, H.; Wells, J.; Hofmann, Ph.; Sun, J.; Pohl, K.; Koroteev, Yu.M.; Bihlmayer, G.; Chulkov, E.V.
2005-08-15
The surface structure of Bi(111) was investigated by low-energy electron diffraction (LEED) intensity analysis for temperatures between 140 and 313 K and by first-principles calculations. The diffraction pattern reveals a (1x1) surface structure and LEED intensity versus energy simulations confirm that the crystal is terminated with a Bi bilayer. Excellent agreement is obtained between the calculated and measured diffraction intensities in the whole temperature range. The first interlayer spacing shows no significant relaxation at any temperature while the second interlayer spacing expands slightly. The Debye temperatures deduced from the optimized atomic vibrational amplitudes for the two topmost layers are found to be significantly lower than in the bulk. The experimental results for the relaxations agree well with those of our first-principles calculation.
Fattebert, Jean-Luc; Lau, Edmond Y; Bennion, Brian J; Huang, Patrick; Lightstone, Felice C
2015-12-01
Enzymes are complicated solvated systems that typically require many atoms to simulate their function with any degree of accuracy. We have recently developed numerical techniques for large scale first-principles molecular dynamics simulations and applied them to the study of the enzymatic reaction catalyzed by acetylcholinesterase. We carried out density functional theory calculations for a quantum-mechanical (QM) subsystem consisting of 612 atoms with an O(N) complexity finite-difference approach. The QM subsystem is embedded inside an external potential field representing the electrostatic effect due to the environment. We obtained finite-temperature sampling by first-principles molecular dynamics for the acylation reaction of acetylcholine catalyzed by acetylcholinesterase. Our calculations show two energy barriers along the reaction coordinate for the enzyme-catalyzed acylation of acetylcholine. The second barrier (8.5 kcal/mol) is rate-limiting for the acylation reaction and in good agreement with experiment. PMID:26642985
Computer-based First-principles Kinetic Model for Aqueous Phase Advanced
Das, Suman
of Technology #12;2 Various AOPs Technologies 1/2 Proved AOPs Advantages Disadvantages H2O2/ UV · Long stability· · Catalyst fouling · Recovery of TiO2 required for slurry application #12;3 Various AOPs Technologies 2/2 Hi Pressure UV system (UV/H2O2) Trojan Tech #12;A Computer-based First-principles Kinetic Model in AOPs Why
Comparison of Jupiter Interior Models Derived from First-Principles Simulations
B. Militzer; W. B. Hubbard
2008-07-27
Recently two groups used first-principles computer simulations to model Jupiter's interior. While both studies relied on the same simulation technique, density functional molecular dynamics, the groups derived very different conclusions. In particular estimates for the size of Jupiter's core and the metallicity of its hydrogen-helium mantle differed substantially. In this paper, we discuss the differences of the approaches and give an explanation for the differing conclusions.
Relative stability of extended interstitial defects in silicon: First-principles calculations
NASA Astrophysics Data System (ADS)
Park, Hyoungki; Wilkins, John W.
2009-06-01
Interstitials stored in {311} or {111} habit planes form rows of interstitial chains elongated in ?011? direction. Exploiting the large aspect ratio to treat chains as infinite, first-principles calculations of large computation supercells reveal a unique formation energy trend for each defect, which is closely correlated with its distinct shape. The most energetically favorable structure changes from {311} rodlike defects to Frank loops as the number of interstitials in the defect increases. These results are consistent with transmission electron microscopy studies.
First-principles study of He point-defects in HCP rare-earth metals
Li, Yang; Chen, Ru; Peng, SM; Long, XG; Wu, Z.; Gao, Fei; Zu, Xiaotao
2011-05-01
He defect properties in Sc, Y, Gd, Tb, Dy, Ho, Er and Lu were studied using first-principles calculations based on density functional theory. The results indicate that the formation energy of an interstitial He atom is smaller than that of a substitutional He atom in all hcp rare-earth metals considered. Furthermore, the tetrahedral interstitial position is more favorable than an octahedral position for He defects. The results are compared with those from bcc and fcc metals.
NASA Astrophysics Data System (ADS)
Liu, X. X.; Liu, L. Z.; Wu, X. L.; Chu, Paul K.
2015-07-01
The defect states and optical absorption enhancement induced by twin boundaries in silicon are investigated by first-principle calculation. The defect states in the forbidden bands are identified and based on the established electronic structures, the dielectric functions and absorption coefficients are derived. An important result of our calculations is that visible light absorption by the twinning configuration is enhanced significantly, indicating that twinning structures possibly play an important role in silicon-based photovoltaic devices.
NASA Astrophysics Data System (ADS)
Yang, J. Y.; Zhang, W. J.; Liu, L. H.
2015-09-01
This work aims at understanding and predicting the high-temperature anisotropic dielectric functions of (0001) sapphire over the entire infrared-visible-ultraviolet spectrum via the state-of-the-art infrared variable angle spectroscopic ellipsometry (IR-VASE) and first-principles method without empirical parameters. Upon measuring the high-symmetry orientation of c-plane surface, the IR-VASE determines the anisotropic infrared dielectric functions of (0001) sapphire for wavelengths ranging from 10 to 25 ?m and temperatures from 300 to 573 K. As ellipsometry experiments indicate, the maxima of ordinary infrared dielectric functions consistently decrease and shift to longer wavelength as temperature increases. By fitting ellipsometry data with the Lorentz oscillator model, the Lorentz parameters, e.g., oscillator strength, resonance frequency and broadening parameter, for infrared-active phonon modes are obtained to interpret the temperature effect. Moreover, the calculated vibration frequencies at varying temperatures by the first-principles method coincide with the positions of infrared absorption peaks, indicating that infrared optical absorption mainly arises from the coupling of incident photon with lattice vibration. In the visible-ultraviolet spectral range, the first-principles and lattice dynamics methods are combined to understand the temperature effect on dielectric functions of (0001) sapphire. This method reproduces the essential feature of previous room-temperature reflectivity experiments and detects the slight change of dielectric functions as temperature increases. The convincing results enable us to predict the high-temperature visible-ultraviolet dielectric functions of (0001) sapphire by the first-principles method.
First principles total energy study of NbCr{sub 2} + V Laves phase ternary system
Ormeci, A.; Chen, S.P.; Wills, J.M.; Albers, R.C.
1999-04-01
The C15 NbCr{sub 2} + V Laves phase ternary system is studied by using a first-principles, self-consistent, full-potential total energy method. Equilibrium lattice parameters, cohesive energies, density of states and formation energies of substitutional defects are calculated. Results of all these calculations show that in the C15 NbCr{sub 2} + V compounds, V atoms substitute Cr atoms only.
Surface energy and relaxation in boron carbide (101¯1) from first principles
NASA Astrophysics Data System (ADS)
Beaudet, Todd D.; Smith, John R.; Adams, Jane W.
2015-10-01
The surface energy of the boron carbide polytype B11Cp(CBC) for planar separations along {101¯1} was determined to be 3.21 J/m2 via first-principles density-functional computations. Surface atomic relaxations are relatively large, thereby lowering the surface energy significantly. The icosahedra are not intact on the surface, i.e., severed polyhedra are the lowest energy surface configuration. Good agreement was found with an experimental average fracture surface energy.
First principles predictions of intrinsic defects in aluminum arsenide, AlAs : numerical supplement.
Schultz, Peter Andrew
2012-04-01
This Report presents numerical tables summarizing properties of intrinsic defects in aluminum arsenide, AlAs, as computed by density functional theory. This Report serves as a numerical supplement to the results published in: P.A. Schultz, 'First principles predictions of intrinsic defects in Aluminum Arsenide, AlAs', Materials Research Society Symposia Proceedings 1370 (2011; SAND2011-2436C), and intended for use as reference tables for a defect physics package in device models.
First-Principles Study of Electron-Conduction Properties of C60 Bridges
NASA Astrophysics Data System (ADS)
Ono, Tomoya; Hirose, Kikuji
2007-01-01
The electron-conduction properties of fullerene-based nanostructures suspended between electrodes are examined by first-principles calculations based on the density functional theory. The electron conductivity of the C60-dimer bridge is low owing to the constraint of the junction of the molecules. When the fullerenes are doped electrons by being inserted Li atoms into the cages, the unoccupied state around the junction is filled and the conductivity can be significantly improved.
Elastocaloric Response of PbTiO3 Predicted from a First-Principles Effective Hamiltonian
NASA Astrophysics Data System (ADS)
Barr, Jordan A.; Beckman, Scott P.; Nishimatsu, Takeshi
2015-02-01
A first-principles effective Hamiltonian is used in a molecular dynamics simulation to study the elastocaloric effect in PbTiO3. It is found that the transition temperature is a linear function of uniaxial tensile stress. A negative temperature change is calculated, when the uniaxial tensile stress is switched off, as a function of the initial temperature ?T(Tinitial). It is predicted that the formation of domain structures under uniaxial tensile stress degrades the effectiveness of the elastocaloric effect.
Investigation of transient heat current from first principles using complex absorbing potential
NASA Astrophysics Data System (ADS)
Yu, Zhizhou; Zhang, Lei; Xing, Yanxia; Wang, Jian
2014-09-01
We report on a first-principles investigation of transient heat current through molecular devices under steplike pulse of external and gate voltages. Using the nonequilibrium Green's function (NEGF) approach, an exact solution of transient heat current is obtained that goes beyond the wide-band limit. Combining with density-functional theory (DFT), we propose a time-dependent NEGF-DFT formalism to study the transient heat current under a steplike pulse for molecular devices from first principles. Anticipating the huge computational cost in the transient regime, we develop an algorithm to speed up the calculation using the complex absorbing potential (CAP). By adding the CAP to replace the Hamiltonian of leads, the effective self-energy of the Green's function becomes independent of energy, allowing analytic calculation of the triple integrations in the exact solution of transient heat current using the theorem of residue. With this linear scaling algorithm, the computational complexity is greatly reduced, and a first-principles calculation of transient heat current of molecular devices becomes possible. As an example, we apply our NEGF-DFT-CAP formalism for a molecular device, the Di-thiol benzene molecule connected by two semi-infinite aluminum leads, and we calculate the transient heat current under an upward gate voltage pulse. The enhancement of heat current is observed.
Phonon thermal transport in strained and unstrained graphene from first principles
NASA Astrophysics Data System (ADS)
Lindsay, L.; Li, Wu; Carrete, Jesús; Mingo, Natalio; Broido, D. A.; Reinecke, T. L.
2014-04-01
A rigorous first principles Boltzmann-Peierls equation (BPE) for phonon transport approach is employed to examine the lattice thermal conductivity, ?L, of strained and unstrained graphene. First principles calculations show that the out-of-plane, flexural acoustic phonons provide the dominant contribution to ?L of graphene for all strains, temperatures, and system sizes considered, supporting a previous prediction that used an optimized Tersoff empirical interatomic potential. For the range of finite system sizes considered, we show that the ?L of graphene is relatively insensitive to strain. This provides validation for use of the BPE approach to calculate ?L for unstrained graphene, which has recently been called into question. The temperature and system size dependence of the calculated ?L of graphene is in good agreement with experimental data. The enhancement of ?L with isotopic purification is found to be relatively small due to strong anharmonic phonon-phonon scattering. This work provides insight into the nature of phonon thermal transport in graphene, and it demonstrates the power of first principles thermal transport techniques.
Zhang, Jian; Zhou, Bin; Sun, Zhenrong; Wang, Xue B.
2015-01-01
Proposed in theory and confirmed to exist, anion–? interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, intrinsic anion–? interaction strengths that are free from complications of condensed phases’ environments, have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl?, Br?, I?, linear thiocyanate SCN?, trigonal planar nitrate NO??, pyramidic iodate IO??, and tetrahedral sulfate SO?²?). The binding energies of the resultant gaseous 1:1 complexes (1•Cl?,1•Br?, 1•I?, 1•SCN?, 1•NO??, 1•IO?? and 1•SO?²?) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion specific effects. The binding strengths of Cl?, NO??, IO?? with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal/mol, but only about 40% of that between 1 and SO?²?. Quantum chemical calculations reveal that all anions reside in the center of the cavity of 1 with anion–? binding motif in the complexes’ optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and natural bond orbital charge distribution analysis further support anion–? binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work illustrates that size-selective photoelectron spectroscopy combined with theoretical calculations represent a powerful technique to probe intrinsic anion–? interactions and has potential to provide quantitative guest-host molecular binding strengths and unravel fundamental insights in specific anion recognitions.
Zhang, Jian; Zhou, Bin; Sun, Zhen-Rong; Wang, Xue-Bin
2015-02-01
Proposed in theory and then their existence confirmed, anion-? interactions have been recognized as new and important non-covalent binding forces. Despite extensive theoretical studies, numerous crystal structural identifications, and a plethora of solution phase investigations, anion-? interaction strengths that are free from complications of condensed-phase environments have not been directly measured in the gas phase. Herein we present a joint photoelectron spectroscopic and theoretical study on this subject, in which tetraoxacalix[2]arene[2]triazine 1, an electron-deficient and cavity self-tunable macrocyclic, was used as a charge-neutral molecular host to probe its interactions with a series of anions with distinctly different shapes and charge states (spherical halides Cl(-), Br(-), I(-), linear thiocyanate SCN(-), trigonal planar nitrate NO3(-), pyramidic iodate IO3(-), and tetrahedral sulfate SO4(2-)). The binding energies of the resultant gaseous 1?:?1 complexes (1·Cl(-), 1·Br(-), 1·I(-), 1·SCN(-), 1·NO3(-), 1·IO3(-) and 1·SO4(2-)) were directly measured experimentally, exhibiting substantial non-covalent interactions with pronounced anion-specific effects. The binding strengths of Cl(-), NO3(-), IO3(-) with 1 are found to be strongest among all singly charged anions, amounting to ca. 30 kcal mol(-1), but only about 40% of that between 1 and SO4(2-). Quantum chemical calculations reveal that all the anions reside in the center of the cavity of 1 with an anion-? binding motif in the complexes' optimized structures, where 1 is seen to be able to self-regulate its cavity structure to accommodate anions of different geometries and three-dimensional shapes. Electron density surface and charge distribution analyses further support anion-? binding formation. The calculated binding energies of the anions and 1 nicely reproduce the experimentally estimated electron binding energy increase. This work illustrates that size-selective photoelectron spectroscopy combined with theoretical calculations represents a powerful technique to probe anion-? interactions and has potential to provide quantitative guest-host molecular binding strengths and unravel fundamental insights in specific anion recognitions. PMID:25515705
NASA Astrophysics Data System (ADS)
Crampton, K. T.; Rathur, A. I.; Nei, Y.-w.; Berden, G.; Oomens, J.; Rodgers, M. T.
2012-09-01
Tautomerization induced by protonation of halouracils may increase their efficacy as anti-cancer drugs by altering their reactivity and hydrogen bonding characteristics, potentially inducing errors during DNA and RNA replication. The gas-phase structures of protonated complexes of five halouracils, including 5-fluorouracil, 5-chlorouracil, 5-bromouracil, 5-iodouracil, and 6-chlorouracil are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy and theoretical electronic structure calculations. IRMPD action spectra were measured for each complex in the IR fingerprint region extending from ~1000 to 1900 cm-1 using the free electron laser (FELIX). Correlations are made between the measured IRMPD action spectra and the linear IR spectra for the stable low-energy tautomeric conformations computed at the B3LYP/6-311+G(2d,2p)//B3LYP/6-31G* level of theory. Absence of an intense band(s) in the IRMPD spectrum arising from the carbonyl stretch(es) that are expected to appear near 1825 cm-1 provides evidence that protonation induces tautomerization and preferentially stabilizes alternative, noncanonical tautomers of these halouracils where both keto functionalities are converted to hydroxyl groups upon binding of a proton. The weak, but measurable absorption, which does occur for these systems near 1835 cm-1 suggests that in addition to the ground-state conformer, very minor populations of excited, low-energy conformers that contain keto functionalities are also present in these experiments.
Roy, S.; Gruenbaum, S. M.; Skinner, J. L.
2014-11-14
Understanding the structure of water near cell membranes is crucial for characterizing water-mediated events such as molecular transport. To obtain structural information of water near a membrane, it is useful to have a surface-selective technique that can probe only interfacial water molecules. One such technique is vibrational sum-frequency generation (VSFG) spectroscopy. As model systems for studying membrane headgroup/water interactions, in this paper we consider lipid and surfactant monolayers on water. We adopt a theoretical approach combining molecular dynamics simulations and phase-sensitive VSFG to investigate water structure near these interfaces. Our simulated spectra are in qualitative agreement with experiments and reveal orientational ordering of interfacial water molecules near cationic, anionic, and zwitterionic interfaces. OH bonds of water molecules point toward an anionic interface leading to a positive VSFG peak, whereas the water hydrogen atoms point away from a cationic interface leading to a negative VSFG peak. Coexistence of these two interfacial water species is observed near interfaces between water and mixtures of cationic and anionic lipids, as indicated by the presence of both negative and positive peaks in their VSFG spectra. In the case of a zwitterionic interface, OH orientation is toward the interface on the average, resulting in a positive VSFG peak.
Theoretical study of core-loss electron energy-loss spectroscopy at graphene nanoribbon edges.
Fujita, N; Hasnip, P J; Probert, M I J; Yuan, J
2015-08-01
A systematic study of simulated atomic-resolution electronic energy-loss spectroscopy (EELS) for different graphene nanoribbons (GNRs) is presented. The results of ab initio studies of carbon [Formula: see text] core-loss EELS on GNRs with different ribbon edge structures and different hydrogen terminations show that theoretical core-loss EELS can distinguish key structural features at the atomic scale. In addition, the combination of polarized core-loss EELS with symmetry resolved electronic partial density of states calculations can be used to identify the origins of all the primary features in the spectra. For example, the nature of the GNR edge structure (armchair, zigzag, etc) can be identified, along with the degree of hydrogenation. Hence it is possible to use the combination of ab initio calculations with high resolution, high energy transmission core-loss EELS experiments to determine the local atomic arrangement and chemical bonding states (i.e. a structural fingerprint) in GNRs, which is essential for future practical applications of graphene. PMID:26173149
Theoretical study of core-loss electron energy-loss spectroscopy at graphene nanoribbon edges
NASA Astrophysics Data System (ADS)
Fujita, N.; Hasnip, P. J.; Probert, M. I. J.; Yuan, J.
2015-08-01
A systematic study of simulated atomic-resolution electronic energy-loss spectroscopy (EELS) for different graphene nanoribbons (GNRs) is presented. The results of ab initio studies of carbon 1s core-loss EELS on GNRs with different ribbon edge structures and different hydrogen terminations show that theoretical core-loss EELS can distinguish key structural features at the atomic scale. In addition, the combination of polarized core-loss EELS with symmetry resolved electronic partial density of states calculations can be used to identify the origins of all the primary features in the spectra. For example, the nature of the GNR edge structure (armchair, zigzag, etc) can be identified, along with the degree of hydrogenation. Hence it is possible to use the combination of ab initio calculations with high resolution, high energy transmission core-loss EELS experiments to determine the local atomic arrangement and chemical bonding states (i.e. a structural fingerprint) in GNRs, which is essential for future practical applications of graphene.
Khokhlov, Alexei; Austin, Joanna
2015-03-02
Hydrogen has emerged as an important fuel across a range of industries as a means of achieving energy independence and to reduce emissions. DDT and the resulting detonation waves in hydrogen-oxygen can have especially catastrophic consequences in a variety of industrial and energy producing settings related to hydrogen. First-principles numerical simulations of flame acceleration and DDT are required for an in-depth understanding of the phenomena and facilitating design of safe hydrogen systems. The goals of this project were (1) to develop first-principles petascale reactive flow Navier-Stokes simulation code for predicting gaseous high-speed combustion and detonation (HSCD) phenomena and (2) demonstrate feasibility of first-principles simulations of rapid flame acceleration and deflagrationto- detonation transition (DDT) in stoichiometric hydrogen-oxygen mixture (2H2 + O2). The goals of the project have been accomplished. We have developed a novel numerical simulation code, named HSCD, for performing first-principles direct numerical simulations of high-speed hydrogen combustion. We carried out a series of validating numerical simulations of inert and reactive shock reflection experiments in shock tubes. We then performed a pilot numerical simulation of flame acceleration in a long pipe. The simulation showed the transition of the rapidly accelerating flame into a detonation. The DDT simulations were performed using BG/Q Mira at the Argonne National Laboratiory, currently the fourth fastest super-computer in the world. The HSCD is currently being actively used on BG/QMira for a systematic study of the DDT processes using computational resources provided through the 2014-2016 INCITE allocation ”First-principles simulations of high-speed combustion and detonation.” While the project was focused on hydrogen-oxygen and on DDT, with appropriate modifications of the input physics (reaction kinetics, transport coefficients, equation of state) the code has a much broader applicability to petascale simulations of high speed combustion and detonation phenomena in reacting gases, and to high speed viscous gaseous flows in general. Project activities included three major steps – (1) development of physical and numerical models, (2) code validation, and (3) demonstration simulation of flame acceleration and DDT in a long pipe.
Electron spectroscopy of carbon materials: experiment and theory
NASA Astrophysics Data System (ADS)
El-Barbary, A. A.; Trasobares, S.; Ewels, C. P.; Stephan, O.; Okotrub, A. V.; Bulusheva, L. G.; Fall, C. J.; Heggie, M. I.
2006-02-01
We present a comparative spectroscopic study of carbon as graphite, diamond and C60 using C1s K-edge electron energy-loss spectroscopy (EELS), X-ray emission spectroscopy, and theoretical modelling. The first principles calculations of these spectra are obtained in the local density approximation using a self-consistent Gaussian basis pseudo-potential method. Calculated spectra show excellent agreement with experiment and are able to discriminate not only between various carbon hybridisations but also local variation in environment. Core-hole effects on the calculated spectra are also investigated. For the first time, the EEL spectrum of carbyne is calculated.
Subramanian, Venkat
Parameter Estimation and Capacity Fade Analysis of Lithium-Ion Batteries Using First parameters of lithium-ion batteries are estimated using a first-principles electrochemical engineering model and understanding of lithium-ion batteries using physics-based first-principles models. These models are based
Kanai, Shun; Tsujikawa, Masahito; Shirai, Masafumi; Miura, Yoshio; Matsukura, Fumihiro Ohno, Hideo
2014-12-01
We study the spin and orbital magnetic moments in Ta/Co{sub 0.4}Fe{sub 0.4}B{sub 0.2}/MgO by x-ray magnetic circular dichroism measurements as well as first-principles calculations, in order to clarify the origin of the perpendicular magnetic anisotropy. Both experimental and theoretical results show that orbital magnetic moment of Fe is more anisotropic than that of Co with respect to the magnetization direction. The anisotropy is larger for thinner CoFeB, indicating that Fe atoms at the interface with MgO contribute more than Co to the observed perpendicular magnetic anisotropy.
Identification of hydrogen defects in SrTiO3 by first principles local vibrational mode calculations
T-Thienprasert, J; Fongkaew, Ittipon; Singh, David J; Du, Mao-Hua; Limpijumnong, Sukit
2012-01-01
For over three decades, the infrared spectroscopy peaks of around 3500 cm{sup -1} observed in hydrogen-doped SrTiO{sub 3} samples have been assigned to an interstitial hydrogen (H{sub i}) attached to a lattice oxygen with two possible configuration models: the octahedral edge (OE) and the cubic face (CF) models. Based on our first-principles calculations of H{sub i} around O, both OE and CF configurations are not energetically stable. Starting from either configuration, the H{sub i} would spontaneously relax into an off axis (OA) site; lowering the energy by 0.25 eV or more. The calculated vibrational frequency of 2745 cm{sup -1} for OA invalidates the assignment of H{sub i} to the observed 3500 cm{sup -1} peak. In addition, the calculated diffusion barrier is low, suggesting that H{sub i} can be easily annealed out. We propose that the observed peaks around 3500 cm{sup -1} are associated with defect complexes. A Sr vacancy (V{sub Sr}) can trap H{sub i} and form a H-V{sub Sr} complex which is both stable and has the frequency in agreement with the observed main peak. The complex can also trap another H{sub i} and form 2H-V{sub Sr}; consistent with the observed additional peaks at slightly higher frequencies (3510-3530 cm{sup -1}).
NASA Astrophysics Data System (ADS)
Nishida, Naohiro; Kanai, Seiji; Tokushima, Takashi; Horikawa, Yuka; Takahashi, Osamu
2015-11-01
We have performed theoretical calculations to reproduce the site-selective X-ray emission spectroscopy (XES) spectra of liquid acetic acid at the oxygen K-edge (OCdbnd O,1s and OOH,1s). Structure sampling of an acetic acid cluster model was performed from the ab initio molecular dynamics trajectory. Relative XES intensities for the core-hole excited state dynamics simulations were calculated using density functional theory. We found that the theoretical XES spectra reproduced well the experimental spectra and that these calculations gave us electronic and molecular structure information about liquid acetic acid.
First-principles study of water on copper and noble metal (110) surfaces
Ren, Jun; Meng, Sheng
2008-02-01
Water structure and dissociation kinetics on a model open metal surface: Cu(110), has been investigated in detail based on first-principles electronic structure calculations. We revealed that in both monomer and overlayer forms, water adsorbs molecularly, with a high tendency for diffusion and/or desorption rather than dissociation on clean surfaces at low temperature. Studying water on other noble metal (110) surfaces confirms that Cu(110) is the borderline between intact and dissociative water adsorption, differing in energy by only 0.08 eV. This may lead to promising applications in hydrogen generation and fuel cells.
Crystal structure prediction from first principles: The crystal structures of glycine
NASA Astrophysics Data System (ADS)
Lund, Albert M.; Pagola, Gabriel I.; Orendt, Anita M.; Ferraro, Marta B.; Facelli, Julio C.
2015-04-01
Here we present the results of our unbiased searches of glycine polymorphs obtained using the genetic algorithms search implemented in MGAC, modified genetic algorithm for crystals, coupled with the local optimization and energy evaluation provided by Quantum Espresso. We demonstrate that it is possible to predict the crystal structures of a biomedical molecule using solely first principles calculations. We were able to find all the ambient pressure stable glycine polymorphs, which are found in the same energetic ordering as observed experimentally and the agreement between the experimental and predicted structures is of such accuracy that the two are visually almost indistinguishable.
NASA Astrophysics Data System (ADS)
Maibam, Jameson; Indrajit Sharma, B.; Bhattacharjee, Ramendu; Thapa, R. K.; Brojen Singh, R. K.
2011-11-01
We have studied the electronic, structural, and elastic properties of scandium carbide and yttrium carbide by means of accurate first principles total energy calculations using the full-potential linearized plane wave method (FP-LAPW). We have used the generalized gradient approximation (GGA) for the exchange and correlation potential. Volume optimization, energy band structure, and density of states (DOS) of the systems are presented. The second order elastic constants have been calculated and other related quantities such as the Zener anisotropy factor, Poisson's ratio, Young's modulus, Kleinman parameter, Debye temperature, and sound velocities have been determined. The band gap calculation shows that YC is relatively more ionic than ScC.
First Principles Calculations of Oxygen Adsorption on the UN(001) Surface
Zhukovskii, Yuri F.; Bocharov, Dmitry; Kotomin, Eugene Alexej; Evarestov, Robert; Bandura, A. V.
2009-01-01
Fabrication, handling and disposal of nuclear fuel materials require comprehensive knowledge of their surface morphology and reactivity. Due to unavoidable contact with air components (even at low partial pressures), UN samples contain considerable amount of oxygen impurities affecting fuel properties. In this study we focus on reactivity of the energetically most stable (001) substrate of uranium nitride towards the atomic oxygen as one of initial stages for further UN oxidation. The basic properties of O atoms adsorbed on the UN(001) surface are simulated here combining the two first principles calculation methods based on the plane wave basis set and that of the localized orbitals.
First principles calculations of oxygen adsorption on the UN(0 0 1) surface
NASA Astrophysics Data System (ADS)
Zhukovskii, Yu. F.; Bocharov, D.; Kotomin, E. A.; Evarestov, R. A.; Bandura, A. V.
2009-01-01
Fabrication, handling and disposal of nuclear fuel materials require comprehensive knowledge of their surface morphology and reactivity. Due to unavoidable contact with air components (even at low partial pressures), UN samples contain considerable amount of oxygen impurities affecting fuel properties. In this study we focus on reactivity of the energetically most stable (0 0 1) substrate of uranium nitride towards the atomic oxygen as one of initial stages for further UN oxidation. The basic properties of O atoms adsorbed on the UN(0 0 1) surface are simulated here combining the two first principles calculation methods based on the plane wave basis set and that of the localized orbitals.
First principles calculation of the energy and structure of two solid surface phases on Ir?100?
NASA Astrophysics Data System (ADS)
Ge, Q.; King, D. A.; Marzari, N.; Payne, M. C.
1998-12-01
The structure and energetics of the hexagonal reconstruction of Ir{100} have been determined with first principles density functional theory calculations based on the local-density approximation with the generalised-gradient correction. The results reproduced the experimentally determined surface buckling and show the presence of some lateral displacement of the reconstructed (1×5) phase with respect to the ideal hexagonal close packed structure. The (1×5) phase is found to be 0.06 eV/(1×1 area) more stable than the (1×1) phase. The reconstruction is analysed by examining surface bonding.
Carrier compensation in semi-insulating CdTe: First-principles calculations
Du, Mao-Hua; Singh, David J
2008-01-01
Carrier compensation in semi-insulating CdTe has been attributed to the compensation of surplus shallow acceptors by deep donors, usually assumed to be Te antisites. However, our first-principles calculations show that intrinsic defects should not have a significant effect on the carrier compensation due either to lack of deep levels near midgap or to low defect concentration. We demonstrate that an extrinsic defect, OTe-H complex, may play an important role in the carrier compensation in CdTe because of its amphoteric character and reasonably high concentration. Our findings have important consequences for improving device performance in CdTe-based radiation detectors and solar cells.
Superlubricity of two-dimensional fluorographene/MoS2 heterostructure: a first-principles study.
Wang, Lin-Feng; Ma, Tian-Bao; Hu, Yuan-Zhong; Zheng, Quanshui; Wang, Hui; Luo, Jianbin
2014-09-26
The atomic-scale friction of the fluorographene (FG)/MoS2 heterostructure is investigated using first-principles calculations. Due to the intrinsic lattice mismatch and formation of periodic Moiré patterns, the potential energy surface of the FG/MoS2 heterostructure is ultrasmooth and the interlayer shear strength is reduced by nearly two orders of magnitude, compared with both FG/FG and MoS2/MoS2 bilayers, entering the superlubricity regime. The size dependency of superlubricity is revealed as being based on the relationship between the emergence of Moiré patterns and the lattice mismatch ratio for heterostructures. PMID:25180979
Zhou, Bin; Guo, Wanlin; Tang, Chun
2008-02-20
We report a systematic investigation of the charging effect on hydrogen molecule chemisorption on (3, 3), (5, 5), (5, 0), and (8, 0) carbon nanotubes by first-principles calculations. The influence of injected charge on the chemisorption energy barriers is found to be sensitive to the nanotube diameter and chirality. The calculated results also indicate that electron injection is more effective in lowering the energy barrier for armchair carbon nanotubes while hole injection is more effective for zigzag nanotubes. The origin of these interesting trends and systematics can be understood by a close examination of the underlying electronic structure and the electron transfer between the hydrogen molecules and the nanotubes. PMID:21817655
First-principles study of lithium adsorption and diffusion on graphene: the effects of strain
NASA Astrophysics Data System (ADS)
Hao, Feng; Chen, Xi
2015-10-01
Large strain is produced within graphene sheets, which serve as a critical component in lithium-ion batteries, due to the expansion of the electrodes. First-principles calculations are therefore employed to investigate the interaction of Li with strained single-layer graphene. It is found that tensile strain enhances Li binding on graphene and significantly reduces the formation energy of divacancies. In addition, Li diffusion through graphene with defects is facilitated by tensile strain, whereas diffusion parallel to the plane of pristine graphene is slightly hindered.
Structure and bonding of dense liquid oxygen from first principles simulations
Burkhard Militzer; Francois Gygi; Giulia Galli
2003-02-25
Using first principles simulations we have investigated the structural and bonding properties of dense fluid oxygen up to 180 GPa. We have found that band gap closure occurs in the molecular liquid, with a "slow" transition from a semi-conducting to a poor metallic state occurring over a wide pressure range. At approximately 80 GPa, molecular dissociation is observed in the metallic fluid. Spin fluctuations play a key role in determining the electronic structure of the low pressure fluid, while they are suppressed at high pressure.
First-principles molecular-dynamics simulations for neutral p-chloranil and its radical anion
NASA Astrophysics Data System (ADS)
Katan, C.; Blöchl, P. E.; Margl, P.; Koenig, C.
1996-05-01
The neutral p-chloranil (2,3,5,6-tetrachloro-p-benzoquinone) and its radical anion have been extensively studied using the Car-Parrinello projector augmented wave method, which is an all-electron electronic structure method for first-principles molecular dynamics based on the local density approximation of density functional theory. Frequencies and eigenmodes are derived by fitting a system of harmonic oscillators to the molecular-dynamics trajectories. The dependence of the bond lengths and vibrational frequencies on the molecular ionicity is discussed, and the electron affinity, Coulomb repulsion, and the spin-splitting parameter of p-chloranil are also derived.
NASA Astrophysics Data System (ADS)
Hu, S. X.; Goncharov, V. N.; Boehly, T. R.; McCrory, R. L.; Skupsky, S.; Collins, L. A.; Kress, J. D.; Militzer, B.
2015-05-01
A comprehensive knowledge of the properties of high-energy-density plasmas is crucial to understanding and designing low-adiabat, inertial confinement fusion (ICF) implosions through hydrodynamic simulations. Warm-dense-matter (WDM) conditions are routinely accessed by low-adiabat ICF implosions, in which strong coupling and electron degeneracy often play an important role in determining the properties of warm dense plasmas. The WDM properties of deuterium-tritium (DT) mixtures and ablator materials, such as the equation of state, thermal conductivity, opacity, and stopping power, were usually estimated by models in hydro-codes used for ICF simulations. In these models, many-body and quantum effects were only approximately taken into account in the WMD regime. Moreover, the self-consistency among these models was often missing. To examine the accuracy of these models, we have systematically calculated the static, transport, and optical properties of warm dense DT plasmas, using first-principles (FP) methods over a wide range of densities and temperatures that cover the ICF "path" to ignition. These FP methods include the path-integral Monte Carlo (PIMC) and quantum-molecular dynamics (QMD) simulations, which treat electrons with many-body quantum theory. The first-principles equation-of-state table, thermal conductivities (?QMD), and first principles opacity table of DT have been self-consistently derived from the combined PIMC and QMD calculations. They have been compared with the typical models, and their effects to ICF simulations have been separately examined in previous publications. In this paper, we focus on their combined effects to ICF implosions through hydro-simulations using these FP-based properties of DT in comparison with the usual model simulations. We found that the predictions of ICF neutron yield could change by up to a factor of ˜2.5; the lower the adiabat of DT capsules, the more variations in hydro-simulations. The FP-based properties of DT are essential for designing ICF ignition targets. Future work on first-principles studies of ICF ablator materials is also discussed.
First-principles theory of quantum well resonance in double barrier magnetic tunnel junctions
Wang, Y.; Lu, Zhong-Yi; Zhang, Xiaoguang; Han, Prof. X. F.
2006-01-01
Quantum well (QW) resonances in Fe(001)/MgO/Fe/MgO/Fe double barrier magnetic tunnel junctions are calculated from the first-principles. By including the Coulomb blockade energy due to the finite size islands of the Fe middle layer, we confirm that the oscillatory differential resistance observed in a recent experiment, T. Nozaki et al, Phys. Rev. Lett. {\\bf 96}, 027208 (2006), originates from the QW resonances from the $\\Delta_1$ band of the Fe majority spin channel. The primary source of smearing at low temperatures is shown to be the variation of the Coulomb blockade energy.
First principles calculation of the effect of Coulomb collisions in partially ionized gases
Donkó, Z.
2014-04-15
Coulomb collisions, at appreciable ratios (?) of the electron to the neutral particle density, influence significantly the electron kinetics in particle swarms and in plasmas of gas discharges. This paper introduces a combination of Molecular Dynamics and Monte Carlo simulation techniques, to provide a novel, approximation-free, first principles calculation method for the velocity distribution function of electrons, and related swarm characteristics, at arbitrary ?. Simulation results are presented for electrons in argon gas, for density ratios between zero and 10{sup ?1}, representing the limits of a negligible electron density and an almost complete Maxwellization of the velocity distribution function, respectively.
A First Principles Investigation of the Electronic Structure of Actinide Oxides
Petit, Leon; Svane, Axel; Szotek, Zdzislawa; Temmerman, Walter M; Stocks, George Malcolm
2010-04-01
The ground state electronic structures of the actinide oxides AO, A{sub 2}O{sub 3} and AO{sub 2} (A=U, Np, Pu, Am, Cm, Bk, Cf) are determined from first-principles calculations using the self-interaction corrected local spin-density approximation. Our study reveals a strong link between preferred oxidation number and degree of localization. The ionic nature of the actinide oxides emerges from the fact that those oxides where the ground state is calculated to be metallic do not exist in nature, as the corresponding delocalized f-states favour the accommodation of additional O atoms into the crystal lattice.
NASA Astrophysics Data System (ADS)
Lazic, Predrag; Sipahi, Guilherme; Kawakami, Roland; Zutic, Igor
2013-03-01
Recent experimental advances in graphene suggest intriguing opportunities for novel spintronic applications which could significantly exceed the state-of-the art performance of their conventional charge-based counterparts. However, for reliable operation of such spintronic devices it is important to achieve an efficient spin injection and large magnetoresistive effects. We use the first principles calculations to guide the choice of a ferromagnetic region and its relative orientation to optimize the desired effects. We propose structures which could enable uniform spin injection, one of the key factors in implementing scalable spintronic circuits. Supported by NSF-NRI, SRC, ONR, Croatian Ministry of Science, Education, and Sports, and CCR at SUNY UB.
Phonon transport in perovskite SrTiO3 from first principles
Feng, Lei; Shiomi, Junichiro
2015-01-01
We investigate phonon transport in perovskite strontium titanate (SrTiO3) which is stable above its phase transition temperature (~105 K) by using first-principles molecular dynamics and anharmonic lattice dynamics. Unlike conventional ground-state-based perturbation methods that give imaginary phonon frequencies, the current calculation reproduces stable phonon dispersion relations observed in experiments. We find the contribution of optical phonons to overall lattice thermal conductivity is larger than 60%, markedly different from the usual picture with dominant contribution from acoustic phonons. The mode- and pseudopotential-dependence analysis suggests the strong attenuation of acoustic phonons transport originated from strong anharmonic coupling with the transversely-polarized ferroelectric modes.
Sum-rules and quantum limits: nonlinear optics from first principles
NASA Astrophysics Data System (ADS)
Pérez-Moreno, Javier; Clays, Koen; Kuzyk, Mark G.
2008-04-01
Much progress has been made in improving the molecular hyperpolarizability by constructing larger structures with lots of pi-delocalized electrons. This bigger-is-better approach does not answer a more fundamental question of what intrinsic molecular properties yield the largest response. We introduce a novel analysis (the quantum limits analysis) which is simple to apply and combines first principles with experimental results. The quantum limits analysis allows us to determine the intrinsic nonlinear efficiency of a structure and highlights the underlying physical principles behind the nonlinear response of molecules.
First-principles calculation of electronic properties of isoelectronic impurity complexes in Si
NASA Astrophysics Data System (ADS)
Iizuka, Shota; Nakayama, Takashi
2015-08-01
The electronic properties of isoelectronic impurity complexes in Si, such as Al+N and Mg+O, are studied by first-principles calculations. It is shown that cation and anion impurity atoms prefer to locate at the nearest-neighboring sites and produce an electron-unoccupied state in the band gap of Si. This state is made up of the 3s orbital of N/O atoms, which hybridizes with 3s and 3p orbitals of the cation and Si, and is localized around N/O atoms. The chemical trend of the isoelectronic impurity complex on changing the type of constituent atom is also discussed.
NASA Astrophysics Data System (ADS)
Lischner, Johannes; Bazhirov, Timur; MacDonald, Allan H.; Cohen, Marvin L.; Louie, Steven G.
2015-01-01
We present first-principles calculations of the coupling of quasiparticles to spin fluctuations in iron selenide and discuss which types of superconducting instabilities this coupling gives rise to. We find that strong antiferromagnetic stripe-phase spin fluctuations lead to large coupling constants for superconducting gaps with s± symmetry, but these coupling constants are significantly reduced by other spin fluctuations with small wave vectors. An accurate description of this competition and an inclusion of band-structure and Stoner parameter renormalization effects lead to a value of the coupling constant for an s±-symmetric gap which can produce a superconducting transition temperature consistent with experimental measurements.
Liquid–liquid phase transition in compressed hydrogen from first-principles simulations
Scandolo, Sandro
2003-01-01
The properties of compressed liquid hydrogen, the most abundant fluid in the universe, have been investigated by means of first-principles molecular dynamics at pressures between 75 and 175 GPa and temperatures closer to the freezing line than so far reported in shock-wave experiments. Evidence for a liquid–liquid transition between a molecular and a dissociated phase is provided. The transition is accompanied by a 6% increase in density and by metallization. This finding has important implications for our understanding of the interiors of giant planets and supports predictions of a quantum fluid state at low temperatures. PMID:12626753
First-principles study of migration mechanisms and diffusion of carbon in GaN
NASA Astrophysics Data System (ADS)
Kyrtsos, Alexandros; Matsubara, Masahiko; Bellotti, Enrico
2015-09-01
Carbon related defects are readily incorporated in GaN due to its abundance during growth both with MBE and CVD techniques. Employing first-principles calculations we compute the migration barrier of neutral carbon interstitials in the wurtzite GaN crystal. The Minimum Energy Path (MEP) and the migration barriers of these defects are obtained using the Nudged Elastic Band (NEB) method with the climbing image modification (CI-NEB). In addition, the Dimer method is used to verify the results. The results yield a quantitative description of carbon diffusion in the crystal allowing for the determination of the most probable migration paths.
First-Principles Study on ?-SiC/BNNT Core/shell Nanocable
NASA Astrophysics Data System (ADS)
Zou, X. C.; Ouyang, J.; Wu, M. S.; Liu, G.; Lei, X. L.; Ouyang, C. Y.; Xu, B.
2013-09-01
In this paper, we studied the structural and electronic properties of core/shell nanocables composed of cubic silicon carbide nanowires (?-SiCNW) and boron nitride nanotubes (BNNT) using first-principles pseudopotential plane wave method within density functional theory. Our results show that the ?-SiC/BNNT heterojunction structures are metallic, which primarily originates from the contributions of the BNNTs and the surfaces of SiCNWs. The BNNTs exhibit metallic characters after the SiC nanowires are inserted. The transition of the BNNTs is attributed to the charge transfer between BNNTs and SiCNWs.
Structural phase transition and elastic properties of hafnium dihydride: A first principles study
Santhosh, M. Rajeswarapalanichamy, R. Sudhapriyanga, G.; Murugan, A.; Chinthia, A. Jemmy; Kanagaprabha, S.; Iyakutti, K.
2014-04-24
The structural and elastic properties of Hafnium dihydride (HfH{sub 2}) are investigated by first principles calculation based on density functional theory using Vienna ab-initio simulation package (VASP). The calculated lattice parameters are in good agreement with the available results. A pressure induced structural phase transition from CaF{sub 2} to FeS{sub 2} phase is observed in HfH{sub 2} at 10.75 GPa. The calculated elastic constants indicate that this hydride is mechanically stable at ambient condition.
Half metallic ferromagnetism in alkali metal nitrides MN (M = Rb, Cs): A first principles study
Murugan, A. Rajeswarapalanichamy, R. Santhosh, M. Sudhapriyanga, G.; Kanagaprabha, S.
2014-04-24
The structural, electronic and elastic properties of two alkali metal nitrides (MN: M= Rb, Cs) are investigated by the first principles calculations based on density functional theory using the Vienna ab-initio simulation package. At ambient pressure the two nitrides are stable in ferromagnetic state with CsCl structure. The calculated lattice parameters are in good agreement with the available results. The electronic structure reveals that these materials are half metallic in nature. A pressure-induced structural phase transition from CsCl to ZB phase is observed in RbN and CsN.
Dielectric Properties of Ice and Liquid Water from First-Principles Calculations
NASA Astrophysics Data System (ADS)
Lu, Deyu; Gygi, François; Galli, Giulia
2008-04-01
We present a first-principles study of the static dielectric properties of ice and liquid water. The eigenmodes of the dielectric matrix ? are analyzed in terms of maximally localized dielectric functions similar, in their definition, to maximally localized Wannier orbitals obtained from Bloch eigenstates of the electronic Hamiltonian. We show that the lowest eigenmodes of ?-1 are localized in real space and can be separated into groups related to the screening of lone pairs, intra-, and intermolecular bonds, respectively. The local properties of the dielectric matrix can be conveniently exploited to build approximate dielectric matrices for efficient, yet accurate calculations of quasiparticle energies.
Van An Dinh; Sato, Kazunori; Katayama-Yoshida, Hiroshi
2010-01-04
A first principle study of half-metallicity and ferromagnetism in half-heusler alloys NiMnZ (Z = Si, P, Ge, As, and Sb) is given. The half-metallicity and ferromagnetism are predicted via the calculation of electronic structure, and Curie temperature. The stability of the orthorhombic and tetragonal structures and C1{sub b} at various values of lattice parameters is also studied by means of the pseudo-potential method. All alloys exhibit the half-metallicity and ferromagnetism above room temperature.
NASA Astrophysics Data System (ADS)
Lee, Hyung-June; Kim, Gunn; Kwon, Young-Kyun
2013-08-01
Using first-principles calculations, we investigate the electronic structures and binding properties of nicotine and caffeine adsorbed on single-walled carbon nanotubes to determine whether CNTs are appropriate for filtering or sensing nicotine and caffeine molecules. We find that caffeine adsorbs more strongly than nicotine. The different binding characteristics are discussed by analyzing the modification of the electronic structure of the molecule-adsorbed CNTs. We also calculate the quantum conductance of the CNTs in the presence of nicotine or caffeine adsorbates and demonstrate that the influence of caffeine is stronger than nicotine on the conductance of the host CNT.
Hydrogen effect on shearing and cleavage of Al: A first-principles study
NASA Astrophysics Data System (ADS)
Apostol, F.; Mishin, Y.
2011-09-01
We report on first-principles calculations of the effect of a (111) hydrogen layer embedded in Al on generalized stacking fault energies and cleavage energy for different choices of the slip and cleavage planes. It is shown that the H layer softens Al against shear by reducing the stable and unstable stacking fault energies relative to pure Al. This finding points to a possible enhancement of plasticity of Al by H. The H layer also reduces the cleavage energy on the (111) plane. The reductions in the cleavage energy and unstable stacking fault energy compensate each other and produce only a moderate change in the Rice criterion of ductile versus brittle fracture.
NASA Astrophysics Data System (ADS)
Guan, Qiushi; Chen, Xiaojun; Gao, Tao; Xiao, Chengjian; Zhao, Linjie; He, Jianchao; Long, Xinggui
2015-10-01
Pentalithium aluminate, Li5AlO4, has attracted increasing attention for its high lithium density and potential uses in tritium breeding materials and thermal batteries. In this work, the structural, electronic, lattice dynamical, and thermodynamic properties of ?- and ?-phase Li5AlO4 were investigated using first-principles density functional theory. The optimized structural parameters were consistent with the experimental values, with the absolute deviation being less than 2.5%. The indirect band gaps of ?- and ?-Li5AlO4 were 4.82 and 5.16 eV, respectively, showing that they are insulators. In addition, the vibrational properties of ?- and ?-Li5AlO4 were computed using density functional perturbation theory. By adding Born effective charges into the phonon calculations, the longitudinal optical-transverse optical (LO-TO) splittings were calculated. The optical modes at the ? point were categorized as Raman- and IR-active modes. Our results show that ?-Li5AlO4 is more polar and anisotropic than ?-Li5AlO4. Furthermore, their thermodynamic functions were determined using the calculated phonon density of states. The results were in good agreement with those of previous theoretical studies. The data presented in this work will help in the further characterization of Li5AlO4, which may be valuable for future experimental studies.
NASA Astrophysics Data System (ADS)
Liu, Qi-Jun; Zhang, Ning-Chao; Liu, Fu-Sheng; Liu, Zheng-Tang
2014-07-01
Titanium dioxide is well known as a semiconductor material, which attracts a great deal of attention for promising applications in many fields due to its outstanding physical and chemical properties. To investigate the structural, elastic, mechanical, electronic and optical properties of various TiO2 phases systematically, we present the ultrasoft pseudopotential planewave method within local density approximation and generalized gradient approximation, as well as the norm-conserving pseudopotential within hybrid functional B3LYP by first-principles calculations on fluorite, pyrite, rutile, anatase, hollandite, brookite, columbite, cotunnite, bronze and baddeleyite TiO2 phases. The structural parameters of ten phases are calculated, which are shown to be consistent with previous theoretical and experimental data. We obtain the elastic constants of ten phases and then estimate the bulk, shear and Young’s moduli, Poisson’s coefficient and Lamé’s constants using the Voigt-Reuss-Hill approximation. The energy band structures, density of states and charge populations of ten phases were obtained and indicated there is covalency in TiO2. Moreover, the complex dielectric function, refractive index and extinction coefficient of the ten phases were calculated; this data can aid future experimental research.
Study of Pb-doped Ge2Sb2Te5 in crystalline phase using first principle calculations
NASA Astrophysics Data System (ADS)
Singh, Janpreet; Singh, Gurinder; Kaura, Aman; Tripathi, S. K.
2015-08-01
To improve the phase change characteristics of Ge2Sb2Te5 (GST), doping is used as one of the effective methods. 4.4 atomic % of Pb doped GST has been studied using first principle calculations. No effect of doping on Te-Ge and Te-Sb bond length has been observed, but the Te-Te bond gets shrink with Pb doping. Due to which the Sb2Te3 segregates as a second phase, with increased doping concentration of Pb in GST alloy. Using such type of calculation, we can calculate the desirable concentration of dopant atoms to prepare the desired material. We can control any segregation in required material with pre-theoretical calculations. The metallic nature of Pd doped GST has been discussed with band structure plots. The metallic character of alloys calculated as in this paper will be helpful to understand the tuning of conductivity of phase change materials, which helps to enhance the phase change properties.
First-principles study of the electronic and structural properties of (CdTe)n/(ZnTe)n superlattices
NASA Astrophysics Data System (ADS)
Boucharef, M.; Benalia, S.; Rached, D.; Merabet, M.; Djoudi, L.; Abidri, B.; Benkhettou, N.
2014-11-01
We present the results of a first-principles study of the electronic and structural properties of binary CdTe and ZnTe compounds and their (CdTe)n/(ZnTe)n superlattices (SLs). The computational method is based on the full-potential linear muffin tin orbitals method (FP-LMTO) augmented by a plane-wave basis (PLW). The exchange and correlation energy is described in the local density approximation (LDA) using the Perdew-Wang parameterization including a generalized gradient approximation (GGA). The calculated structural properties of CdTe and ZnTe compounds are in good agreement with available experimental and theoretical data. We have also carried out band-structure calculations for the binary CdTe and ZnTe compounds and their (CdTe)n/(ZnTe)n superlattices (SLs). From the results of the electronic properties, we find that the parent material CdTe and ZnTe and their superlattices have a direct band gaps. The fundamental band gap decreases with increasing the number of monolayer n.
NASA Astrophysics Data System (ADS)
Djoudi, L.; Merabet, M.; Boucharef, M.; Benalia, S.; Rached, D.
2014-11-01
Structural, electronic and optical properties of binary BeTe and CdS compounds and their (BeTe)n/(CdS)n superlattices (SLs) are investigated using the first-principles full potential linear muffin-tin orbitals method (FP-LMTO). The exchange-correlation potential is treated with the local density approximation of Perdew and Wang (LDA-PW). The ground-state properties are determined for the bulk materials (BeTe, CdS, and (BeTe)n/(CdS)n) in cubic phase. The calculated structural properties of BeTe and CdS compounds are in good agreement with available experimental and theoretical data. It is found that BeTe exhibit an indirect fundamental band gap and CdS and their superlattices (SLs) exhibit a direct fundamental band gap, which might make (BeTe)n/(CdS)n superlattices (SLs) materials promising and useful for optoelectronic applications. The fundamental band gap decreases with increasing the number of monolayer n.
NASA Astrophysics Data System (ADS)
Zhang, Z. Y.; Si, M. S.; Peng, S. L.; Zhang, F.; Wang, Y. H.; Xue, D. S.
2015-11-01
Blue phosphorene (BP) was theoretically predicted to be thermally stable recently. Considering its similar in-layer hexagonal lattice to MoS2, MoS2 could be an appropriate substrate to grow BP in experiments. In this work, the van der Waals (vdW) heterostructures are constructed by stacking BP on top of MoS2. The thermal stability and electronic structures are evaluated based on first principles calculations with vdW-corrected exchange-correlation functional. The formation of the heterostructures is demonstrated to be exothermic and the most stable stacking configuration is confirmed. The heterostructures BP/MoS2 preserve both the properties of BP and MoS2 but exhibit relatively narrower bandgaps due to the interlayer coupling effect. The band structures can be further engineered by applying external electric fields. An indirect-direct bandgap transition in bilayer BP/MoS2 is demonstrated to be controlled by the symmetry property of the built-in electric dipole fields.
NASA Astrophysics Data System (ADS)
Kondo, Kei-Ichi
2010-09-01
We give a theoretical framework to obtain a low-energy effective theory of quantum chromodynamics (QCD) towards a first-principle derivation of confinement/deconfinement and chiral-symmetry breaking/restoration crossover transitions. In fact, we demonstrate that an effective theory obtained using simple but nontrivial approximations within this framework enables us to treat both transitions simultaneously on equal footing. A resulting effective theory is regarded as a modified and improved version of nonlocal Polyakov-loop extended Nambu-Jona-Lasinio (nonlocal PNJL) models proposed recently by Hell, Rössner, Cristoforetti, and Weise, and Sasaki, Friman, and Redlich, extending the original (local) PNJL model by Fukushima and others. A novel feature is that the nonlocal NJL coupling depends explicitly on the temperature and Polyakov loop, which affects the entanglement between confinement and chiral-symmetry breaking, together with the cross term introduced through the covariant derivative in the quark sector considered in the conventional PNJL model. The chiral-symmetry breaking/restoration transition is controlled by the nonlocal NJL interaction, while the confinement/deconfinement transition in the pure gluon sector is specified by the nonperturbative effective potential for the Polyakov loop obtained recently by Braun, Gies, Marhauser, and Pawlowski. The basic ingredients are a reformulation of QCD based on new variables and the flow equation of the Wetterich type in the Wilsonian renormalization group. This framework can be applied to investigate the QCD phase diagram at finite temperature and density.
Energetics and magnetism of Co-doped GaN(0001) surfaces: A first-principles study
Qin, Zhenzhen; Xiong, Zhihua Chen, Lanli; Qin, Guangzhao
2014-12-14
A comprehensive first-principles study of the energetics, electronic, and magnetic properties of Co-doped GaN(0001) thin films are presented and the effect of surface structure on the magnetic coupling between Co atoms is demonstrated. It is found that Co atoms prefer to substitute the surface Ga sites in different growth conditions. In particular, a CoN/GaN interface structure with Co atoms replacing the first Ga layer is preferred under N-rich and moderately Ga-rich conditions, while CoGa{sub x}/GaN interface is found to be energetically stable under extremely Ga-rich conditions. It is worth noted that the antiferromagnetic coupling between Co atoms is favorable in clean GaN(0001) surface, but the existence of ferromagnetism would be expected to occur as Co concentration increased in Ga-bilayer GaN(0001) surface. Our study provides the theoretical understanding for experimental research on Co-doped GaN films and might promise the Co:GaN system potential applications in spin injection devices.
NASA Astrophysics Data System (ADS)
Thore, A.; Dahlqvist, M.; Alling, B.; Rosén, J.
2014-09-01
In this paper, we report the by first-principles predicted properties of the recently discovered magnetic MAX phase Mn2GaC. The electronic band structure and vibrational dispersion relation, as well as the electronic and vibrational density of states, have been calculated. The band structure close to the Fermi level indicates anisotropy with respect to electrical conductivity, while the distribution of the electronic and vibrational states for both Mn and Ga depend on the chosen relative orientation of the Mn spins across the Ga sheets in the Mn-Ga-Mn trilayers. In addition, the elastic properties have been calculated, and from the five elastic constants, the Voigt bulk modulus is determined to be 157 GPa, the Voigt shear modulus 93 GPa, and the Young's modulus 233 GPa. Furthermore, Mn2GaC is found relatively elastically isotropic, with a compression anisotropy factor of 0.97, and shear anisotropy factors of 0.9 and 1, respectively. The Poisson's ratio is 0.25. Evaluated elastic properties are compared to theoretical and experimental results for M2AC phases where M = Ti, V, Cr, Zr, Nb, Ta, and A = Al, S, Ge, In, Sn.
Thore, A. Dahlqvist, M. E-mail: bjoal@ifm.liu.se Alling, B. E-mail: bjoal@ifm.liu.se Rosén, J. E-mail: bjoal@ifm.liu.se
2014-09-14
In this paper, we report the by first-principles predicted properties of the recently discovered magnetic MAX phase Mn?GaC. The electronic band structure and vibrational dispersion relation, as well as the electronic and vibrational density of states, have been calculated. The band structure close to the Fermi level indicates anisotropy with respect to electrical conductivity, while the distribution of the electronic and vibrational states for both Mn and Ga depend on the chosen relative orientation of the Mn spins across the Ga sheets in the Mn–Ga–Mn trilayers. In addition, the elastic properties have been calculated, and from the five elastic constants, the Voigt bulk modulus is determined to be 157?GPa, the Voigt shear modulus 93?GPa, and the Young's modulus 233?GPa. Furthermore, Mn?GaC is found relatively elastically isotropic, with a compression anisotropy factor of 0.97, and shear anisotropy factors of 0.9 and 1, respectively. The Poisson's ratio is 0.25. Evaluated elastic properties are compared to theoretical and experimental results for M?AC phases where M?=?Ti, V, Cr, Zr, Nb, Ta, and A?=?Al, S, Ge, In, Sn.
Cao, Xiaoxiao; Su, Yan; Zhao, Jijun
2015-07-01
Natural gas mixtures are inclusion compounds composed of major light hydrocarbon gaseous molecules (CH4, C2H6, C3H6, and C3H8). Previous ab initio calculations were mainly limited by the cluster models. For the first time, we report first-principles calculations on the stability and vibrational properties of the gas molecules inside the crystalline lattice of type II clathrate. In accordance with our calculations, the larger the size of guest molecule, the more stable the clathrate hydrate for small-sized alkane guest molecules (CnHm, n ? 3, m ? 8). The interaction energy per guest molecule gradually increases as the number of guest molecules increase for both sII pure and sII mixed hydrates. In addition, the vibrational frequencies of guest molecules trapped in sII hydrate are also simulated. The C-C stretching frequency shows a blue shift as the amount of guest molecules increase. Our theoretical results prove to be valuable insight for identifying the types of guest molecules from experimental spectroscopic data. PMID:26073359
Kei-Ichi Kondo
2010-08-16
We give a theoretical framework to obtain a low-energy effective theory of quantum chromodynamics (QCD) towards a first-principle derivation of confinement/deconfinement and chiral-symmetry breaking/restoration crossover transitions. In fact, we demonstrate that an effective theory obtained using simple but non-trivial approximations within this framework enables us to treat both transitions simultaneously on equal footing. A resulting effective theory is regarded as a modified and improved version of nonlocal Polyakov-loop extended Nambu-Jona-Lasinio (nonlocal PNJL) models proposed recently by Hell, R\\"ossner, Cristoforetti and Weise, and Sasaki, Friman and Redlich, extending the original (local) PNJL model by Fukushima and others. A novel feature is that the nonlocal NJL coupling depends explicitly on the temperature and Polyakov loop, which affects the entanglement between confinement and chiral symmetry breaking, together with the cross term introduced through the covariant derivative in the quark sector considered in the conventional PNJL model. The chiral symmetry breaking/restoration transition is controlled by the nonlocal NJL interaction, while the confinement/deconfinement transition in the pure gluon sector is specified by the nonperturbative effective potential for the Polyakov loop obtained recently by Braun, Gies, Marhauser and Pawlowski. The basic ingredients are a reformulation of QCD based on new variables and the flow equation of the Wetterich type in the Wilsonian renormalization group. This framework can be applied to investigate the QCD phase diagram at finite temperature and density.
Kondo, Kei-Ichi
2010-09-15
We give a theoretical framework to obtain a low-energy effective theory of quantum chromodynamics (QCD) towards a first-principle derivation of confinement/deconfinement and chiral-symmetry breaking/restoration crossover transitions. In fact, we demonstrate that an effective theory obtained using simple but nontrivial approximations within this framework enables us to treat both transitions simultaneously on equal footing. A resulting effective theory is regarded as a modified and improved version of nonlocal Polyakov-loop extended Nambu-Jona-Lasinio (nonlocal PNJL) models proposed recently by Hell, Roessner, Cristoforetti, and Weise, and Sasaki, Friman, and Redlich, extending the original (local) PNJL model by Fukushima and others. A novel feature is that the nonlocal NJL coupling depends explicitly on the temperature and Polyakov loop, which affects the entanglement between confinement and chiral-symmetry breaking, together with the cross term introduced through the covariant derivative in the quark sector considered in the conventional PNJL model. The chiral-symmetry breaking/restoration transition is controlled by the nonlocal NJL interaction, while the confinement/deconfinement transition in the pure gluon sector is specified by the nonperturbative effective potential for the Polyakov loop obtained recently by Braun, Gies, Marhauser, and Pawlowski. The basic ingredients are a reformulation of QCD based on new variables and the flow equation of the Wetterich type in the Wilsonian renormalization group. This framework can be applied to investigate the QCD phase diagram at finite temperature and density.
First principle study of elastic and thermodynamic properties of FeB{sub 4} under high pressure
Zhang, Xinyu E-mail: jiaqianqin@gmail.com Ning, Jinliang; Sun, Xiaowei; Li, Xinting; Ma, Mingzhen; Liu, Riping E-mail: jiaqianqin@gmail.com; Qin, Jiaqian E-mail: jiaqianqin@gmail.com
2013-11-14
The elastic properties, elastic anisotropy, and thermodynamic properties of the lately synthesized orthorhombic FeB{sub 4} at high pressures are investigated using first-principles density functional calculations. The calculated equilibrium parameters are in good agreement with the available experimental and theoretical data. The obtained normalized volume dependence of high pressure is consistent with the previous experimental data investigated using high-pressure synchrotron x-ray diffraction. The complete elastic tensors and crystal anisotropies of the FeB{sub 4} are also determined in the pressure range of 0–100?GPa. By the elastic stability criteria and vibrational frequencies, it is predicted that the orthorhombic FeB{sub 4} is stable up to 100 GPa. In addition, the calculated B/G ratio reveals that FeB{sub 4} possesses brittle nature in the range of pressure from 0 to 100?GPa. The calculated elastic anisotropic factors suggest that FeB{sub 4} is elastically anisotropic. By using quasi-harmonic Debye model, the compressibility, bulk modulus, the coefficient of thermal expansion, the heat capacity, and the Grüneisen parameter of FeB{sub 4} are successfully obtained in the present work.
NASA Astrophysics Data System (ADS)
Tsumuraya, Takao; Song, Jung-Hwan; Freeman, Arthur J.
2012-08-01
Linear optical properties of regio-regular-poly(3-hexythiophene) (rr-P3HT) and regio-regular-poly(3-hexyselenophene) (rr-P3HS) are investigated in relation to their anisotropic crystal structure by means of first-principles density functional calculations. The optical spectra are evaluated by calculating its dielectric functions, focusing on the frequency dependence of the imaginary part. The optical transition along the ? conjugation-connecting backbone direction is found to be the most significant at the band edges. A group-theoretical analysis of the matrix elements is given to explain the interband transitions. The optical spectra, electronic structures, and structural stabilities are calculated using the all-electron full-potential linearized augmented plane wave (FLAPW) method within the local-density approximation. We proposed several possible crystal structures of rr-P3HT and performed structural optimizations to determine a stable structure. Comparing the total energy differences among these relaxed structures, a base-centered monoclinic structure belonging to the space group A2 is found to be the most stable structure. In the electronic structure, C and S orbitals belonging to polythiophene backbones are the biggest contributors at the valence band maximum and conduction band minimum, but there is almost no contribution from the hexyl side chains. Last, the differences in electronic and optical properties between rr-P3HT and rr-P3HS are discussed.
2D Electrides as Promising Anode Materials for Na-Ion Batteries from First-Principles Study.
Hu, Junping; Xu, Bo; Yang, Shengyuan A; Guan, Shan; Ouyang, Chuying; Yao, Yugui
2015-11-01
Searching for suitable anodes with good performance is a key challenge for rechargeable Na-ion batteries (NIBs). Using the first-principles method, we predict that 2D nitrogen electride materials can be served as anode materials for NIBs. Particularly, we show that Ca2N meets almost all the requirements of a good NIB anode. Each formula unit of a monolayer Ca2N sheet can absorb up to four Na atoms, corresponding to a theoretical specific capacity of 1138 mAh·g(-1). The metallic character for both pristine Ca2N and its Na intercalated state NaxCa2N ensures good electronic conduction. Na diffusion along the 2D monolayer plane can be very fast even at room temperature, with a Na migration energy barrier as small as 0.084 eV. These properties are key to the excellent rate performance of an anode material. The average open-circuit voltage is calculated to be 0.18 V vs Na/Na(+) for the chemical stoichiometry of Na2Ca2N and 0.09 V for Na4Ca2N. The relatively low average open-circuit voltage is beneficial to the overall voltage of the cell. In addition, the 2D monolayers have very small lattice change upon Na intercalation, which ensures a good cycling stability. All these results demonstrate that the Ca2N monolayer could be an excellent anode material for NIBs. PMID:26461467
NASA Astrophysics Data System (ADS)
Andrés, Juan; Gracia, Lourdes; Fernandes Gouveia, Amanda; Meneghetti Ferrer, Mateus; Longo, Elson
2015-10-01
Morphology is a key property of materials. Owing to their precise structure and morphology, crystals and nanocrystals provide excellent model systems for joint experimental and theoretical investigations into surface-related properties. Faceted polyhedral crystals and nanocrystals expose well-defined crystallographic planes depending on the synthesis method, which allow for thoughtful investigations into structure-reactivity relationships under practical conditions. This feature article introduces recent work, based on the combined use of experimental findings and first-principles calculations, to provide deeper knowledge of the electronic, structural, and energetic properties controlling the morphology and the transformation mechanisms of different metals and metal oxides: Ag, anatase TiO2, BaZrO3, and ?-Ag2WO4. According to the Wulff theorem, the equilibrium shapes of these systems are obtained from the values of their respective surface energies. These investigations are useful to gain further understanding of how to achieve morphological control of complex three-dimensional crystals by tuning the ratio of the surface energy values of the different facets. This strategy allows the prediction of possible morphologies for a crystal and/or nanocrystal by controlling the relative values of surface energies.
NASA Astrophysics Data System (ADS)
Fang, Chang-Ming; Ahuja, Rajeev
2006-08-01
We report first-principles calculations on the structures and stabilities of the ABO 3 (A = Mg and Ca; B = Si and Ge) orthorhombic perovskites (OPvs) under high pressures. Calculations have also been performed for CdGeO 3 and CdTiO 3 OPvs. The calculations showed that MgSiO 3, MgGeO 3, CaGeO 3, CdGeO 3 and CdTiO 3 OPvs transform to the orthorhombic post-perovskites (OPPvs) at about 101, 47, 55, 78 and 64 GPa, respectively, while CaSiO 3 OPv is stable under high pressures. The theoretical results are in good agreement with the available experiments. The lattice distortions with pressure have been studied by analyzing the lattice deviations from the corresponding cubic perovskite (CPv). The lattice distortions increase with pressure for MgSiO 3, MgGeO 3, CaGeO 3 and CdTiO 3 OPvs, while CaSiO 3 OPv has very small lattice distortions under high-pressures and the lattice distortions of CdGeO 3 OPv even decrease with increasing pressure. The OPPvs have large distortions for the a-axis (about -10%).
First principles study and variable range hopping conductivity in disordered Al/Ti/Mn-doped ZnO
NASA Astrophysics Data System (ADS)
Plugaru, Rodica; Sandu, Titus; Plugaru, Neculai
2012-01-01
Based on first principles electronic structure calculations using the Coherent Potential Approximation (CPA) in the Blackman-Esterling-Berk (BEB) multiscattering formalism and the variable range hopping (VRH) model proposed by Mott, we evaluate the low temperature dc conductivity and its temperature dependence for n-doped wurtzite-type M:ZnO, with M = Al, Ti, Mn, at concentrations of 2, 5 and 10 at.% respectively. We theoretically determine the phenomenologic quantities in the expression of the hopping conductivity, as well as the temperature range in which the VRH model is applicable to the investigated compounds. We show that self-consistent CPA-BEB and LSDA+U calculations yield reasonable band gaps, dopant state localization and also spin magnetic moments for the Ti and Mn systems. These results are discussed in comparison with reported data obtained by supercell LSDA+U calculations for similar systems. The results in this study point to 2-5 at.% Ti and approximately 2 at.% Al codoping in wurtzite-type ZnO as an interesting option to obtain a material with an increased low temperature dc conductivity and ferromagnetic background.
NASA Astrophysics Data System (ADS)
Yuan, Nini; Bai, Hongcun; Ma, Yujia; Ji, Yongqiang
2014-11-01
This work presented theoretical studies of structures, energies and properties of armchair carbon nanotubes (CNTs) upon the silicon substitutional doping by using first-principle calculations. The doping effects on quantitative description from viewpoint of the pi-orbital axis vector theory, relative stability, defect formation energy, electronic structure, nonlinear optical property and aromaticity of the tubes has been addressed systemically and in details. The obtained pyramidalization angles of the silicon are much larger than those of carbon according to the pi-orbital axis vector analysis. The results of defect formation energy suggest that the Si-doping would be contained easier in small CNTs. A quantitative relation about the curvature-dependent defect formation energy is obtained. The silicon atoms exhibit large distributions for the frontier molecular orbital of doped tubes. As for the nonlinear optical property, the hyperpolarizability of the tubes is dramatically enhanced upon silicon defect. The doping effect on the aromaticity is also studied. It is found that the aromaticity/anti-aromaticity transition is even occurred at the selected positions based on the probe of nuclear independent chemical shift.
Hu, S X; Collins, L A; Goncharov, V N; Kress, J D; McCrory, R L; Skupsky, S
2015-10-01
Obtaining an accurate equation of state (EOS) of polystyrene (CH) is crucial to reliably design inertial confinement fusion (ICF) capsules using CH/CH-based ablators. With first-principles calculations, we have investigated the extended EOS of CH over a wide range of plasma conditions (?=0.1to100g/cm^{3} and T=1000to4000000K). When compared with the widely used SESAME-EOS table, the first-principles equation of state (FPEOS) of CH has shown significant differences in the low-temperature regime, in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic target implosions on OMEGA using the FPEOS table of CH have predicted ?30% decrease in neutron yield in comparison with the usual SESAME simulations. This is attributed to the ?5% reduction in implosion velocity that is caused by the ?10% lower mass ablation rate of CH predicted by FPEOS. Simulations using CH-FPEOS show better agreement with measurements of Hugoniot temperature and scattered light from ICF implosions. PMID:26565353
Structures and magnetic properties of Co-Zr-B magnets studied by first-principles calculations
NASA Astrophysics Data System (ADS)
Zhao, Xin; Ke, Liqin; Nguyen, Manh Cuong; Wang, Cai-Zhuang; Ho, Kai-Ming
2015-06-01
The structures and magnetic properties of Co-Zr-B alloys near the composition of Co5Zr with B at. % ?6% were studied using adaptive genetic algorithm and first-principles calculations. The energy and magnetic moment contour maps as a function of chemical composition were constructed for the Co-Zr-B magnet alloys through extensive structure searches and calculations. We found that Co-Zr-B system exhibits the same structure motif as the "Co11Zr2" polymorphs, and such motif plays a key role in achieving strong magnetic anisotropy. Boron atoms were found to be able to substitute cobalt atoms or occupy the "interruption" sites. First-principles calculations showed that the magnetocrystalline anisotropy energies of the boron-doped alloys are close to that of the high-temperature rhombohedral Co5Zr phase and larger than that of the low-temperature Co5.25Zr phase. Our calculations provide useful guidelines for further experimental optimization of the magnetic performances of these alloys.
Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro
2015-01-01
Alkali-doped fullerides A3C60 (A = K, Rb, Cs) are surprising materials where conventional phonon-mediated superconductivity and unconventional Mott physics meet, leading to a remarkable phase diagram as a function of volume per C60 molecule. We address these materials with a state-of-the-art calculation, where we construct a realistic low-energy model from first principles without using a priori information other than the crystal structure and solve it with an accurate many-body theory. Remarkably, our scheme comprehensively reproduces the experimental phase diagram including the low-spin Mott-insulating phase next to the superconducting phase. More remarkably, the critical temperatures Tc’s calculated from first principles quantitatively reproduce the experimental values. The driving force behind the surprising phase diagram of A3C60 is a subtle competition between Hund’s coupling and Jahn-Teller phonons, which leads to an effectively inverted Hund’s coupling. Our results establish that the fullerides are the first members of a novel class of molecular superconductors in which the multiorbital electronic correlations and phonons cooperate to reach high Tc s-wave superconductivity.
Hu, S. X.; Collins, L. A.; Goncharov, V. N.; Kress, J. D.; McCrory, R. L.; Skupsky, S.
2015-10-14
Obtaining an accurate equation of state (EOS) of polystyrene (CH) is crucial to reliably design inertial confinement fusion (ICF) capsules using CH/CH-based ablators. Thus, with first-principles calculations, we have investigated the extended EOS of CH over a wide range of plasma conditions (? = 0.1 to 100 g/cm^{3} and T = 1,000 to 4,000,000 K). When compared with the widely used SESAME-EOS table, the first-principles equation of state (FPEOS) of CH has shown significant differences in the low-temperature regime, in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic target implosions on OMEGA using the FPEOS table of CH have predicted ~5% reduction in implosion velocity and ~30% decrease in neutron yield in comparison with the usual SESAME simulations. This is attributed to the ~10% lower mass ablation rate of CH predicted by FPEOS. Simulations using CH-FPEOS show better agreement with measurements of Hugoniot temperature and scattered lights from ICF implosions.
Lee, B; Rudd, R E
2006-10-19
We report the results of first-principles density functional theory calculations of the Young's modulus and other mechanical properties of hydrogen-passivated Si {l_angle}001{r_angle} nanowires. The nanowires are taken to have predominantly {l_brace}100{r_brace}surfaces, with small {l_brace}110{r_brace} facets according to the Wulff shape. The Young's modulus, the equilibrium length and the constrained residual stress of a series of prismatic beams of differing sizes are found to have size dependences that scale like the surface area to volume ratio for all but the smallest beam. The results are compared with a continuum model and the results of classical atomistic calculations based on an empirical potential. We attribute the size dependence to specific physical structures and interactions. In particular, the hydrogen interactions on the surface and the charge density variations within the beam are quantified and used both to parameterize the continuum model and to account for the discrepancies between the two models and the first-principles results.
Terahertz spectra of biotin based on first principle, molecular mechanical, and hybrid simulations.
Bykhovski, Alexei; Woolard, Dwight
2013-07-01
Terahertz (THz) absorption of biotin was simulated using the first principle and the density functional theory (DFT) both in the harmonic approximation and with corrections for the anharmonicity. Anharmonicity corrections were calculated using two different approaches. First, the perturbation theory-based first principle calculations were performed to include third- and fourth-order anharmonicity corrections in atomic displacements to harmonic vibrational states. Second, the atom-centered density matrix propagation molecular dynamics model that provides a good energy conservation was used to calculate the atomic trajectories, velocities, and a dipole moment time history of biotin at low and room temperatures. Predicted low-THz lines agree well with the experimental spectra. The influence of the polyethylene (PE) matrix embedment on the THz spectra of biotin at the nanoscale was studied using the developed hybrid DFT/molecular mechanical approach. While PE is almost transparent at THz frequencies, additional low-THz lines are predicted in the biotin/PE system, which reflects a dynamic interaction between biotin and a surrounding PE cavity. PMID:25055303
First-Principles Modeling of Hydrogen Storage in Metal Hydride Systems
J. Karl Johnson
2011-05-20
The objective of this project is to complement experimental efforts of MHoCE partners by using state-of-the-art theory and modeling to study the structure, thermodynamics, and kinetics of hydrogen storage materials. Specific goals include prediction of the heats of formation and other thermodynamic properties of alloys from first principles methods, identification of new alloys that can be tested experimentally, calculation of surface and energetic properties of nanoparticles, and calculation of kinetics involved with hydrogenation and dehydrogenation processes. Discovery of new metal hydrides with enhanced properties compared with existing materials is a critical need for the Metal Hydride Center of Excellence. New materials discovery can be aided by the use of first principles (ab initio) computational modeling in two ways: (1) The properties, including mechanisms, of existing materials can be better elucidated through a combined modeling/experimental approach. (2) The thermodynamic properties of novel materials that have not been made can, in many cases, be quickly screened with ab initio methods. We have used state-of-the-art computational techniques to explore millions of possible reaction conditions consisting of different element spaces, compositions, and temperatures. We have identified potentially promising single- and multi-step reactions that can be explored experimentally.
Quantum Mechanics and First-Principles Molecular Dynamics Selection of Polymer Sensing Materials
NASA Astrophysics Data System (ADS)
Blanco, Mario; Shevade, Abhijit V.; Ryan, Margaret A.
We present two first-principles methods, density functional theory (DFT) and a molecular dynamics (MD) computer simulation protocol, as computational means for the selection of polymer sensing materials. The DFT methods can yield binding energies of polymer moieties to specific vapor bound compounds, quantities that were found useful in materials selection for sensing of organic and inorganic compounds for designing sensors for the electronic nose (ENose) that flew on the International Space Station (ISS) in 2008-2009. Similarly, we present an MD protocol that offers high consistency in the estimation of Hildebrand and Hansen solubility parameters (HSP) for vapor bound compounds and amorphous polymers. HSP are useful for fitting measured polymer sensor responses with physically rooted analytical models. We apply the method to the JPL electronic nose (ENose), an array of sensors with conducting leads connected through thin film polymers loaded with carbon black. Detection relies on a change in electric resistivity of the polymer film as function of the amount of swelling caused by the presence of the analyte chemical compound. The amount of swelling depends upon the chemical composition of the polymer and the analyte molecule. The pattern is unique and it unambiguously identifies the compound. Experimentally determined changes in relative resistivity of fifteen polymer sensor materials upon exposure to ten vapors were modeled with the first-principles HSP model.
First-principles calculation of Z2 topological invariants within the FP-LAPW formalism
Feng, wanxiang; Wen, Jun; Zhou, Jinjian; Yao, yugui
2012-01-01
n this paper, we report the implementation of first-principles calculations of Z2 topological invariants within the full-potential linearized augmented plane-wave (FP-LAPW) formalism. In systems with both time-reversal and spatial inversion symmetry (centrosymmetric), one can use the parity analysis of Bloch functions at time-reversal invariant momenta to determine the Z2 invariants. In systems without spatial inversion symmetry (noncentrosymmetric), however, a more complex and systematic method in terms of the Berry gauge potential and the Berry curvature is required to identify the band topology. We show in detail how both methods are implemented in FP-LAPW formalism and applied to several classes of materials including centrosymmetric compounds Bi2Se3 and Sb2Se3 and noncentrosymmetric compounds LuPtBi, AuTlS2 and CdSnAs2. Our work provides an accurate and effective implementation of first-principles calculations to speed up the search of new topological insulators.
Hu, S. X.; Collins, L. A.; Goncharov, V. N.; Kress, J. D.; McCrory, R. L.; Skupsky, S.
2015-10-14
Obtaining an accurate equation of state (EOS) of polystyrene (CH) is crucial to reliably design inertial confinement fusion (ICF) capsules using CH/CH-based ablators. Thus, with first-principles calculations, we have investigated the extended EOS of CH over a wide range of plasma conditions (? = 0.1 to 100 g/cm3 and T = 1,000 to 4,000,000 K). When compared with the widely used SESAME-EOS table, the first-principles equation of state (FPEOS) of CH has shown significant differences in the low-temperature regime, in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic target implosionsmore »on OMEGA using the FPEOS table of CH have predicted ~5% reduction in implosion velocity and ~30% decrease in neutron yield in comparison with the usual SESAME simulations. This is attributed to the ~10% lower mass ablation rate of CH predicted by FPEOS. Simulations using CH-FPEOS show better agreement with measurements of Hugoniot temperature and scattered lights from ICF implosions.« less
Electronic and optical properties of AlN/GaN superlattices from first-principles calculations
NASA Astrophysics Data System (ADS)
Bayerl, Dylan; Kioupakis, Emmanouil
2015-03-01
Group-III-nitrides are important materials for efficient light emitters in the ultraviolet and visible range. Superlattices of AlN/GaN quantum wells are especially promising for ultraviolet light emission. We use first-principles calculations to investigate the electronic and optical properties of AlN/GaN quantum well superlattices. Density functional theory with quasiparticle corrections from the GW method provides accurate electronic band structures. We then solve the Bethe-Salpeter equation to predict exciton binding energies and fundamental optical emission energies from first principles, yielding good agreement with available experimental measurements. Ultimately, we elucidate the relationship between optical emission energy and well/barrier thickness, as well as demonstrate mitigation of the quantum confined Stark effect in ultra-narrow wells for enhanced radiative recombination efficiency. This research was supported by the J. Robert Beyster Computational Innovation Graduate Fellowship and in part by CSTEC, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science. Computational resources were provided by the DOE NERSC facility.
Liu, Xuan L; Gheno, Thomas; Lindahl, Bonnie B; Lindwall, Greta; Gleeson, Brian; Liu, Zi-Kui
2015-01-01
The phase relations and thermodynamic properties of the condensed Al-Co-Cr ternary alloy system are investigated using first-principles calculations based on density functional theory (DFT) and phase-equilibria experiments that led to X-ray diffraction (XRD) and electron probe micro-analysis (EPMA) measurements. A thermodynamic description is developed by means of the calculations of phase diagrams (CALPHAD) method using experimental and computational data from the present work and the literature. Emphasis is placed on modeling the bcc-A2, B2, fcc-?, and tetragonal-? phases in the temperature range of 1173 to 1623 K. Liquid, bcc-A2 and fcc-? phases are modeled using substitutional solution descriptions. First-principles special quasirandom structures (SQS) calculations predict a large bcc-A2 (disordered)/B2 (ordered) miscibility gap, in agreement with experiments. A partitioning model is then used for the A2/B2 phase to effectively describe the order-disorder transitions. The critically assessed thermodynamic description describes all phase equilibria data well. A2/B2 transitions are also shown to agree well with previous experimental findings. PMID:25875037
First principles calculation of the shift current photovoltaic effect in ferroelectrics.
Young, Steve M; Rappe, Andrew M
2012-09-14
We calculate the bulk photovoltaic response of the ferroelectrics BaTiO(3) and PbTiO(3) from first principles by applying the "shift current" theory to the electronic structure from density functional theory. The first principles results for BaTiO(3) reproduce experimental photocurrent direction and magnitude as a function of light frequency, as well as the dependence of current on light polarization, demonstrating that shift current is the dominant mechanism of the bulk photovoltaic effect in BaTiO(3). Additionally, we analyze the relationship between response and material properties in detail. Photocurrent does not depend simply or strongly on the magnitude of material polarization, as has been previously assumed; instead, electronic states with delocalized, covalent bonding that is highly asymmetric along the current direction are required for strong shift current enhancements. The complexity of the response dependence on both external and material parameters suggests applications not only in solar energy conversion, but in photocatalysis and sensor and switch type devices as well. PMID:23005660
Structures and magnetic properties of Co-Zr-B magnets studied by first-principles calculations
Zhao, Xin; Ke, Liqin; Nguyen, Manh Cuong; Wang, Cai -Zhuang; Ho, Kai -Ming
2015-06-23
The structures and magnetic properties of Co-Zr-B alloys near the composition of Co5Zr with B at. % ?6% were studied using adaptive genetic algorithm and first-principles calculations. The energy and magnetic moment contour maps as a function of chemical composition were constructed for the Co-Zr-B magnet alloys through extensive structure searches and calculations. We found that Co-Zr-B system exhibits the same structure motif as the “Co11Zr2”polymorphs, and such motif plays a key role in achieving strong magnetic anisotropy. Boronatoms were found to be able to substitute cobalt atoms or occupy the “interruption” sites. First-principles calculations showed that the magnetocrystalline anisotropymore »energies of the boron-doped alloys are close to that of the high-temperature rhombohedral Co5Zr phase and larger than that of the low-temperature Co5.25Zr phase. As a result, our calculations provide useful guidelines for further experimental optimization of the magnetic performances of these alloys.« less
First-Principles Calculations, Experimental Study, and Thermodynamic Modeling of the Al-Co-Cr System
Liu, Xuan L.; Gheno, Thomas; Lindahl, Bonnie B.; Lindwall, Greta; Gleeson, Brian; Liu, Zi-Kui
2015-01-01
The phase relations and thermodynamic properties of the condensed Al-Co-Cr ternary alloy system are investigated using first-principles calculations based on density functional theory (DFT) and phase-equilibria experiments that led to X-ray diffraction (XRD) and electron probe micro-analysis (EPMA) measurements. A thermodynamic description is developed by means of the calculations of phase diagrams (CALPHAD) method using experimental and computational data from the present work and the literature. Emphasis is placed on modeling the bcc-A2, B2, fcc-?, and tetragonal-? phases in the temperature range of 1173 to 1623 K. Liquid, bcc-A2 and fcc-? phases are modeled using substitutional solution descriptions. First-principles special quasirandom structures (SQS) calculations predict a large bcc-A2 (disordered)/B2 (ordered) miscibility gap, in agreement with experiments. A partitioning model is then used for the A2/B2 phase to effectively describe the order-disorder transitions. The critically assessed thermodynamic description describes all phase equilibria data well. A2/B2 transitions are also shown to agree well with previous experimental findings. PMID:25875037
First-principles equation of state and electronic properties of warm dense oxygen
NASA Astrophysics Data System (ADS)
Driver, K. P.; Soubiran, F.; Zhang, Shuai; Militzer, B.
2015-10-01
We perform all-electron path integral Monte Carlo (PIMC) and density functional theory molecular dynamics (DFT-MD) calculations to explore warm dense matter states of oxygen. Our simulations cover a wide density-temperature range of 1-100 g cm-3 and 104-109 K. By combining results from PIMC and DFT-MD, we are able to compute pressures and internal energies from first-principles at all temperatures and provide a coherent equation of state. We compare our first-principles calculations with analytic equations of state, which tend to agree for temperatures above 8 × 106 K. Pair-correlation functions and the electronic density of states reveal an evolving plasma structure and ionization process that is driven by temperature and density. As we increase the density at constant temperature, we find that the ionization fraction of the 1s state decreases while the other electronic states move towards the continuum. Finally, the computed shock Hugoniot curves show an increase in compression as the first and second shells are ionized.
First-principles equation of state and electronic properties of warm dense oxygen.
Driver, K P; Soubiran, F; Zhang, Shuai; Militzer, B
2015-10-28
We perform all-electron path integral Monte Carlo (PIMC) and density functional theory molecular dynamics (DFT-MD) calculations to explore warm dense matter states of oxygen. Our simulations cover a wide density-temperature range of 1-100 g cm(-3) and 10(4)-10(9) K. By combining results from PIMC and DFT-MD, we are able to compute pressures and internal energies from first-principles at all temperatures and provide a coherent equation of state. We compare our first-principles calculations with analytic equations of state, which tend to agree for temperatures above 8 × 10(6) K. Pair-correlation functions and the electronic density of states reveal an evolving plasma structure and ionization process that is driven by temperature and density. As we increase the density at constant temperature, we find that the ionization fraction of the 1s state decreases while the other electronic states move towards the continuum. Finally, the computed shock Hugoniot curves show an increase in compression as the first and second shells are ionized. PMID:26520527
Surface design of alloy protection against CO-poisoning from first principles.
Yuge, Koretaka; Koyama, Yukinori; Kuwabara, Akihide; Tanaka, Isao
2014-09-01
Pt-based alloy catalysts are of significant importance in fuel cells due to enhanced electrode reactivity and selectivity. Designing alloy surfaces suitable for catalyst via first-principles predictions has long played a central role in identifying promising candidates. We propose surface design for polymer electrolyte fuel cell (PEFC) based on the use of thermodynamically stable alloy surfaces. Using first-principles calculation, we have explored stable Pt alloy surfaces that possess superior catalytic properties for CO-despoisoning in hydrogen-related reactions of fuel cells. The stable Pt(25)M(75) (M = Rh, Cu) alloy surfaces both exhibited weaker CO and stronger H binding compared to the pure Pt surface, which yielded a significant increase in H coverage by around one order. These modifications of molecular adsorption are attributed to the deeper band centre of surface d electrons. Understanding the adsorption properties of the stable atomic structure at surfaces will help us to design suitable alloy surfaces with high-catalytic activity and prolonged actuation in fuel cells. PMID:25078032
First-principles Simulations of a Graphene-Based Field Effect Transistor
NASA Astrophysics Data System (ADS)
Wang, Yun-Peng; Cheng, Hai-Ping
2014-03-01
We propose a first-principles method to simulate the effect of a gate voltage on a two-dimensional channel. Because of the aperiodic structure of field effect devices, we adopt the effective screening medium (ESM) method, which enables us to solve the Poisson equation with free boundary conditions, to simulate nanoscale field effect devices. With this approach, we investigated a graphene-based vertical field effect tunneling transistor with a graphene | h -BN |graphene multilayer structure. The calculated carrier density on the graphene away from the gate electrode is sublinear with respect to the gate voltage, and decreases as the thickness of the h-BN barrier increases. The band structure of graphene layers near the Fermi energy exhibit a ~ 0 . 05 eV gap opening due to interactions with h-BN, as well as the chemical potential difference between the two graphene monolayers. This work paves the road to first-principles simulations of nanoscale field effect transistors and opens a new avenue towards computational guided device design. This work is supported by DOE/BES-DE-FG02-02ER45995. Computations are performed using facilities at NERSC.
Structures and magnetic properties of Co-Zr-B magnets studied by first-principles calculations
Zhao, Xin; Ke, Liqin; Nguyen, Manh Cuong; Wang, Cai -Zhuang; Ho, Kai -Ming
2015-06-23
The structures and magnetic properties of Co-Zr-B alloys near the composition of Co_{5}Zr with B at. % ?6% were studied using adaptive genetic algorithm and first-principles calculations. The energy and magnetic moment contour maps as a function of chemical composition were constructed for the Co-Zr-B magnet alloys through extensive structure searches and calculations. We found that Co-Zr-B system exhibits the same structure motif as the “Co_{11}Zr_{2}”polymorphs, and such motif plays a key role in achieving strong magnetic anisotropy. Boronatoms were found to be able to substitute cobalt atoms or occupy the “interruption” sites. First-principles calculations showed that the magnetocrystalline anisotropy energies of the boron-doped alloys are close to that of the high-temperature rhombohedral Co_{5}Zr phase and larger than that of the low-temperature Co_{5.25}Zr phase. As a result, our calculations provide useful guidelines for further experimental optimization of the magnetic performances of these alloys.
Nomura, Yusuke; Sakai, Shiro; Capone, Massimo; Arita, Ryotaro
2015-08-01
Alkali-doped fullerides A 3C60 (A = K, Rb, Cs) are surprising materials where conventional phonon-mediated superconductivity and unconventional Mott physics meet, leading to a remarkable phase diagram as a function of volume per C60 molecule. We address these materials with a state-of-the-art calculation, where we construct a realistic low-energy model from first principles without using a priori information other than the crystal structure and solve it with an accurate many-body theory. Remarkably, our scheme comprehensively reproduces the experimental phase diagram including the low-spin Mott-insulating phase next to the superconducting phase. More remarkably, the critical temperatures T c's calculated from first principles quantitatively reproduce the experimental values. The driving force behind the surprising phase diagram of A 3C60 is a subtle competition between Hund's coupling and Jahn-Teller phonons, which leads to an effectively inverted Hund's coupling. Our results establish that the fullerides are the first members of a novel class of molecular superconductors in which the multiorbital electronic correlations and phonons cooperate to reach high T c s-wave superconductivity. PMID:26601242
First-principles-based phase diagram of the cubic BNC ternary system
NASA Astrophysics Data System (ADS)
Yuge, Koretaka; Seko, Atsuto; Koyama, Yukinori; Oba, Fumiyasu; Tanaka, Isao
2008-03-01
The phase diagram for the cubic BNC ternary system in a heterodiamond structure was examined by Monte Carlo simulations and the cluster expansion technique based on first-principles calculations. All the atomic arrangements exhibit positive formation energies, indicating phase separation into cubic BN (c-BN) and diamond. These arrangements show a strong preference for B-N and C-C bonds and disfavor B-C, C-N, B-B, and N-N bonds along the first nearest neighbor coordination. This can be naturally attributed to the oversaturation and undersaturation of the number of electrons for respective first nearest neighbor bonds. First-principles-based lattice-dynamics calculations reveal that the formation of a solid solution between c-BN and diamond decreases vibrational free energy, resulting in a significant enhancement of the solubility for both c-BN and diamond-rich phases. Complete miscibility is achieved over T=4500K , which is higher than the melting points of both diamond and c-BN .
Huang, Zuocai; Zhang, Lei; Pan, Wei
2013-09-15
Pure zircon and scheelite LuVO{sub 4} were prepared by solid state reaction and high-pressure route, respectively. Structure, elastic constants, lattice dynamics and thermodynamics of LuVO{sub 4} polymorphs were studied by experiments and first principles calculation. Calculations here are in good agreement with the experimental results. The phonon dispersions of LuVO{sub 4} polymorphs were studied by the linear response method. The calculated phonon dispersions show that zircon and scheelite LuVO{sub 4} phases are dynamically stable. Raman-active frequencies were measured and assigned to different modes according to the calculations. The internal frequencies shift downward after phase transition from zircon to scheelite. Born effective charge tensors elements for both phases are analyzed. The finite temperature thermodynamic properties of LuVO{sub 4} polymorphs were calculated from the obtained phonon density of states by quasi-harmonic approach. - Graphical abstract: Lutetium orthovanadate polymorphs were synthesized by SSR and HP methods and their physical and chemical properties, including lattice dynamical properties, were determined by DFT calculations and experiments. Display Omitted - Highlights: • Pure zircon and scheelite LuVO{sub 4} polymorphs were synthesized by solid state reaction and high-pressure route. • Chemical and physical properties of LuVO4 polymorphs were studied by experiments and first principles calculation. • Raman-active frequencies were measured and assigned to different modes according to the calculations. • Lattice dynamics of polymorphs were discussed in details.
NASA Astrophysics Data System (ADS)
Hu, S. X.; Collins, L. A.; Goncharov, V. N.; Kress, J. D.; McCrory, R. L.; Skupsky, S.
2015-10-01
Obtaining an accurate equation of state (EOS) of polystyrene (CH) is crucial to reliably design inertial confinement fusion (ICF) capsules using CH/CH-based ablators. With first-principles calculations, we have investigated the extended EOS of CH over a wide range of plasma conditions (? =0.1 to 100 g /cm3 and T =1000 to 4 000 000 K ). When compared with the widely used SESAME-EOS table, the first-principles equation of state (FPEOS) of CH has shown significant differences in the low-temperature regime, in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic target implosions on OMEGA using the FPEOS table of CH have predicted ˜30% decrease in neutron yield in comparison with the usual SESAME simulations. This is attributed to the ˜5% reduction in implosion velocity that is caused by the ˜10% lower mass ablation rate of CH predicted by FPEOS. Simulations using CH-FPEOS show better agreement with measurements of Hugoniot temperature and scattered light from ICF implosions.
First principles calculations of magnetic properties of Fe and Fe3C at finite temperature
NASA Astrophysics Data System (ADS)
Eisenbach, Markus; Brown, Gregory; Rusanu, Aurelian; Nicholson, Don M.
2011-03-01
We demonstrate a method to investigate finite temperature magnetism from first principles that harnesses massively parallel computers to obtain the free energy, specific heat, magnetization, susceptibility, and other quantities as function of temperature by combining classical Wang-Landau Monte-Carlo calculations with a first principles electronic structure code that allows the energy calculation of constrained magnetic states. Here we will present our calculations of finite temperature properties such as specific heat, magnetization and susceptibility of Fe and Fe3C using this approach where we find the Curie temperatures to be in good agreement with experiment at 980K and 425K respectively. This work was conducted at Oak Ridge National Laboratory (ORNL), which is managed by UT-Battelle for the U.S. Department of Energy (US DOE) under contract DE-AC05-00OR22725 and sponsored in parts by the Center for Nanophase Material Sciences, Scientific User Facilities Division, the Center for Defect Physics, an Energy Frontier Research Center funded by the US DOE Office of Basic Energy Sciences and by the US DOE Office of Energy Efficiency and Renewable Energy, Industrial Technologies Program. This research used resources of the Oak Ridge Leadership Computing Facility at ORNL, which is supported by the US DOE, Office of Science.
Degenerate four-wave mixing spectroscopy with short-pulse lasers: theoretical analysis
NASA Astrophysics Data System (ADS)
Reichardt, Thomas A.; Lucht, Robert P.
1996-12-01
The use of picosecond lasers for degenerate four-wave mixing (DFWM) diagnostics of atmospheric pressure flames has been suggested as a means of overcoming the complicated collision-rate dependence of the DFWM signal in the nanosecond-laser pulse-length regime. In this paper DFWM spectroscopy in the regime in which the laser pulse length ( tau L) is less than the characteristic collisional time ( tau C) is investigated theoretically. DFWM signal levels for the phase-conjugate geometry (counterpropagating pump beams) are calculated by integration of the time-dependent density-matrix equations at numerous grid points along the phase-matching axis and by summing of the polarization contribution from each of these grid points. Both purely homogeneously broadened resonances and resonances that are both collision broadened and Doppler broadened are considered. DFWM signal generation for these two types of resonances in the fully transient regime ( tau L << tau C) is strikingly different. For a homogeneously broadened resonance, the DFWM signal persists long after the laser beam has passed through the medium. The decay rate of the DFWM signal is determined by the collision rate in the medium, and the integrated DFWM signal is still dependent on the collision rate even in this fully transient regime. However, when the Doppler broadening of the resonance is much greater than the collisional broadening, the DFWM signal decays with a fall time close to that of the laser pulse. For tau L << tau C, we find that it is the laser spectral width, rather than the collisional width, that dictates the range of velocity groups with which the pulses effectively interact. The signal decays with a fall time close to that of the laser pulse because the excited velocity groups radiate out of phase with one another. In a medium in which the Doppler width is much greater than the collisional width, the DFWM reflectivity is independent of collision rate for tau L<< tau C, but the signal level is dependent on the Doppler width. Finally, we investigate the effect of different laser pulse lengths on reflectivity saturation curves for resonances with different levels of Doppler broadening. .
NASA Astrophysics Data System (ADS)
Liang, Liangbo
Since its fabrication in 2004, graphene has attracted huge attention due to its exceptional electronic properties, and is now considered as one of the most promising candidates to replace the current semiconductor technology as silicon approaches its miniaturization limit. However, the absence of an electronic band gap in pristine graphene makes it ill-suited for many electronic applications. Semiconducting character can be imparted by a variety of methods, including chemical or structural modifications. For instance, a band gap can be opened by confining the electronic wave function in one dimension by cutting graphene to form graphene nanoribbons (GNRs). To possess a band gap comparable to conventional semiconductors like silicon, GNRs are required to have a width less than 3 nm and must also display sharp edges, which remains a great experimental challenge. Recently, a breakthrough advance has been achieved with the controlled synthesis of atomically precise nanoribbons using a bottom-up approach where small aromatic molecules chemically assemble into high-quality subnanometer ribbons. This method not only allows for the synthesis of high-quality straight GNRs, but also for more complex structures like wiggle-like GNRs, called graphene nanowiggles (GNWs). In Part I of this thesis, first-principles density functional theory (DFT) calculations are carried out on a variety of GNWs to reveal their unusual electronic and magnetic properties that are absent in their individual GNRs components, such as tunable band gaps and versatile magnetic states. The relationship between the band gap and the geometry is dictated by the armchair or zigzag characters of the corresponding parallel and oblique sectors, enabling GNWs to offer a broader set of geometrical parameters to tune the electronic structures compared to GNRs. In addition, first-principles many-body Green's function calculations within the GW approximation are performed to yield a quantitative prediction of GNWs' electronic properties. The enhanced electron-electron interaction in the quasi-one-dimensional GNWs results in significant self-energy corrections to their DFT band gaps. Consequently, the quasiparticle band gaps are typically more than twice of the DFT band gaps and are within the most interesting range 0.0-3.7 eV. In Part II of this thesis, we venture beyond graphene-based systems and investigate graphene-like materials: transition metal dichalcogenides MX 2(M = Mo, W; X = S). Similar to graphite, they are also layered structures stacked by weak van der Waals (vdW) forces. Single-layer MoS2 and WS2 have been synthesized and found to show enhanced carrier charge mobilities and strong photoluminescence with direct band gaps, and thus they have been considered as replacements or complements to graphene for applications. Raman spectroscopy is often considered as one of the most popular tools to characterize them. Despite extensive experimental Raman studies on MoS 2 and WS2, it remains unclear how Raman intensities and especially intensity ratio of Raman modes E2g1 and A1g depend on the materials' thickness, due to the large spectrum of seemingly contradictory findings. In the final part of the thesis (Part III), we highlight the experimental collaboration project with Prof. Plummer's group from Louisiana State University: spin-dependent surface reconstruction of layered Fe-based superconductors CaFe2As2. Low energy electron diffraction, scanning tunneling microscopy and spectroscopy, and first-principles spin-polarized DFT are utilized to investigate the geometric, electronic, and magnetic structures of the stripe-ordered (1x2) surface of Ca(Fe1-xCox) 2As2 (x=0, 0.075). The surface is terminated with a 50% Ca layer. Compared to the bulk, the surface Ca layer has a large inward relaxation (˜ 0.5 A), and the underneath As-Fe2-As layer displays a significant buckling. First-principles calculations show that the (1x2) phase is stabilized by the bulk anti-ferromagnetic spin ordering through the spin-charge-lattice coupling. Strikingly, a superconducting gap (˜7 meV
Doe, Robert E.
First principles calculations have been used to explore the Li–Bi–F ternary phase diagram. Our results confirm the thermodynamic stability of previously observed phases and find no new phases in this system. Electrochemical ...
Celino, M.
The structure of glassy GeS[subscript 2] is studied in the framework of density functional theory, by using a fully self-consistent first-principles molecular dynamics (FPMD) scheme. A comparative analysis is performed ...
NASA Astrophysics Data System (ADS)
Lee, Ming-Hsien; Liu, Po-Liang; Hong, Yung-An; Chou, Yen-Ting; Hong, Jia-Yang; Siao, Yu-Jin
2013-02-01
We conduct first-principles total-energy density functional calculations to study the band structures in Ge1-xSnx infrared semiconductor alloys. The norm-conserving optimized pseudopotentials of Ge and Sn have been constructed for electronic structure calculations. The composition-bandgap relationships in Ge1-xSnx lattices are evaluated by a detailed comparison of structural models and their electronic band structures. The critical Sn composition related to the transition from indirect- to direct-gap in Ge1-xSnx alloys is estimated to be as low as x ˜ 0.016 determined from the parametric fit. Our results show that the crossover Sn concentration occurs at a lower critical Sn concentration than the values predicted from the absorption measurements. However, early results indicate that the reliability of the critical Sn concentration from such measurements is hard to establish, since the indirect gap absorption is much weaker than the direct gap absorption. We find that the direct band gap decreases exponentially with the Sn composition over the range 0
First-principles study of the rotational transitions of H2 physisorbed over benzene
NASA Astrophysics Data System (ADS)
Hamel, Sébastien; Côté, Michel
2004-12-01
In the ongoing search for promising compounds for hydrogen storage, novel porous metal-organic frameworks (MOFs) have been discovered recently [M. Eddadoudi, J. Kim, N. L. Rosi, D. Vodak, J. Wachter, M. O'Keeffe, and O. M. Yaghi, Science 295, 469 (2002); N. L. Rosi, J. Eckert, M. Eddadoudi, D. Vodak, J. Kim, M. O'Keeffe, and O. M. Yaghi, Science 300, 1127 (2003)]. Binding sites in these MOFs were deduced from inelastic neutron scattering (INS) spectroscopy of the rotational transitions of the adsorbed molecular hydrogen. In light of this discovery, it is important to have a fundamental understanding of hydrogen adsorption at different sites in this class of MOF materials. As a first step, here we study the case of H2 adsorbed on benzene as a model of the organic linkers in the microporous crystal. We access the density functional theory results by comparing with correlated ab initio methods, e.g., second-order Møller-Plesset and coupled cluster with noniterative triple excitations. Different approximations for the exchange-correlation potentials were accessed for a set of relevant properties (binding energy, energetically favored configuration, and distance between the adsorbents and adsorbates). In particular, theoretical rotational spectra of the adsorbed H2 were obtained that could be compared to the experimental INS spectra.
Lanphere, Marvin A.; Dalrymple, G. Brent
2000-01-01
We describe the analytical procedure for first-principles calibrations of 38Ar tracers in the U.S. Geological Survey (USGS) Laboratory in Menlo Park, California. The ages of fluence monitors determined in the USGS laboratory and those reported in the literature differ by nearly 2 percent. However, the radiogenic-40Ar content of the primary mineral standard on which these ages are based has never been verified by first-principles measurement in other laboratories.
First-principles study of electric polarization in piezoelectric and magnetoelectric materials
NASA Astrophysics Data System (ADS)
Malashevich, Andrei
First-principles calculations based on the density-functional theory (DFT) have proven to be extremely useful in the study of properties of matter. Not only do they provide a sufficient accuracy to reproduce experimental results, but also they make it possible to predict materials with enhanced or even new properties. Often first-principles calculations become a cheap alternative to real experiments or even allow one to investigate regimes not accessible experimentally either in principle or because of limitations of experimental techniques. But the real power of methods based on computer simulations is that they can help one to understand the microscopic mechanisms of physical processes inside the materials. In my thesis work I will analyze electric polarization properties of several materials and their dependence on some physical parameters such as strain, chemical doping, and magnetic order. In the first part of my thesis I will present an ab-initio study of wurtzite ZnO doped with Mg. Several ordered structures modeling the Zn1-xMgxO alloy are analyzed with different Mg concentrations. The electric polarization is studied as a function of Mg concentration x under different strain conditions. We find that to a good approximation the polarization depends linearly on x. We show that a simple model based on the piezoelectric response of pure ZnO can reproduce the results fairly well. In the second part, we study the magnetoelectric coupling in a spiral magnet TbMnO3. It is known from experiment that at low temperatures a ferroelectric phase appears simultaneously with the onset of a cycloidal magnetic order. Using first-principles methods, we demonstrate that ferroelectricity in this material is indeed driven by magnetic order. We show that spin-orbit coupling is essential for the electric polarization to appear. We also demonstrate that the ionic displacements induced by a cycloidal magnetic order, though tiny, play a crucial role in producing polarization. We do a detailed analysis of the forces on ions and ionic displacements from the mode-decomposition viewpoint, and find that simple models based only on nearest-neighbor interactions between Mn ions through oxygen are not able to account fully for the results.
First-principles computation of mantle materials in crystalline and amorphous phases
NASA Astrophysics Data System (ADS)
Karki, Bijaya B.
2015-03-01
First-principles methods based on density functional theory are used extensively in the investigation of the behavior and properties of mantle materials over broad ranges of pressure, temperature, and composition that are relevant. A review of computational results reported during the last couple of decades shows that essentially all properties including structure, phase transition, equation of state, thermodynamics, elasticity, alloying, conductivity, defects, interfaces, diffusivity, viscosity, and melting have been calculated from first principles. Using MgO, the second most abundant oxide of Earth's mantle, as a primary example and considering many other mantle materials in their crystalline and amorphous phases, we have found that most properties are strongly pressure dependent, sometimes varying non-monotonically and anomalously, with the effects of temperature being systematically suppressed with compression. The overall agreement with the available experimental data is excellent; it is remarkable that the early-calculated results such as shear wave velocities of two key phases, MgO and MgSiO3 perovskite, were subsequently reproduced by experimentation covering almost the entire mantle pressure regime. As covered in some detail, the defect formation and migration enthalpies of key mantle materials increase with pressure. The predicted trend is that partial MgO Schottky defects are energetically most favorable in Mg-silicates but their formation enthalpies are high. So, the diffusion in the mantle is likely to be in the extrinsic regime. Preliminary results on MgO and forsterite hint that the grain boundaries can accommodate point defects (including impurities) and enhance diffusion rates at all pressures. The structures are highly distorted in the close vicinity of the defects and at the interface with excess space. Recent simulations of MgO-SiO2 binary and other silicate melts have found that the melt self-diffusion and viscosity vary by several orders of magnitudes with pressure, temperature, and composition. The predicted high compressibility and complex dynamical behavior can be associated with structural changes (involving non-bridging oxygen, oxygen tri-clusters, Si-O pentahedra, etc.) occurring on compression. We envision future prospect for massively parallel/distributed computing of unprecedented magnitude and scope in the study of relevant materials for Earth, super-Earth, and other planets. A renewed computational theme perhaps should be the first-principles simulations of large systems (with long runs) that are necessary to explore realistic (natural) compositions, polycrystalline phases, multi-component melts, crystal/melt interfaces, trace element partitioning, etc.
NASA Astrophysics Data System (ADS)
de Brito Mota, F.; de Castilho, C. M. C.
2006-10-01
Single wall carbon nanotubes (SWCN’s) have attracted scientific interest as a result of their remarkable mechanical and electrical properties. Metallic SWCN’s can carry electrical current due to ? electrons propagating along their graphitelike surface. This work theoretically considers the effects resulting from the possibility of connecting nanotubes to a partially hydrogenated Si-rich ?-SiC(100) (3×2) surface. This is done with the perspective that they can improve the metallic character of the surface. Calculations were performed using a first-principles pseudopotential methodology within the density-functional theory and local-density approximation. Results indicates the formation of a covalent bond between nanotube carbon atoms and surface silicon atoms. The structural and electronic properties of this theoretical system are presented and comparison with previous calculations for related systems is also done.
Energy band modulation of graphane by hydrogen-vacancy chains: A first-principles study
Wu, Bi-Ru; Yang, Chih-Kai
2014-08-15
We investigated a variety of configurations of hydrogen-vacancy chains in graphane by first-principles density functional calculation. We found that graphane with two zigzag H-vacancy chains segregated by one or more H chain is generally a nonmagnetic conductor or has a negligible band gap. However, the same structure is turned into a semiconductor and generates a magnetic moment if either one or both of the vacancy chains are blocked by isolated H atoms. If H-vacancy chains are continuously distributed, the structure is similar to a zigzag graphene nanoribbon embedded in graphane. It was also found that the embedded zigzag graphene nanoribbon is antiferromagnetic, and isolated H atoms left in the 2-chain nanoribbon can tune the band gap and generate net magnetic moments. Similar effects are also obtained if bare carbon atoms are present outside the nanoribbon. These results are useful for designing graphene-based nanoelectronic circuits.
NASA Astrophysics Data System (ADS)
Ranjbar, Ahmad; Khazaei, Mohammad; Venkataramanan, Natarajan Sathiyamoorthy; Lee, Hoonkyung; Kawazoe, Yoshiyuki
2011-03-01
Using first-principles density functional theory, we investigated the hydrogen storage capacity of Li-functionalized adamantane. We showed that if one of the acidic hydrogen atoms of adamantane is replaced by Li/Li+, the resulting complex is activated and ready to adsorb hydrogen molecules at a high gravimetric weight percent of around ~7.0%. Due to polarization of hydrogen molecules under the induced electric field generated by positively charged Li/Li+, they are adsorbed on ADM.Li/Li+ complexes with an average binding energy of ~-0.15 eV/H2, desirable for hydrogen storage applications. We also examined the possibility of the replacement of a larger number of acidic hydrogen atoms of adamantane by Li/Li+ and the possibility of aggregations of formed complexes in experiments. The stability of the proposed structures was investigated by calculating vibrational spectra and doing MD simulations.
Cold Baryogenesis from first principles in the Two-Higgs Doublet model with Fermions
Zong-Gang Mou; Paul M. Saffin; Anders Tranberg
2015-05-27
We present a first-principles numerical computation of the baryon asymmetry in electroweak-scale baryogenesis. For the scenario of Cold Baryogenesis, we consider a one fermion-family reduced CP-violating two Higgs-doublet model, including a classical SU(2)-gauge/two-Higgs sector coupled to one quantum left-handed fermion doublet and two right-handed singlets. Separately, the C(CP) breaking of the two-Higgs potential and the C and P breaking of the gauge-fermion interactions do not provide a baryon asymmetry. Only when combined does baryogenesis occur. Through large-scale computer simulations, we compute the asymmetry for one particularly favourable scalar potential. The numerical signal is at the boundary of what is numerically discernible with the available computer resources, but we tentatively find an asymmetry of $|\\eta|\\leq 3.5\\times 10^{-7}$.
First-principles approach to calculating energy level alignment at aqueous semiconductor interfaces
Kharche, Neerav; Muckerman, James T.; Hybertsen, Mark S.
2014-10-21
A first-principles approach is demonstrated for calculating the relationship between an aqueous semiconductor interface structure and energy level alignment. The physical interface structure is sampled using density functional theory based molecular dynamics, yielding the interface electrostatic dipole. The GW approach from many-body perturbation theory is used to place the electronic band edge energies of the semiconductor relative to the occupied 1b? energy level in water. The application to the specific cases of nonpolar (101¯0 ) facets of GaN and ZnO reveals a significant role for the structural motifs at the interface, including the degree of interface water dissociation and themore »dynamical fluctuations in the interface Zn-O and O-H bond orientations. As a result, these effects contribute up to 0.5 eV.« less
Optical properties of ?-, ?-, ?-, and 6,6,12-graphyne structures: First-principle calculations
NASA Astrophysics Data System (ADS)
Shao, Zhi-Gang; Sun, Zhen-Long
2015-11-01
We have investigated optical properties of ?-, ?-, ?-, and 6,6,12-graphyne structures using first-principle calculations. In our calculations, the dielectric function, reflectivity, and absorption coefficient are calculated under both parallel and perpendicular electric field polarizations. Similar to graphene, graphynes are shown to exhibit a structure with broad frequency photoresponse. Remarkably, the results show that the optical spectra of all these graphynes are anisotropic under these two polarizations, i.e., all these graphynes have strong reflectivity in low frequency region under the parallel polarization, but very weak reflectivity under the perpendicular polarization. Moreover, the absorption spectra of all these graphynes under the parallel polarization exhibit high values ranging from the far infrared region to the ultra-violet one. All of these features of graphynes indicate that graphynes would be good potential materials for optoelectronics.
Cold Baryogenesis from first principles in the two-Higgs doublet model with fermions
NASA Astrophysics Data System (ADS)
Mou, Zong-Gang; Saffin, Paul M.; Tranberg, Anders
2015-06-01
We present a first-principles numerical computation of the baryon asymmetry in electroweak-scale baryogenesis. For the scenario of Cold Baryogenesis, we consider a one fermion-family reduced CP-violating two Higgs-doublet model, including a classical SU(2)-gauge/two-Higgs sector coupled to one quantum left-handed fermion doublet and two right-handed singlets. Separately, the C(CP) breaking of the two-Higgs potential and the C and P breaking of the gauge-fermion interactions do not provide a baryon asymmetry. Only when combined does baryogenesis occur. Through large-scale computer simulations, we compute the asymmetry for one particularly favourable scalar potential. The numerical signal is at the boundary of what is numerically discernible with the available computer resources, but we tentatively find an asymmetry of | ?| ? 3.5 × 10-7.
First-Principles Studies of Hydrogen Adsorption at Pd-SiO2 Interfaces
Irokawa, Yoshihiro; Usami, Mamoru
2015-01-01
The interaction of hydrogen with Pd-SiO2 interfaces has been investigated for the first time using first-principles calculations based on density functional theory. The hydrogen-induced polarization at the Pd-SiO2 interfaces was evaluated using Pd-SiO2 interface supercells. As a result, the potential change induced by interfacial hydrogen atoms was not observed even for hydrogen concentration of ~1.3 × 1015 cm?2 at the Pd-SiO2 interface. This result implies that hydrogen does not create an electric double layer at the Pd-SiO2 interface but change the property of the SiO2 region, resulting in the hydrogen sensitivity of the devices. PMID:26110410
Aidhy, Dilpuneet S.; Liu, Bin; Zhang, Yanwen; Weber, William J.
2015-03-01
We study the chemical expansion for neutral and charged oxygen vacancies in fluorite, rocksalt, perovskite and pyrochlores materials using first principles calculations. We show that the neutral oxygen vacancy leads to lattice expansion whereas the charged vacancy leads to lattice contraction. In addition, we show that there is a window of strain within which an oxygen vacancy is stable; beyond that range, the vacancy can become unstable. Using CeO2|ZrO2 interface structure as an example, we show that the concentration of oxygen vacancies can be manipulated via strain, and the vacancies can be preferentially stabilized. These results could serve as guiding principles in predicting oxygen vacancy stability in strained systems and in the design of vacancy stabilized materials.
On Developing a European First Principles Geomagnetically Induced Current Forecasting System
NASA Astrophysics Data System (ADS)
Honkonen, I. J.; Viljanen, A.; Vanhamäki, H.
2012-12-01
Geomagnetically induced currents (GIC) during space storms pose a risk to power transmission grids across the globe. As part of the European Risk from Geomagnetically Induced Currents (EURISGIC) EU/FP7 project the Finnish Meteorological Institute is developing a first principles based GIC forecasting and warning system. The system is given as input the solar wind plasma parameters measured by the ACE spacecraft and the final output consists of the ground electric field and GIC in a simplified model of European high-voltage power grids. We describe the different steps involved in obtaining the final GIC solution and implementation of the required software components. We also present a comparison between simulated electrojet indicators and those derived from the magnetic field measurements of the IMAGE magnetometer network. Additionally the simulated GIC are compared to natural gas pipeline observations in Mäntsälä, Finland.
Liquid iron-hydrogen alloys at outer core conditions by first-principles calculations
NASA Astrophysics Data System (ADS)
Umemoto, Koichiro; Hirose, Kei
2015-09-01
We examined the density, bulk sound (compressional) velocity, and Grüneisen parameter of liquid pure Fe, Fe100H28 (0.50 wt % H), Fe88H40 (0.81 wt % H), and Fe76H52 (1.22 wt % H) at Earth's outer core pressure and temperature (P-T) conditions (~100 to 350 GPa, 4000 to 7000 K) based on first-principles molecular dynamics calculations. The results demonstrate that the thermodynamic Grüneisen parameter of liquid iron alloy decreases with increasing pressure, temperature, and hydrogen concentration, indicating a relatively small temperature gradient in the outer core when hydrogen is present. Along such temperature profile, both the density and compressional velocity of liquid iron containing ~1 wt % hydrogen match seismological observations. It suggests that hydrogen could be a primary light element in the core, although the shear velocity of the inner core is not reconciled with solid Fe-H alloy and thus requires another impurity element.
Stability of FeAl(110) alloy surface structures: a first-principles study
NASA Astrophysics Data System (ADS)
Pan, J. L.; Ni, J.; Yang, B.
2010-02-01
We have studied the stability of FeAl(110) alloy surface structures by first-principles calculations. A general method is employed to determine the allowed chemical potential range for the surface structures of alloys with several bulk ground state structures. We show that there are three stable surface structures, the Fe:Al=1:1, Fe:Al=1:2 and Fe:Al=1:3 surface structures, within the allowed chemical potential range for FeAl bulk. In the three stable surface structures, surface buckling extends deep into the bulk layers. For the Fe:Al=1:1 surface structure, the surface Al atoms displace outwards and surface Fe atoms move inwards relative to their bulk positions. The Fe:Al=1:2 and Fe:Al=1:3 surfaces show large surface rippling due to composition reconstruction of the surface.
Reactivity of adducts relevant to the deposition of hexagonal BN from first-principles calculations
NASA Astrophysics Data System (ADS)
Freitas, R. R. Q.; Gueorguiev, G. K.; de Brito Mota, F.; de Castilho, C. M. C.; Stafström, S.; Kakanakova-Georgieva, A.
2013-09-01
First-principles calculations, which also implement the nudged elastic band (NEB) code, are performed to investigate (i) the stability of the (C2H5)3B:NH3 adduct formed by the initial precursor molecules triethylborane (C2H5)3B and ammonia NH3 in the metal-chemical-vapor-deposition (MOCVD) of hexagonal BN, and (ii) the energy barrier to the first ethane elimination through consistent unimolecular, ammonia-assisted, and adduct-assisted reaction pathways. Comparison is done with the reference case of the (CH3)3Al:NH3 adduct, notoriously known for its high degree of stability and reactivity, which determines an overall severe parasitic gas-phase chemical reaction mechanism in the deposition of AlN.
First-principles approach to nonlinear lattice dynamics: anomalous spectra in PbTe.
Chen, Yue; Ai, Xinyuan; Marianetti, C A
2014-09-01
Here we introduce a new approach to compute the finite temperature lattice dynamics from first principles via the newly developed slave mode expansion. We study PbTe where inelastic neutron scattering reveals strong signatures of nonlinearity as evidenced by anomalous features which emerge in the phonon spectra at finite temperature. Using our slave mode expansion in the classical limit, we compute the vibrational spectra and show remarkable agreement with temperature dependent inelastic neutron scattering measurements. Furthermore, we resolve an experimental controversy by showing that there are no appreciable local nor global spontaneously broken symmetries at finite temperature and that the anomalous spectral features simply arise from two anharmonic interactions. Our approach should be broadly applicable across the periodic table. PMID:25238367
Jet shapes for boosted jet two-prong decays from first-principles
Dasgupta, Mrinal; Soyez, Gregory
2015-01-01
Several boosted jet techniques use jet shape variables to discriminate the multi-pronged signal from Quantum Chromodynamics backgrounds. In this paper, we provide a first-principles study of an important class of jet shapes all of which put a constraint on the subjet mass: the mass-drop parameter ($\\mu^2$), the $N$-subjettiness ratio ($\\tau_{21}^{(\\beta=2)}$) and energy correlation functions ($C_2^{(\\beta=2)}$ or $D_2^{(\\beta=2)}$). We provide analytic results both for QCD background jets as well as for signal processes. We further study the situation where cuts on these variables are applied recursively with Cambridge-Aachen de-clustering of the original jet. We also explore the effect of the choice of axis for $N$-subjettiness and jet de-clustering. Our results bring substantial new insight into the nature, gain and relative performance of each of these methods, which we expect will influence their future application for boosted object searches.
Detection of nucleic acids by graphene-based devices: A first-principles study
Zhang, Hua; Xu, Hui E-mail: ouyangfp06@tsinghua.org.cn; Ni, Xiang; Lin Peng, Sheng; Liu, Qi; Ping OuYang, Fang E-mail: ouyangfp06@tsinghua.org.cn
2014-04-07
Based on first-principles quantum transport calculations, we design a graphene-based biosensor device, which is composed of graphene nanoribbons electrodes and a biomolecule. It is found that when different nucleobases or poly nucleobase chains are located in the nanogap, the device presents completely different transport properties, showing different current informations. And the change of currents from 2 to 5 orders of magnitude for four different nucleobases suggests a great ability of discrimination by utilizing such a device. The physical mechanism of this phenomenon originates from their different chemical composition and structure. Moreover, we also explore the coupling effect of several neighboring bases and the size effect of the nanogap on transport properties. Our results show the possibility of rapid sequencing DNA by measuring such a transverse-current of the device, and provide a new idea for sequencing DNA.
Liquid iron-sulfur alloys at outer core conditions by first-principles calculations
NASA Astrophysics Data System (ADS)
Umemoto, Koichiro; Hirose, Kei; Imada, Saori; Nakajima, Yoichi; Komabayashi, Tetsuya; Tsutsui, Satoshi; Baron, Alfred Q. R.
2014-10-01
We perform first-principles calculations to investigate liquid iron-sulfur alloys (Fe, Fe56S8, Fe52S12, and Fe48S16) under high-pressure and high-temperature (150-300 GPa and 4000-6000 K) conditions corresponding to the Earth's outer core. Considering only the density profile, the best match with the preliminary reference Earth model is by liquid Fe-14 wt % S (Fe50S14), assuming sulfur is the only light element. However, its bulk sound velocity is too high, in particular in the deep outer core, suggesting that another light component such as oxygen is required. An experimental check using inelastic X-ray scattering shows good agreement with the calculations. In addition, a present study demonstrates that the Birch's law does not hold for liquid iron-sulfur alloy, consistent with a previous report on pure liquid iron.
Lattice thermal conductivity in ? - Ga 2 O 3 from first principles
NASA Astrophysics Data System (ADS)
Santia, Marco D.; Tandon, Nandan; Albrecht, J. D.
2015-07-01
The lattice thermal conductivity for bulk ? - Ga 2 O 3 is computed from the phonon Boltzmann transport equation using first-principles methods to obtain scattering rates. Force constants for both the second and third order potential interactions are computed with a real-space finite-displacement approach. Phonon band structures as well as anharmonic properties are then computed and used to calculate the bulk thermal conductivity tensor ?, for temperatures ranging from 25 K to 1050 K. The calculated conductivity tensor components and analytic fits to their temperature dependences are elaborated. We compare our results with available data and show good agreement with experimentally observed values. Decomposing ? into mode contributions reveals that optical phonon modes contribute significantly to the overall thermal conductivity, as much as 44% at 300 K in the [010] direction, which differs from previous interpretations of experimentally observed thermal conductivity tensor anisotropy.
Elastic properties of sulphur and selenium doped ternary PbTe alloys by first principles
Bali, Ashoka Chetty, Raju Mallik, Ramesh Chandra
2014-04-24
Lead telluride (PbTe) is an established thermoelectric material which can be alloyed with sulphur and selenium to further enhance the thermoelectric properties. Here, a first principles study of ternary alloys PbS{sub x}Te{sub (1?x)} and PbSe{sub x}Te{sub (1?x)} (0?x?1) based on the Virtual Crystal Approximation (VCA) is presented for different ratios of the isoelectronic atoms in each series. Equilibrium lattice parameters and elastic constants have been calculated and compared with the reported data. Anisotropy parameter calculated from the stiffness constants showed a slight improvement in anisotropy of elastic properties of the alloys over undoped PbTe. Furthermore, the alloys satisfied the predicted stability criteria from the elastic constants, showing stable structures, which agreed with the previously reported experimental results.
The Interface between Gd and Monolayer MoS2: A First-Principles Study
Zhang, Xuejing; Mi, Wenbo; Wang, Xiaocha; Cheng, Yingchun; Schwingenschlögl, Udo
2014-01-01
We analyze the electronic structure of interfaces between two-, four- and six-layer Gd(0001) and monolayer MoS2 by first-principles calculations. Strong chemical bonds shift the Fermi energy of MoS2 upwards into the conduction band. At the surface and interface the Gd f states shift to lower energy and new surface/interface Gd d states appear at the Fermi energy, which are strongly hybridized with the Mo 4d states and thus lead to a high spin-polarization (ferromagnetically ordered Mo magnetic moments of 0.15??B). Gd therefore is an interesting candidate for spin injection into monolayer MoS2. PMID:25482498
Protein-Protein Interactions from Linear-Scaling First Principles Quantum Mechanical Calculations
NASA Astrophysics Data System (ADS)
Cole, Daniel; Skylaris, Chris-Kriton; Rajendra, Eeson; Venkitaraman, Ashok; Payne, Mike
2010-03-01
A modification of the MM-PBSA technique for calculating binding affinities of biomolecular complexes is presented. Classical molecular dynamics is used to explore the motion of the extended interface between two peptides derived from the BRC4 repeat of BRCA2 and the eukaryotic recombinase RAD51. The resulting trajectory is sampled using the linear-scaling density functional theory code, onetep, to determine from first principles, and with high computational efficiency, the relative free energies of binding of the ˜2800 atom receptor-ligand complexes. This new method provides the basis for computational interrogation of protein-protein and protein-ligand interactions, within fields ranging from chemical biological studies to small molecule binding behaviour, with both unprecedented chemical accuracy and affordable computational expense.
Protein-protein interactions from linear-scaling first-principles quantum-mechanical calculations
NASA Astrophysics Data System (ADS)
Cole, D. J.; Skylaris, C.-K.; Rajendra, E.; Venkitaraman, A. R.; Payne, M. C.
2010-08-01
A modification of the MM-PBSA technique for calculating binding affinities of biomolecular complexes is presented. Classical molecular dynamics is used to explore the motion of the extended interface between two peptides derived from the BRC4 repeat of BRCA2 and the eukaryotic recombinase RAD51. The resulting trajectory is sampled using the linear-scaling density functional theory code, onetep, to determine from first principles, and with high computational efficiency, the relative free energies of binding of the ~2800 atom receptor-ligand complexes. This new method provides the basis for computational interrogation of protein-protein and protein-ligand interactions within fields ranging from chemical biological studies to small-molecule binding behaviour, with both unprecedented chemical accuracy and affordable computational expense.
C4 Carbon allotropes with triple-bonds predicted by first-principles calculations
NASA Astrophysics Data System (ADS)
Kim, Bog G.; Sim, Hyunsu; Park, Jooeun
2013-09-01
New structures of body-centered, tetragonal C4 carbon allotropes containing a mixture of sp (triple yne bond) and sp3 (single bond) hybridization were designed using first-principles calculations. These three structures named 1-Yne, 2-Yne and 3-Yne C4 carbon not only maintained the tetragonal space group (SG# 139) of C4 carbon, but also exhibited unique physical and chemical properties due to triple-like bonding. The dynamic stability of these structures was confirmed using phonon calculations, and the entire structure showed a unique phonon spectrum with an Eigen-frequency of ~2250 cm-1, which is a characteristic of a triple bond. Structure prediction by X-ray simulations was performed and the band structure due to triple bond modification was identified. Details of the bulk properties, such as lattice constant, bond length and bulk modulus, could be explained well by a simple physical picture due to the triple bond.
Dynamic process of H-controlled oxygen concentration in LBE: A first-principles study
NASA Astrophysics Data System (ADS)
Li, Dongdong; Zhang, Y. G.; He, H. Y.; Liu, C. S.; Pan, B. C.
2015-12-01
First-principles molecular dynamics simulations have been performed to study the behaviors of H and the dynamic process of H-controlled O concentration in the liquid lead bismuth eutectic (LBE). Our calculations show that H2 molecules in LBE are dissociated to be diffusive H atoms, taking the forms of H-metal clusters. Meanwhile, H prefers to interact with O in LBE to form HO radicals and H2O molecules, reducing the O concentration in LBE. With the mass action analysis, we quantitatively predict the variation of the O concentration in LBE with the amount of the introduced H2 at different temperatures. Our results are practical for the H-controlled O concentration in LBE experiments.
NASA Astrophysics Data System (ADS)
Giannozzi, P.; De Angelis, F.; Car, R.
2004-04-01
We present a plane-wave ultrasoft pseudopotential implementation of first-principle molecular dynamics, which is well suited to model large molecular systems containing transition metal centers. We describe an efficient strategy for parallelization that includes special features to deal with the augmented charge in the contest of Vanderbilt's ultrasoft pseudopotentials. We also discuss a simple approach to model molecular systems with a net charge and/or large dipole/quadrupole moments. We present test applications to manganese and iron porphyrins representative of a large class of biologically relevant metalorganic systems. Our results show that accurate density-functional theory calculations on systems with several hundred atoms are feasible with access to moderate computational resources.
Coinage metal (4, 4) nanotubes, simulated by first-principles calculations.
Fa, Wei; Zhou, Jian; Dong, Jinming; Kawazoe, Y
2011-06-28
The structural stability of coinage metal nanotubes with a square cross-section has been investigated by the first-principles numerical simulations. In addition to the reported (4, 4) silver tube, it is found that the hollow (4, 4) copper and gold nanotubes can also be formed by applying an appropriate stress to an 8(A)/8(B) fcc wire. The stability of these coinage metal (4, 4) nanotubes, formed by tip-stretching the wires, has been explained by a local minimum in the string tension variation with their tube lengths. Interestingly, we have explained why a low-stress stretching is needed to obtain the (4, 4) Cu tube in contrast to a higher one for both the (4, 4) Ag and Au tubes due to the larger stiffness coefficient of copper than those of silver and gold, which could be proved by future experiments. PMID:21721640
Fa, Wei; Zhou, Jian; Dong, Jinming
2013-04-01
Substitutional doping of gold and copper atoms in a (4, 4) silver single-wall nanotube has been investigated using first-principles simulations. It is found that the Au- and Cu-substitutional doping of the tip-suspended (4, 4) Ag tube can maintain the hollow tubular structure at different alloy compositions due to the existence of a local minimum in the string tension variation with their unit cell lengths. The bonding energy differences between the mono-elements and hetero-elements and string tension may play important roles in suppressing the "self-purification" effects so that the nanoalloy tubes can be formed. Analysis of the band structure suggests that the number of conduction channels of the Ag-Au alloy tubes may lie between the pure (4, 4) Ag and Au tubes. PMID:23423486
Coinage metal (4, 4) nanotubes, simulated by first-principles calculations
NASA Astrophysics Data System (ADS)
Fa, Wei; Zhou, Jian; Dong, Jinming; Kawazoe, Y.
2011-06-01
The structural stability of coinage metal nanotubes with a square cross-section has been investigated by the first-principles numerical simulations. In addition to the reported (4, 4) silver tube, it is found that the hollow (4, 4) copper and gold nanotubes can also be formed by applying an appropriate stress to an 8A/8B fcc wire. The stability of these coinage metal (4, 4) nanotubes, formed by tip-stretching the wires, has been explained by a local minimum in the string tension variation with their tube lengths. Interestingly, we have explained why a low-stress stretching is needed to obtain the (4, 4) Cu tube in contrast to a higher one for both the (4, 4) Ag and Au tubes due to the larger stiffness coefficient of copper than those of silver and gold, which could be proved by future experiments.
Glass polymorphism in amorphous germanium probed by first-principles computer simulations.
Mancini, G; Celino, M; Iesari, F; Di Cicco, A
2016-01-13
The low-density (LDA) to high-density (HDA) transformation in amorphous Ge at high pressure is studied by first-principles molecular dynamics simulations in the framework of density functional theory. Previous experiments are accurately reproduced, including the presence of a well-defined LDA-HDA transition above 8 GPa. The LDA-HDA density increase is found to be about 14%. Pair and bond-angle distributions are obtained in the 0-16 GPa pressure range and allowed us a detailed analysis of the transition. The local fourfold coordination is transformed in an average HDA sixfold coordination associated with different local geometries as confirmed by coordination number analysis and shape of the bond-angle distributions. PMID:26642884
Intrinsic spin Hall effect in monolayers of group-VI dichalcogenides: A first-principles study
NASA Astrophysics Data System (ADS)
Feng, Wanxiang; Yao, Yugui; Zhu, Wenguang; Zhou, Jinjian; Yao, Wang; Xiao, Di
2012-10-01
Using first-principles calculations within density functional theory, we investigate the intrinsic spin Hall effect in monolayers of group-VI transition-metal dichalcogenides MX2 (M=Mo,W and X=S,Se). MX2 monolayers are direct band-gap semiconductors with two degenerate valleys located at the corners of the hexagonal Brillouin zone. Because of the inversion symmetry breaking and the strong spin-orbit coupling, charge carriers in opposite valleys carry opposite Berry curvature and spin moment, giving rise to both a valley-Hall and a spin-Hall effect. We also show that the intrinsic spin Hall conductivity in inversion-symmetric bulk dichalcogenides is an order of magnitude smaller compared to monolayers. Our result demonstrates monolayer dichalcogenides as an ideal platform for the integration of valleytronics and spintronics.
First-principles diffusion-barrier calculation for atomic oxygen on Pt(111)
NASA Astrophysics Data System (ADS)
Bogicevic, Alexander; Strömquist, Johan; Lundqvist, Bengt I.
1998-02-01
An inconsistency is pointed out in adsorption energy values for O diffusion on Pt(111) in three recent studies: (A) the scanning tunneling microscope (STM)-deduced value of 0.43 eV for the diffusion barrier [J. Wintterlin, R. Schuster, and G. Ertl, Phys. Rev. Lett. 77, 123 (1996)]; (B) the calculated fcc-hcp adsorption-energy difference [P. J. Fiebelman, E. Stefanie, and M. Thomas, ibid.77, 2257 (1997)]; and (C) the STM-identified metastability of O in hcp sites [B. C. Stipe et al., ibid.78, 4410 (1997)]. Using accurate first-principles density-functional methods we obtain full agreement with (B) and (C) and a diffusion barrier of 0.58 eV, consistent with a reinterpretation of the raw data in (A). We further report on oxygen-induced surface buckling.
Yu, Shuyin; Zeng, Qingfeng; Oganov, Artem R; Frapper, Gilles; Zhang, Litong
2015-05-01
We have performed first-principles evolutionary searches for stable Ti-N compounds and have found, in addition to the well-known rock-salt TiN, new ground states Ti3N2, Ti4N3, Ti6N5 at atmospheric pressure, and Ti2N and TiN2 at higher pressures. The latter nitrogen-rich structure contains encapsulated N2 dumbbells with a N-N distance of 1.348 Å at 60 GPa. TiN2 is predicted to be mechanically stable and quenchable. Our calculations on the mechanical properties (bulk modulus, shear modulus, Young's modulus, Poisson's ratio, and hardness) are in excellent agreement with the available experimental data. Further analyses of the electronic density of states, crystal orbital Hamilton population and the electron localization function reveal that the hardness is enhanced by strengthening directional covalent bonds and disappearance of Ti-Ti metallic bonding. PMID:25869225
Mn Monolayer Modified Rh for Syngas-to-Ethanol Conversion: A First-Principles Study
Li, Fengyu; Jiang, Deen; Zeng, X.C.; Chen, Zhongfang
2012-01-01
Rh is unique in its ability to convert syngas to ethanol with the help of promoters. We performed systematic first-principles computations to examine the catalytic performance of pure and Mn modified Rh(100) surfaces for ethanol formation from syngas. CO dissociation on the surface as well as CO insertion between the chemisorbed CH{sub 3} and the surface are the two key steps. The CO dissociation barrier on the Mn monolayer modified Rh(100) surface is remarkably lowered by {approx}1.5 eV compared to that on Rh(100). Moreover, the reaction barrier of CO insertion into the chemisorbed CH{sub 3} group on the Mn monolayer modified Rh(100) surface is 0.34 eV lower than that of methane formation. Thus the present work provides new mechanistic insight into the role of Mn promoters in improving Rh's selectivity to convert syngas to ethanol.
Azuri, Ido; Adler-Abramovich, Lihi; Gazit, Ehud; Hod, Oded; Kronik, Leeor
2014-01-22
The diphenylalanine peptide self-assembles to form nanotubular structures of remarkable mechanical, piezolelectrical, electrical, and optical properties. The tubes are unexpectedly stiff, with reported Young's moduli of 19-27 GPa that were extracted using two independent techniques. Yet the physical basis for the remarkable rigidity is not fully understood. Here, we calculate the Young's modulus for bulk diphenylalanine peptide from first principles, using density functional theory with dispersive corrections. The calculation demonstrates that at least half of the stiffness of the material is the result of dispersive interactions. We further quantify the nature of various inter- and intramolecular interactions. We reveal that despite the porous nature of the lattice, there is an array of rigid nanotube backbones with interpenetrating "zipper-like" aromatic interlocks that result in stiffness and robustness. This presents a general strategy for the analysis of bioinspired functional materials and may pave the way for rational design of bionanomaterials. PMID:24368025
First-principles study of transition-metal-doped single-walled carbon nanotubes
NASA Astrophysics Data System (ADS)
Mao, Yu-Liang; Yan, Xiao-Hong; Xiao, Yang
2005-12-01
We study the effect of doping transition metals (TMs) into single-wall carbon nanotubes by using first-principles calculations. For metallic isolated (3,3) single-wall carbon nanotubes, doping of Mn, Fe and Co makes them semi-metallic, while Ni doping leads to semiconductors. For (3,3) nanotube bundles, a Co atom in the unit cell makes it exhibit semiconductor character. With two or three Co and Ni atoms doped into the bundle, the impurity atoms change the nanotube to semi-metal. In particular, the Mn2C12 and Mn3C12 bundle have comparable large magnetic moments, suggesting that such TM-doped nanotubes could be useful as nanomagnets.
First-principles study of the noble metal-doped BN layer
Zhou, Yungang; Yang, Ping; Sun, Xin; Wang, Zhiguo; Zu, Xiaotao T.; Gao, Fei
2011-04-18
Intriguing electronic and magnetic properties of BN layer with noble metal (Pd, Pt, Ag and Au) doping are obtained by first-principles calculations. Adsorbed Pd (or Pt) reduces the band gap of BN sheet owing to the induction of impurity states. The unpaired electrons in the Ag (or Au)-adsorbed and the Pd (or Pt)-substituted BN layers are polarized, and thus exhibit a magnetic moment of 1.0 µB, leading to these BN configurations to be magnetic semiconductors. The half-metallic feature of the Ag-substituted BN layer, along with the delocalization of spin states, renders this configuration an excellent spin filter material. Thus, these findings offer a unique opportunity for developing BN-based nanoscale devices.
First principles calculation of CH4 decomposition on nickel (111) surface
NASA Astrophysics Data System (ADS)
Arifin, Rizal; Shibuta, Yasushi; Shimamura, Kohei; Shimojo, Fuyuki
2015-11-01
The mechanism of the CH4 decomposition on the nickel (111) surface is investigated by first principles calculations. The activation energy of each reaction is calculated using nudged elastic band method. The activation energy of hydrogen dissociation from a CH2 fragment is found much lower than the one of a CH3 fragment. This result is consistent with the fact, observed in our previous molecular dynamics (MD) simulations, that the CH3 fragment is dissociated into a CH fragment and two hydrogen atoms spontaneously. The effects of finite temperature at 1500 K on the decomposition reaction of a CH4 molecule and its fragments are also investigated using constraint MD method. While the temperature effects are barely visible in CH4 and CH2 dissociation processes, they reduce the activation free energy of hydrogen dissociation from CH3 and CH fragments largely.
High pressure phase transformation in thorium carbide: A first principle study
NASA Astrophysics Data System (ADS)
Sahoo, B. D.; Joshi, K. D.; Gupta, Satish C.
2013-06-01
First principles calculations using full potential linearized augmented plane wave (FP-LAPW) method have been carried out to analyze structural, electronic and elastic properties of ThC under hydrostatic compression. Our calculations carried out within the generalized gradient approximation (GGA) predict a structural phase transition from rocksalt type (B1) phase to CsCl type cubic (B2) structure at ˜ 45 GPa. The same transition is predicted to occur at ˜ 35 GPa by the calculations performed within local density approximation (LDA). Various physical quantities such as equilibrium volume, bulk modulus, pressure derivative of bulk modulus and elastic constants determined for both the phases at zero pressure are compared with data available in literature. We find that at zero pressure the B2 structure is unstable elastically also. However, it emerges as elastically stable structure before it stabilizes energetically at high pressure. Further, the activation barrier between these structures has been calculated at various pressures.
First-principles determination of the surface-phonon dispersion curves of metals.
NASA Astrophysics Data System (ADS)
Quong, Andrew A.
1996-03-01
With experimental techniques such as HREELS and inelastic He atom scattering, surface phonon dispersion curves of a wide range of materials have been measured. In the case of metals, the electron screening at the surface is modified and introduces changes in the interatomic force constants at the surface. Semi-empirical and empirical models fit the experimental data very well, but these models often describe the bonding at the surface in very different ways and are often contradictory. In the present study, the interatomic force constants are determined from first-principles for s-p bonded metals. The calculations are based upon linear response and density functional theory with non-local pseudopotentials taken to represent the ion-electron interaction. Comparison with experiment is very good, and large changes in the bonding at the surface are found. Supported by the U.S. Department of Energy, Office of Basic Energy Sciences, Division of Material Sciences.
Adsorption and diffusion of adatoms on Ru(0 0 0 1): A first-principles study
NASA Astrophysics Data System (ADS)
Lu, Yunhao; Sun, Q.; Jia, Yu; He, P.
2008-07-01
Using first-principles total energy calculations within density functional theory, we investigated adsorption and diffusion of various elements (S, Ge, Pd, Ag and Pt) on the Ru(0 0 0 1) surface. It was found that the hcp hollow site is the preferred adsorption site for all atoms considered (S, Ge, Pd and Pt) except Ag which has equal probability to be adsorbed at the hcp hollow site, fcc hollow site, and the bridge site. Furthermore, S and Ge addlayers become unstable when the coverage goes beyond 0.25 monolayer (ML) due to the repulsive interaction between adsorbates. In contrary, the binding energies of the metal adsorbates Pd, Ag and Pt increase with coverage, all the way up to full coverage (1 ML). The diffusion barriers of the five adsorbates on Ru(0 0 0 1) are investigated and their relationships with the covalent radii of the adsorbates are discussed.
Novel electronic and magnetic properties in AlN nanoribbons: First-principles prediction
NASA Astrophysics Data System (ADS)
Luan, Hang-Xing; Zhang, Chang-Wen; Yan, Shi-Shen
2013-08-01
Based on first-principles calculations, we investigate the electronic structure and magnetic properties of bare and hydrogen-terminated AlN nanoribbons (NRs). When both Al and N edges are terminated by hydrogen, it exhibits a semiconducting behavior with a direct band gap of 2.76 eV. The H-terminations at the Al edge lead to a ferromagnetic (FM) ground state with a net magnetic moment of 1.0\\mu_{B} per unit cell, while the H-terminated N edge state exhibits an antiferromagnetic property. For bare AlNNRs, the half-metallic, semiconducting, or metallic characters are all obtained, dependent on spin alignments of Al and N edge states. These predicted diverse and tunable electronic properties endow AlNNRs potential applications in electronics and spintronics.
Substrate-induced magnetism in BN layer: A first-principles study
Zhou, Yungang; Zu, Xiaotao T.; Gao, Fei
2011-06-01
We predict an accepted configuration of hexagonal boron nitride (BN) layer on Co(111) surface by first-principles calculations. The calculated adsorption energy of this configuration is around -0.51 eV with a corrugation close to 0.1 Å. Polarized spin states are induced in BN layer due to the hybridization of the BN layer with the substrate Co, which gives rise to a magnetic moment of 0.2 ?B on each pair of BN. The finding of high spin polarization on the absorbed BN layer ensures a high degree of passage of the preferred spin and is important in the development of nanoscale devices for spintronics applications.
Conductance of ferro- and antiferro-magnetic single-atom contacts: A first-principles study
Tan, Zhi-Yun; Zheng, Xiao-long; Ye, Xiang; Xie, Yi-qun; Ke, San-Huang
2013-08-14
We present a first-principles study on the spin dependent conductance of five single-atom magnetic junctions consisting of a magnetic tip and an adatom adsorbed on a magnetic surface, i.e., the Co-Co/Co(001) and Ni-X/Ni(001) (X = Fe, Co, Ni, Cu) junctions. When their spin configuration changes from ferromagnetism to anti-ferromagnetism, the spin-up conductance increases while the spin-down one decreases. For the junctions with a magnetic adatom, there is nearly no spin valve effect as the decreased spin-down conductance counteracts the increased spin-up one. For the junction with a nonmagnetic adatom (Ni-Cu/Ni(001)), a spin valve effect is obtained with a variation of 22% in the total conductance. In addition, the change in spin configuration enhances the spin filter effect for the Ni-Fe/Ni(001) junction but suppresses it for the other junctions.
First Principles Study of Dihydride Chains on H-Terminated Si(100)-2×1 Surface
NASA Astrophysics Data System (ADS)
Suwa, Yuji; Fujimori, Masaaki; Heike, Seiji; Terada, Yasuhiko; Yoshimoto, Yoshihide; Akagi, Kazuto; Sugino, Osamu; Hashizume, Tomihiro
2006-03-01
Scanning-tunneling-microscopy observation of an H-terminated Si(100)-2×1 surface often shows the existence of a single dihydride-chain structure parallel to step edges. This chain is located near an SB step edge, but away from it by more than one Si-dimer’s distance. In order to discuss the mechanism of the formation of such a structure, we have performed first-principles calculations. As a result, we have found that the rebonded step edge of the clean Si surface turns into one dihydride chain and a non-rebonded step edge after hydrogen termination. We have also found that the chain adjacent to the step edge is energetically less stable than in a distant position from the step.
First Principles Study of Dihydride-Chain Structures on H-Terminated Si(100) Surface
NASA Astrophysics Data System (ADS)
Suwa, Yuji; Fujimori, M.; Heike, S.; Terada, Y.; Hashizume, T.
2006-06-01
On a H-terminated Si(100)-2×1 surface, a dihydride-chain structure parallel to the step edge is often found by Scanning Tunneling Microscopy. The chain is located near an SB step edge, but away from it by more than one Si-dimer's distance. We performed first principles calculations to determine the mechanism of the chain formation. As a result, we found that the rebonded step edge of the clean Si surface turns into a combination of a dihydride chain and a non-rebonded step edge after hydrogen termination. We also found that the chain adjacent to the step edge is energetically less stable than that at one Si-dimer distance away from the step.
Role of Rate of Specific Growth Rate in Different Growth Processes: A First Principle Approach
Biswas, Dibyendu; Patra, Sankar Nayaran
2015-01-01
In the present communication, effort is given for the development of a common platform that helps to address several growth processes found in literature. Based on first principle approach, the role of rate of specific growth rate in different growth processes has been considered in an unified manner. It is found that different growth equations can be derived from the same rate equation of specific growth rate. The dependence of growth features of different growth processes on the parameters of the rate equation of specific growth rate has been examined in detail. It is found that competitive environment may increase the saturation level of population size. The exponential growth could also be addressed in terms of two important factors of growth dynamics, as reproduction and competition. These features are, most probably, not reported earlier.
Effect of stacking faults on the magnetocrystalline anisotropy of hcp Co: a first-principles study
NASA Astrophysics Data System (ADS)
Aas, C. J.; Szunyogh, L.; Evans, R. F. L.; Chantrell, R. W.
2013-07-01
In terms of the fully relativistic screened Korringa-Kohn-Rostoker method we investigate the effect of stacking faults on the magnetic properties of hexagonal close-packed (hcp) cobalt. In particular, we consider the formation energy and the effect on the magnetocrystalline anisotropy energy (MAE) of four different stacking faults in hcp cobalt—an intrinsic growth fault, an intrinsic deformation fault, an extrinsic fault and a twin-like fault. We find that the intrinsic growth fault has the lowest formation energy, in good agreement with previous first-principles calculations. With the exception of the intrinsic deformation fault which has a positive impact on the MAE, we find that the presence of a stacking fault generally reduces the MAE of bulk Co. Finally, we consider a pair of intrinsic growth faults and find that their effect on the MAE is not additive, but synergic.
NASA Astrophysics Data System (ADS)
Hsu, Hsiao-Hsuan; Cheng, Chun-Hu; Lin, Yu-Li; Chiou, Shan-Haw; Huang, Chiung-Hui; Cheng, Chin-Pao
2013-07-01
This study demonstrates the feasibility of producing a tantalum nitride (TaN) thin film as a diffusion barrier and buffer layer for p-type bismuth telluride [(Bi,Sb)2Te3] thermoelectric devices. A network of TaN with nitrogen (N) incorporation is structurally more stable on (Bi,Sb)2Te3 than the conventional Ni diffusion barrier because of less inter-diffusion and a greater likelihood of stoichiometry in the TaN/(Bi,Sb)2Te3 interface. The atomic inter-diffusion between the barrier layers and (Bi,Sb)2Te3 was evaluated in terms of interface adhesion energy using nanoscratching, and proved with first-principles calculations.
First-principles study of alkali metal-graphite intercalation compounds
NASA Astrophysics Data System (ADS)
Nobuhara, Kunihiro; Nakayama, Hideki; Nose, Masafumi; Nakanishi, Shinji; Iba, Hideki
2013-12-01
First-principles calculations were carried out for the alkali (Li, Na, K) metal-graphite intercalation compounds (AM-GICs). From the calculated formation energies (?E) of the AM-GICs, it was determined that each Li-GIC and K-GIC were energetically stable until the high alkali metal density LiC6 and KC8. On the other hand, even the low Na density NaC16 and NaC12 are already not stable. Furthermore, the NaC8 and NaC6 are unstable. It has been experimentally reported that Na hardly intercalates into the graphite contrary to the Li and K. Our calculation results agree with these facts. In addition, based on the calculated energy barriers of the Li, Na and K ion jumps between sites in the graphite, it can be deduced that larger radius ions more smoothly diffuse in the graphite.
First-Principles Determination of Ultralow Thermal Conductivity of monolayer WSe2
Zhou, Wu-Xing; Chen, Ke-Qiu
2015-01-01
By using first-principles calculations combined with the phonon Boltzmann transport equation, we systematically investigate the phonon transport of monolayer WSe2. Compared with other 2D materials, the monolayer WSe2 is found to have an ultralow thermal conductivity due to the ultralow Debye frequency and heavy atom mass. The room temperature thermal conductivity for a typical sample size of 1??m is 3.935 ?W/m K, which is one order of magnitude lower than that of MoS2. And the room temperature thermal conductivity can be further decreased by about 95% in 10?nm sized samples. Moreover, we also find the ZA phonons have the dominant contribution to the thermal conductivity, and the relative contribution is almost 80% at room temperature, which is remarkably higher than that for monolayer MoS2. This is because the ZA phonons have longer lifetime than that of LA and TA phonons in monolayer WSe2. PMID:26464052
A first-principles characterization of water adsorption on forsterite grains.
Asaduzzaman, Abu Md; Laref, Slimane; Deymier, P A; Runge, Keith; Cheng, H-P; Muralidharan, Krishna; Drake, M J
2013-07-13
Numerical simulations examining chemical interactions of water molecules with forsterite grains have demonstrated the efficacy of nebular gas adsorption as a viable mechanism for water delivery to the terrestrial planets. Nevertheless, a comprehensive picture detailing the water-adsorption mechanisms on forsterite is not yet available. Towards this end, using accurate first-principles density functional theory, we examine the adsorption mechanisms of water on the (001), (100), (010) and (110) surfaces of forsterite. While dissociative adsorption is found to be the most energetically favourable process, two stable associative adsorption configurations are also identified. In dual-site adsorption, the water molecule interacts strongly with surface magnesium and oxygen atoms, whereas single-site adsorption occurs only through the interaction with a surface Mg atom. This results in dual-site adsorption being more stable than single-site adsorption. PMID:23734049
First-principles prediction of the Raman shifts in parahydrogen clusters
NASA Astrophysics Data System (ADS)
Faruk, Nabil; Schmidt, Matthew; Li, Hui; Le Roy, Robert J.; Roy, Pierre-Nicholas
2014-07-01
We report a first-principles prediction of the Raman shifts of parahydrogen (pH2) clusters of sizes N = 4-19 and 33, based on path integral ground-state simulations with an ab initio potential energy surface. The Raman shifts are calculated, using perturbation theory, as the average of the difference-potential energy surface between the potential energy surfaces for vibrationally excited and ground-state parahydrogen monomers. The radial distribution of the clusters is used as a weight function in this average. Very good overall agreement with experiment [G. Tejeda, J. M. Fernández, S. Montero, D. Blume, and J. P. Toennies, Phys. Rev. Lett. 92, 223401 (2004)] is achieved for p(H2)2-8,13,33. A number of different pair potentials are employed for the calculation of the radial distribution functions. We find that the Raman shifts are sensitive to slight variations in the radial distribution functions.
Mechanical and electronic properties of Rh and Rh3Zr from first-principles calculation
NASA Astrophysics Data System (ADS)
Zhang, Suhong; Zhang, Xinyu; Zhu, Yan; Sun, Na; Qin, Jiaqian; Liu, Riping
2014-07-01
To give insight on developing Rh-based superalloys, systematic investigations on mechanical and electronic properties of fcc Rh and L12 Rh3Zr are conducted by first-principles calculation. Basic mechanical parameters including bulk modulus, elastic constants, shear modulus, Young's modulus, Poisson's ratio, and elastic anisotropy are calculated. Additionally, the ideal strengths are investigated under tensile and shear loading. Our results reveal that L12 Rh3Zr has lower mechanical strength but higher ductility than fcc Rh. The analysis of density of states reveals that the Rh-d electrons in L12 Rh3Zr become more localized, whereas the Zr-d electrons become more delocalized, than in pure bulk, due to the interaction of Rh and Zr.
First-principles study of group V and VII impurities in SnS2
NASA Astrophysics Data System (ADS)
Xia, Congxin; Zhao, Xu; Peng, Yuting; Zhang, Heng; Wei, Shuyi; Jia, Yu
2015-09-01
Based on density functional theory, the electronic structure, formation energy and transition level of group V and VII atoms-doped SnS2 are investigated by means of first-principles methods. Numerical results show that the formation energy and transition level are dependent highly on the atom number in the periodic table. Group V atom substituting S atom has high formation energy and can create deep acceptor impurity level inside the band gap of SnS2. However, our calculations also show that group VII atom substituting S atom may serve as a promising n-type doping in the SnS2 due to its negative formation energy and shallow transition level under the Sn-rich growth conditions.
NASA Astrophysics Data System (ADS)
Lischner, Johannes; Bazhirov, Timur; MacDonald, Allan H.; Cohen, Marvin L.; Louie, Steven G.
2015-03-01
We present first-principles calculations of the coupling of quasiparticles to spin fluctuations in iron selenide and discuss which types of superconducting instabilities this coupling gives rise to. We find that strong antiferromagnetic stripe-phase spin fluctuations lead to large coupling constants for superconducting gaps with s +/- -symmetry, but these coupling constants are significantly reduced by other spin fluctuations with small wave vectors. An accurate description of this competition and an inclusion of band structure and Stoner parameter renormalization effects lead to a value of the coupling constant for an s +/- symmetric gap which can produce a superconducting transition temperature consistent with experimental measurements. This work was supported by NSF Grant No. DMR10-1006184 and by DOE under Contract No. DE-AC02-05CH11231. Computational resources have been provided by the DOE at NERSC.
Structural stability and electronic properties of InSb nanowires: A first-principles study
Zhang, Yong; Tang, Li-Ming Ning, Feng; Chen, Ke-Qiu; Wang, Dan
2015-03-28
Using first-principles calculations, we investigate the structural stability and electronic properties of InSb nanowires (NWs). The results show that, in contrast to the bulk InSb phase, wurtzite (WZ) NWs are more stable than zinc-blende (ZB) NWs when the NW diameter is smaller than 10?nm. Nonpassivated ZB and WZ NWs are found to be metallic and semiconducting, respectively. After passivation, both ZB and WZ NWs exhibit direct-gap semiconductor character, and the band gap magnitude of the NWs strongly depends on the suppression of surface states by the charge-compensation ability of foreign atoms to surface atoms. Moreover, the carrier mobility of the NW can be strengthened by halogen passivation.
NASA Astrophysics Data System (ADS)
Kim, Sol; Jhi, Seung-Hoon
2015-12-01
We study Fe13 nanoparticles supported on doped graphene and investigate the dissociative adsorption of CO on the nanoparticles using first-principle calculations. It is found that boron doping enhances the binding energy of Fe13 on the graphene but nitrogen doping reduces it. We show that difference in the work-function and subsequently in the charge transfer causes such behavior in the binding energies. Calculated d-band width and d-band center are well correlated with the Fe binding energy, mostly because of the orbital hybridization effect. We also show that the dissociative adsorption of CO on the Fe-graphene substrate is strongly correlated with the d-band center, which is in turn modulated by the doping concentration.
First-principles calculation of the bulk photovoltaic effect in bismuth ferrite.
Young, Steve M; Zheng, Fan; Rappe, Andrew M
2012-12-01
We compute the bulk photovoltaic effect (BPVE) in BiFeO(3) using first-principles shift current theory, finding good agreement with experimental results. Furthermore, we reconcile apparently contradictory observations: by examining the contributions of all photovoltaic response tensor components and accounting for the geometry and ferroelectric domain structure of the experimental system, we explain the apparent lack of BPVE response in striped polydomain samples that is at odds with the significant response observed in monodomain samples. We reveal that the domain-wall-driven response in striped polydomain samples is partially mitigated by the BPVE, suggesting that enhanced efficiency could be obtained in materials with cooperative rather than antagonistic interaction between the two mechanisms. PMID:23368233
Nanoparticle shapes by using Wulff constructions and first-principles calculations
Barmparis, Georgios D; Lodziana, Zbigniew; Lopez, Nuria
2015-01-01
Summary Background: The majority of complex and advanced materials contain nanoparticles. The properties of these materials depend crucially on the size and shape of these nanoparticles. Wulff construction offers a simple method of predicting the equilibrium shape of nanoparticles given the surface energies of the material. Results: We review the mathematical formulation and the main applications of Wulff construction during the last two decades. We then focus to three recent extensions: active sites of metal nanoparticles for heterogeneous catalysis, ligand-protected nanoparticles generated as colloidal suspensions and nanoparticles of complex metal hydrides for hydrogen storage. Conclusion: Wulff construction, in particular when linked to first-principles calculations, is a powerful tool for the analysis and prediction of the shapes of nanoparticles and tailor the properties of shape-inducing species. PMID:25821675
Novel phases of lithium-aluminum binaries from first-principles structural search.
Sarmiento-Pérez, Rafael; Cerqueira, Tiago F T; Valencia-Jaime, Irais; Amsler, Maximilian; Goedecker, Stefan; Romero, Aldo H; Botti, Silvana; Marques, Miguel A L
2015-01-14
Intermetallic Li-Al compounds are on the one hand key materials for light-weight engineering, and on the other hand, they have been proposed for high-capacity electrodes for Li batteries. We determine from first-principles the phase diagram of Li-Al binary crystals using the minima hopping structural prediction method. Beside reproducing the experimentally reported phases (LiAl, Li3Al2, Li9Al4, LiAl3, and Li2Al), we unveil a structural variety larger than expected by discovering six unreported binary phases likely to be thermodynamically stable. Finally, we discuss the behavior of the elastic constants and of the electric potential profile of all Li-Al stable compounds as a function of their stoichiometry. PMID:25591380
Novel phases of lithium-aluminum binaries from first-principles structural search
Sarmiento-Pérez, Rafael; Cerqueira, Tiago F. T.; Botti, Silvana; Marques, Miguel A. L.; Valencia-Jaime, Irais; Amsler, Maximilian; Goedecker, Stefan; Romero, Aldo H.
2015-01-14
Intermetallic Li–Al compounds are on the one hand key materials for light-weight engineering, and on the other hand, they have been proposed for high-capacity electrodes for Li batteries. We determine from first-principles the phase diagram of Li–Al binary crystals using the minima hopping structural prediction method. Beside reproducing the experimentally reported phases (LiAl, Li{sub 3}Al{sub 2}, Li{sub 9}Al{sub 4}, LiAl{sub 3}, and Li{sub 2}Al), we unveil a structural variety larger than expected by discovering six unreported binary phases likely to be thermodynamically stable. Finally, we discuss the behavior of the elastic constants and of the electric potential profile of all Li–Al stable compounds as a function of their stoichiometry.
Correa, Alfredo A.; Bonev, Stanimir A.; Galli, Giulia
2006-01-01
At high pressure and temperature, the phase diagram of elemental carbon is poorly known. We present predictions of diamond and BC8 melting lines and their phase boundary in the solid phase, as obtained from first-principles calculations. Maxima are found in both melting lines, with a triple point located at ?850 GPa and ?7,400 K. Our results show that hot, compressed diamond is a semiconductor that undergoes metalization upon melting. In contrast, in the stability range of BC8, an insulator to metal transition is likely to occur in the solid phase. Close to the diamond/liquid and BC8/liquid boundaries, molten carbon is a low-coordinated metal retaining some covalent character in its bonding up to extreme pressures. Our results provide constraints on the carbon equation of state, which is of critical importance for devising models of Neptune, Uranus, and white dwarf stars, as well as of extrasolar carbon-rich planets. PMID:16432191
First-principles DFT+U modeling of defect behaviors in anti-ferromagnetic uranium mononitride
Lan, Jian-Hui; Zhao, Zi-Chen; Wu, Qiong; Zhao, Yu-Liang; Shi, Wei-Qun; Chai, Zhi-Fang; School of Radiological and Interdisciplinary Sciences, Soochow University, 215123 Suzhou
2013-12-14
A series of point defects in uranium mononitride (UN) have been studied by first-principles DFT+U calculations. The influence of intrinsic defects on the properties of UN was explored by considering the anti-ferromagnetic (AFM) order along the [001] direction. Our results show that all the point defects lead to obvious volume swelling of UN crystal. Energetically, the interstitial nitrogen defect is the most favorable one among single-point defects in UN crystal with the formation energy of 4.539 eV, while the N-Frenkel pair becomes the most preferable one among double-point defects. The AFM order induces obvious electron spin polarization of uranium towards neighboring uranium atoms with opposite spin orientations in UN crystal.
Impact of rattlers on thermal conductivity of a thermoelectric clathrate: a first-principles study.
Tadano, Terumasa; Gohda, Yoshihiro; Tsuneyuki, Shinji
2015-03-01
We investigate the role of rattling guest atoms on the lattice thermal conductivity of a type-I clathrate Ba_{8}Ga_{16}Ge_{30} by first-principles lattice dynamics. Comparing phonon properties of filled and empty clathrates, we show that rattlers cause tenfold reductions in the relaxation time of phonons by increasing the phonon-phonon scattering probability. Contrary to the resonant scattering scenario, the reduction in the relaxation time occurs in a wide frequency range, which is crucial for explaining the unusually low thermal conductivities of clathrates. We also find that the impact of rattlers on the group velocity of phonons is secondary because the flattening of phonon dispersion occurs only in a limited phase space in the Brillouin zone. PMID:25793824
First principles investigation of Ti adsorption and migration on Si(100) surfaces
Briquet, Ludovic G. V.; Wirtz, Tom; Philipp, Patrick
2013-12-28
The titanium adsorption on Si(100) is investigated using first principles computer modelling methods. Two new subsurface adsorption sites are described. They are located at the edge of the cavity topped by a surface silicon dimer. The migration of the titanium from the surface to the subsurface sites is facilitated when occurring via one of these sites. The ejection of one of the silicon atoms forming the surface dimer is also investigated. The actual step of the ejection requires more energy than previously thought although, when considering the global picture of a titanium atom on the surface leading to the ejection of a silicon atom, the overall rate is compensated by the facilitated migration of the titanium to the subsurface sites. The consecutive adsorption of a second and third titanium atom is also investigated. It is shown that titanium grows evenly on the surface in normal condition, showing no intermixing of the titanium and silicon beyond the silicon layer.
First-principles investigation of spin polarized conductance in atomic carbon wires
NASA Astrophysics Data System (ADS)
Senapati, L.; Pati, R.; Mailman, M.; Whaley, K. B.; Nayak, S. K.
2004-03-01
We present results of spin-dependent energetics and conductance for one dimensional (1D) atomic carbon wires consisting of magnetic (Co) and nonmagnetic (C) atoms sandwiched between gold electrodes, obtained employing first-principles gradient corrected density functional theory and Landauer's formalism. Our calculation at zero bias limit shows a spin-valve behavior with a parallel spin configuration state between the Co giving higher conductance than the corresponding anti-parallel state. The length dependence calculations reveal a non-monotonic variation of conductance with the length of the wires. Ground state of carbon wires containing up to 13 carbon atoms are found to have anti-parallel spin configurations between Co, but the wire with 14 carbon atoms is found to have parallel spin configuration in the ground state.
NASA Astrophysics Data System (ADS)
Yuasa, Motohiro; Nakazawa, Takumi; Mabuchi, Mamoru
2012-07-01
Sliding behaviors of ?9(221) grain boundary bicrystals have been investigated in pure metals (Al, Ag, Au, Cu, Pt and Co) and in segregated metals (Cu segregated by Al, Ag, Au, Pt and Co) by molecular dynamics simulations and first-principles calculations. The grain boundary energy, the atomic size and the electronegativity of the segregated elements were not critical for the occurrence of grain boundary sliding. On the other hand, the sliding rate increased as the minimum charge density decreased at the bond critical point. This was the case for both pure grain boundary models and segregated grain boundary models. Therefore, it seems that the sliding rate depends on atomic movement at sites with minimum charge density, irrespective of the elements involved and of the presence of segregated atoms.
Wang, Zhiguo; Zhang, Chunlai; Li, Jingbo; Gao, Fei; Weber, William J.
2010-12-01
The electronic properties of hydrogen-saturated GaN nanowires with different orientations and sizes are investigated using first-principles calculations, and three types of nanowires oriented along the [001], [110] and [1-10] crystal directions are considered. The electronic properties show little dependence on orientation. The hydrogen-saturated GaN nanowires show semiconducting behavior with a direct band gap larger than that of bulk wurtzite GaN. Quantum confinement leads to a decrease in the band gap of the nanowires with increasing nanowire size. The [001]-oriented nanowires with hexagonal cross sections are energetically more favorable than the [100]- and [1-10]-oriented nanowires with triangular cross-sections.
Impact of Rattlers on Thermal Conductivity of a Thermoelectric Clathrate: A First-Principles Study
NASA Astrophysics Data System (ADS)
Tadano, Terumasa; Gohda, Yoshihiro; Tsuneyuki, Shinji
2015-03-01
We investigate the role of rattling guest atoms on the lattice thermal conductivity of a type-I clathrate Ba8Ga16Ge30 by first-principles lattice dynamics. Comparing phonon properties of filled and empty clathrates, we show that rattlers cause tenfold reductions in the relaxation time of phonons by increasing the phonon-phonon scattering probability. Contrary to the resonant scattering scenario, the reduction in the relaxation time occurs in a wide frequency range, which is crucial for explaining the unusually low thermal conductivities of clathrates. We also find that the impact of rattlers on the group velocity of phonons is secondary because the flattening of phonon dispersion occurs only in a limited phase space in the Brillouin zone.
Sawada, Keisuke; Ishii, Fumiyuki; Saito, Mineo
2014-04-07
We studied magnetism in bilayer and multilayer zigzag graphene nanoribbons (ZGNRs) through first-principles density functional theory calculations. We found that the magnetic ground state of bilayer ZGNRs is the C-type antiferromagnetic (AFM) state, which is the AFM order between intraplane-edge carbon atoms and ferromagnetic (FM) order between interplane edge carbon atoms. In the cases of infinitely stacked multilayer ZGNRs, i.e., zigzag graphite nanoribbons, the C-type AFM state is also the most stable. By carrier doping, we found that the magnetic ground state changed from the C-AFM state to the FM state and, thus, realized two-dimensional FM surface (edge) states of graphite with a metallic conductivity.
Thermal properties of black and blue phosphorenes from a first-principles quasiharmonic approach
NASA Astrophysics Data System (ADS)
Aierken, Yierpan; ?ak?r, Deniz; Sevik, Cem; Peeters, Francois M.
2015-08-01
Different allotropes of phosphorene are possible of which black and blue phosphorus are the most stable. While blue phosphorus has isotropic properties, black phosphorus is strongly anisotropic in its electronic and optical properties due to its anisotropic crystal structure. In this work, we systematically investigated the lattice thermal properties of black and blue phosphorene by using first-principles calculations based on the quasiharmonic approximation approach. Similar to the optoelectronic and electronic properties, we predict that black phosphorene has highly anisotropic thermal properties, in contrast to the blue phase. The linear thermal expansion coefficients along the zigzag and armchair direction differ up to 20% in black phosphorene. The armchair direction of black phosphorene is more expandable as compared to the zigzag direction and the biaxial expansion of blue phosphorene under finite temperature. Our comparative analysis reveals that the inclusion of finite-temperature effects makes the blue phase thermodynamically more stable over the black phase above 135 K.
The mechanical exfoliation mechanism of black phosphorus to phosphorene: A first-principles study
NASA Astrophysics Data System (ADS)
Mu, Yunsheng; Si, M. S.
2015-11-01
Today, the renaissance of black phosphorus largely depends on the mechanical exfoliation method, which is accessible to produce few-layer forms from the bulk counterpart. However, the deep understanding of the exfoliation mechanism is missing. To this end, we resolve this issue by simulating the sliding processes of bilayer phosphorene based on first-principles calculations. It is found that the interlayer Coulomb interactions dictate the optimal sliding pathway, leading to the minimal energy barrier as low as ?60 \\text{meV} , which gives a comparable surface energy of ?59 \\text{mJ/m}2 in experiment. This means that black phosphorus can be exfoliated by the sliding approach. In addition, considerable bandgap modulations along these sliding pathways are obtained. The study like ours builds up a fundamental understanding of how black phosphorus is exfoliated to few-layer forms, providing a good guide to experimental research.
Zhang Zhuhua; Zeng Xiao Cheng; Guo Wanlin
2010-07-15
Since electrons injected to a homogenous wire always tend to concentrate on its surface, heterogeneous coaxial structures are generally necessary to make nanocables with an insulating sheath. Here we reveal from first-principles calculations that double-walled boron-nitride nanotubes could be natural homogeneous nanocables as injected electrons prefer abnormally to concentrate on the inner semiconducting tube while the outer tube remains insulating. The ratio of extra electrons on the inner tube to total carriers in the double-walled nanotubes can be tuned widely by changing either the tube diameter or the local tube curvature through radial deformation, both attributed to the predominant band filling and weak enhancement in Coulomb interaction within the inner wall where the sublattice asymmetry is strongly attenuated by curvature effect. This exotic charge screening is universal for any form of electron-doping sources.
A genetic algorithm for first principles global structure optimization of supported nano structures
Vilhelmsen, Lasse B.; Hammer, Bjørk
2014-07-28
We present a newly developed publicly available genetic algorithm (GA) for global structure optimisation within atomic scale modeling. The GA is focused on optimizations using first principles calculations, but it works equally well with empirical potentials. The implementation is described and benchmarked through a detailed statistical analysis employing averages across many independent runs of the GA. This analysis focuses on the practical use of GA’s with a description of optimal parameters to use. New results for the adsorption of M{sub 8} clusters (M = Ru, Rh, Pd, Ag, Pt, Au) on the stoichiometric rutile TiO{sub 2}(110) surface are presented showing the power of automated structure prediction and highlighting the diversity of metal cluster geometries at the atomic scale.
A genetic algorithm for first principles global structure optimization of supported nano structures
NASA Astrophysics Data System (ADS)
Vilhelmsen, Lasse B.; Hammer, Bjørk
2014-07-01
We present a newly developed publicly available genetic algorithm (GA) for global structure optimisation within atomic scale modeling. The GA is focused on optimizations using first principles calculations, but it works equally well with empirical potentials. The implementation is described and benchmarked through a detailed statistical analysis employing averages across many independent runs of the GA. This analysis focuses on the practical use of GA's with a description of optimal parameters to use. New results for the adsorption of M8 clusters (M = Ru, Rh, Pd, Ag, Pt, Au) on the stoichiometric rutile TiO2(110) surface are presented showing the power of automated structure prediction and highlighting the diversity of metal cluster geometries at the atomic scale.
Thermal Conductivity and Large Isotope Effect in GaN from First Principles
Lindsay, L.; Broido, D. A.; Reinecke, T. L.
2012-08-28
We present atomistic first principles results for the lattice thermal conductivity of GaN and compare them to those for GaP, GaAs, and GaSb. In GaN we find a large increase to the thermal conductivity with isotopic enrichment, ~65% at room temperature. We show that both the high thermal conductivity and its enhancement with isotopic enrichment in GaN arise from the weak coupling of heat-carrying acoustic phonons with optic phonons. This weak scattering results from stiff atomic bonds and the large Ga to N mass ratio, which give phonons high frequencies and also a pronounced energy gap between acoustic and optic phonons compared to other materials. Rigorous understanding of these features in GaN gives important insights into the interplay between intrinsic phonon-phonon scattering and isotopic scattering in a range of materials.
Magnetism and electronic structure in La-doped CoO: A first-principles study
NASA Astrophysics Data System (ADS)
Liu, R. X.; Wang, X. C.; Chen, G. F.; Yang, B. H.
2015-11-01
The electronic structure and magnetism of La-doped CoO systems have been studied by first-principles calculations based on density functional theory. The La dopant concentrations are set to 3.125% and 2.083%, respectively. It is found that La substitution makes the system presents a half-metallic characteristic. Interestingly, La impurity induces the density of states at Fermi level from its surrounding Co and O atoms, while La itself didn't contribute to density of states. By changing the concentration of La dopant, the band gap and charge density of systems are changed. The total magnetic moments of all the La-doped systems are about 2.118 ?B, which is not dependent on the impurity concentration. The tendency of structures, band gap, density of states and magnetic moments are the same by LDA and PBE methods.
Mundy, C; Kuo, I W
2005-06-08
The field of atmospheric science is very rich in problems ranging from the molecular to the regional and global scale. These problems are often extremely complex, and although the statement of a particular atmospheric science question may be clear, finding a single, concise computational approach to address this question can be daunting. As a result, the broad scope of scientific problems that lie within the umbrella of atmospheric science require a multi-discipline approach. Of particular interest to atmospheric chemists is the role that heterogeneous chemistry plays in the important processes that take place throughout the atmosphere. The definition of heterogeneous is: consisting of dissimilar elements or parts. The chemical environment induced by the presence of the interface can be dramatically different than the corresponding gas- or condensed phase homogeneous environment and can give rise to novel chemistry. Although the importance of heterogeneous chemistry in the atmosphere has been known for decades, a challenge to both experimentalists and theorists in provide simplified models and experiments that can yield insight into the field measurements of the atmospheric process. The use of molecular modeling has been widely used to provide a particle-based picture of atmospherically relevant interfaces to deduce the novel chemistry that is taking place. Unfortunately, even with the most computationally efficient particle-based approach, it is still impossible to model the full ice-crystal in the stratosphere or the sea-salt aerosol in the troposphere. Figure 1 depicts a caricature of the actual system of interest, and highlights the region where efficient molecular modeling can be employed. Although there is seemingly a large disconnect between reality and the model, we hope to convince the reader that there is still much insight to be gained from a particle-based picture. There is a myriad of different approaches to molecular modeling that have been successfully applied to studying the complex problems put forth by atmospheric chemists. To date, the majority of the molecular models of atmospherically relevant interfaces have been comprised of two genres of molecular models. The first is based on empirical interaction potentials. The use of an empirical interaction potential suffers from at least two shortcomings. First, empirical potentials are usually fit to reproduce bulk thermodynamic states, or gas phase spectroscopic data. Thus, without the explicit inclusion of charge transfer, it is not at all obvious that empirical potentials can faithfully reproduce the structure at a solid-vapor, or liquid-vapor interface where charge rearrangement is known to occur (see section 5). One solution is the empirical inclusion of polarization effects. These models are certainly an improvement, but still cannot offer insight into charge transfer processes and are usually difficult to parameterize. The other shortcoming of empirical models is that, in general, they cannot describe bond-making/breaking events, i.e. chemistry. In order to address chemistry one has to consider an ab initio (to be referred to as first-principles throughout the remaining text) approach to molecular modeling that explicitly treats the electronic degrees of freedom. First-principles modeling also give a direct link to spectroscopic data and chemistry, but at a large computational cost. The bottle-neck associated with first-principles modeling is usually determined by the level of electronic structure theory that one chooses to study a particular problem. High-level first-principles approaches, such as MP2, provide accurate representation of the electronic degrees of freedom but are only computationally tractable when applied to small system sizes (i.e. 10s of atoms). Nevertheless, this type of modeling has been extremely useful in deducing reaction mechanisms of atmospherically relevant chemistry that will be discussed in this review (see section 4). However, to solve problems relating to heterogeneous chemistry at interfaces where the interfacial syste
First-principles calculation of the electron dynamics in crystalline SiO(2).
Otobe, T; Yabana, K; Iwata, J-I
2009-02-11
We present a first-principles description for electron dynamics in crystalline SiO(2) induced by an optical field in both weak and intense regimes. We rely upon the time-dependent density-functional theory with the adiabatic local-density approximation, and a real-space and real-time method is employed to solve the time-dependent Kohn-Sham equation. The response calculation to a weak field provides us with information on the dielectric function, while the response to an intense field shows the optical dielectric breakdown. We discuss the critical threshold for the dielectric breakdown of crystalline SiO(2), in comparison with the results for diamond. PMID:21715926
Graphene oxide as a candidate material for natural gas storage: A first principles study
NASA Astrophysics Data System (ADS)
Chouhan, Rajiv Kumar; Ulman, Kanchan; Narasimhan, Shobhana
2015-03-01
Alternative sources of clean energy will be much in demand in the coming days. To store methane (CH4) in sorbent materials at ambient conditions for on-board vehicular usage, minimum adsorption energy of 18.8 KJ/mol is desirable. In this work, we have investigated methane adsorption on graphene oxide using first principles calculations. To accurately capture the weak interactions between CH4 and the substrate we have included van der Waals interactions in our calculations. We show that the adsorption energy falls within the target range. Careful analysis of the various contributions to the binding shows that the enhancement in adsorption energy on going from graphene to graphene oxide arises from a subtle synergy between various effects. Funding agencies CSIR, India, DST Nanomission and JNCASR. Computational facilities provided by TUE-CMS, JNCASR.
NASA Astrophysics Data System (ADS)
Gao, Qin; Yao, Sanxi; Widom, Michael
2015-03-01
Density functional theory (DFT) provides an accurate and first-principles description of solid structures and total energies. However, it is highly time-consuming to calculate structures with hundreds of atoms in the unit cell and almost not possible to calculate thousands of atoms. We apply and adapt machine learning algorithms, including compressive sensing, support vector regression and artificial neural networks to fit the DFT total energies of substitutionally disordered boron carbide. The nonparametric kernel method is also included in our models. Our fitted total energy model reproduces the DFT energies with prediction error of around 1 meV/atom. The assumptions of these machine learning models and applications of the fitted total energies will also be discussed. Financial support from McWilliams Fellowship and the ONR-MURI under the Grant No. N00014-11-1-0678 is gratefully acknowledged.
NASA Astrophysics Data System (ADS)
Pham, Tuan Anh; Li, Tianshu; Gygi, Francois; Galli, Giulia
2011-03-01
Silicon Nitride (Si3N4) is a possible candidate material to replace or be alloyed with SiO2 to form high-K dielectric films on Si substrates, so as to help prevent leakage currents in modern CMOS transistors. Building on our previous work on dielectric properties of crystalline and amorphous Si3N4 slabs, we present an analysis of the band offsets and dielectric properties of crystalline-Si/amorphous Si3N4 interfaces based on first principles calculations. We discuss shortcomings of the conventional bulk-plus line up approach in band offset calculations for systems with an amorphous component, and we present the results of band offsets obtained from calculations of local density of states. Finally, we describe the role of bonding configurations in determining band edges and dielectric constants at the interface. We acknowledge financial support from Intel Corporation.
Vasileia Filidou; Davide Ceresoli; John J. L. Morton; Feliciano Giustino
2012-01-27
The study of hyperfine interactions in optically excited fullerenes has recently acquired importance within the context of nuclear spin entanglement for quantum information technology. We here report a first-principles pseudopotential study of the hyperfine coupling parameters of optically excited fullerene derivatives as well as small organic radicals. The calculations are performed within the gauge-invariant projector-augmented wave method [C. Pickard and F. Mauri, Phys. Rev. B. 63, 245101 (2001)]. In order to establish the accuracy of this methodology we compare our results with all-electron calculations and with experiment. In the case of fullerene derivatives we study the hyperfine coupling in the spin-triplet exciton state and compare our calculations with recent electron paramagnetic resonance measurements [M. Schaffry et al., Phys. Rev. Lett. 104, 200501 (2010)]. We discuss our results in light of a recent proposal for entangling remote nuclear spins in photo-excited chromophores.
Superconducting properties of Mo3Os, Mo3Pt, Mo3Ir from first principle calculations
NASA Astrophysics Data System (ADS)
Subhashree, G.; Sankar, S.; Krithiga, R.
2014-12-01
Self-consistent first principle calculations were carried out to investigate the structural, electronic, thermal and superconducting properties of Mo3X (X = Os, Ir, Pt) compounds of A15 phase that are studied by using the tight-binding linear muffin-tin orbital method. The E and k convergence have been checked to analyze the ground state properties. The band structure and DOS histograms are plotted from the calculated equilibrium lattice parameter. The bulk modulus (BB), Debye temperature (?D), density of states (N(EF)), electron-phonon coupling constant (?), superconducting transition temperature (Tc) and electronic specific heat coefficient (?) have been calculated from the electronic band structure results. The calculated values have been compared with the available experimental results of literature.
Lindsay, L; Broido, D A; Reinecke, T L
2013-07-12
We have calculated the thermal conductivities (?) of cubic III-V boron compounds using a predictive first principles approach. Boron arsenide is found to have a remarkable room temperature ? over 2000 W m(-1) K(-1); this is comparable to those in diamond and graphite, which are the highest bulk values known. We trace this behavior in boron arsenide to an interplay of certain basic vibrational properties that lie outside of the conventional guidelines in searching for high ? materials, and to relatively weak phonon-isotope scattering. We also find that cubic boron nitride and boron antimonide will have high ? with isotopic purification. This work provides new insight into the nature of thermal transport at a quantitative level and predicts a new ultrahigh ? material of potential interest for passive cooling applications. PMID:23889420
NASA Astrophysics Data System (ADS)
Lindsay, L.; Broido, D. A.; Reinecke, T. L.
2013-07-01
We have calculated the thermal conductivities (?) of cubic III-V boron compounds using a predictive first principles approach. Boron arsenide is found to have a remarkable room temperature ? over 2000Wm-1K-1; this is comparable to those in diamond and graphite, which are the highest bulk values known. We trace this behavior in boron arsenide to an interplay of certain basic vibrational properties that lie outside of the conventional guidelines in searching for high ? materials, and to relatively weak phonon-isotope scattering. We also find that cubic boron nitride and boron antimonide will have high ? with isotopic purification. This work provides new insight into the nature of thermal transport at a quantitative level and predicts a new ultrahigh ? material of potential interest for passive cooling applications.