WorldWideScience

Sample records for density function theory

  1. density functional theory approach

    Indian Academy of Sciences (India)

    YOGESH ERANDE

    2017-07-27

    Jul 27, 2017 ... a key role in all optical switching devices, since their optical properties can be .... optimized in the gas phase using Density Functional Theory. (DFT).39 The ...... The Mediation of Electrostatic Effects by Sol- vents J. Am. Chem.

  2. Quantal density functional theory

    CERN Document Server

    Sahni, Viraht

    2016-01-01

    This book deals with quantal density functional theory (QDFT) which is a time-dependent local effective potential theory of the electronic structure of matter. The treated time-independent QDFT constitutes a special case. In the 2nd edition, the theory is extended to include the presence of external magnetostatic fields. The theory is a description of matter based on the ‘quantal Newtonian’ first and second laws which is in terms of “classical” fields that pervade all space, and their quantal sources. The fields, which are explicitly defined, are separately representative of electron correlations due to the Pauli exclusion principle, Coulomb repulsion, correlation-kinetic, correlation-current-density, and correlation-magnetic effects. The book further describes Schrödinger theory from the new physical perspective of fields and quantal sources. It also describes traditional Hohenberg-Kohn-Sham DFT, and explains via QDFT the physics underlying the various energy functionals and functional derivatives o...

  3. Density functional theory

    International Nuclear Information System (INIS)

    Das, M.P.

    1984-07-01

    The state of the art of the density functional formalism (DFT) is reviewed. The theory is quantum statistical in nature; its simplest version is the well-known Thomas-Fermi theory. The DFT is a powerful formalism in which one can treat the effect of interactions in inhomogeneous systems. After some introductory material, the DFT is outlined from the two basic theorems, and various generalizations of the theorems appropriate to several physical situations are pointed out. Next, various approximations to the density functionals are presented and some practical schemes, discussed; the approximations include an electron gas of almost constant density and an electron gas of slowly varying density. Then applications of DFT in various diverse areas of physics (atomic systems, plasmas, liquids, nuclear matter) are mentioned, and its strengths and weaknesses are pointed out. In conclusion, more recent developments of DFT are indicated

  4. Density functional theory

    International Nuclear Information System (INIS)

    Freyss, M.

    2015-01-01

    This chapter gives an introduction to first-principles electronic structure calculations based on the density functional theory (DFT). Electronic structure calculations have a crucial importance in the multi-scale modelling scheme of materials: not only do they enable one to accurately determine physical and chemical properties of materials, they also provide data for the adjustment of parameters (or potentials) in higher-scale methods such as classical molecular dynamics, kinetic Monte Carlo, cluster dynamics, etc. Most of the properties of a solid depend on the behaviour of its electrons, and in order to model or predict them it is necessary to have an accurate method to compute the electronic structure. DFT is based on quantum theory and does not make use of any adjustable or empirical parameter: the only input data are the atomic number of the constituent atoms and some initial structural information. The complicated many-body problem of interacting electrons is replaced by an equivalent single electron problem, in which each electron is moving in an effective potential. DFT has been successfully applied to the determination of structural or dynamical properties (lattice structure, charge density, magnetisation, phonon spectra, etc.) of a wide variety of solids. Its efficiency was acknowledged by the attribution of the Nobel Prize in Chemistry in 1998 to one of its authors, Walter Kohn. A particular attention is given in this chapter to the ability of DFT to model the physical properties of nuclear materials such as actinide compounds. The specificities of the 5f electrons of actinides will be presented, i.e., their more or less high degree of localisation around the nuclei and correlations. The limitations of the DFT to treat the strong 5f correlations are one of the main issues for the DFT modelling of nuclear fuels. Various methods that exist to better treat strongly correlated materials will finally be presented. (author)

  5. Density functional theory of nuclei

    International Nuclear Information System (INIS)

    Terasaki, Jun

    2008-01-01

    The density functional theory of nuclei has come to draw attention of scientists in the field of nuclear structure because the theory is expected to provide reliable numerical data in wide range on the nuclear chart. This article is organized to present an overview of the theory to the people engaged in the theory of other fields as well as those people in the nuclear physics experiments. At first, the outline of the density functional theory widely used in the electronic systems (condensed matter, atoms, and molecules) was described starting from the Kohn-Sham equation derived on the variational principle. Then the theory used in the field of nuclear physics was presented. Hartree-Fock and Hartree-Fock-Bogolyubov approximation by using Skyrme interaction was explained. Comparison of the results of calculations and experiments of binding energies and ground state mean square charge radii of some magic number nuclei were shown. The similarity and dissimilarity between the two streams were summarized. Finally the activities of the international project of Universal Nuclear Energy Density Functional (UNEDF) which was started recently lead by US scientist was reported. This project is programmed for five years. One of the applications of the project is the calculation of the neutron capture cross section of nuclei on the r-process, which is absolutely necessary for the nucleosynthesis research. (S. Funahashi)

  6. Density functional theory: Foundations reviewed

    Energy Technology Data Exchange (ETDEWEB)

    Kryachko, Eugene S., E-mail: eugene.kryachko@ulg.ac.be [Bogolyubov Institute for Theoretical Physics, Kiev, 03680 (Ukraine); Ludeña, Eduardo V., E-mail: popluabe@yahoo.es [Centro de Química, Instituto Venezolano de Investigaciones Científicas, IVIC, Apartado 21827, Caracas 1020-A (Venezuela, Bolivarian Republic of); Prometheus Program, Senescyt (Ecuador); Grupo Ecuatoriano para el Estudio Experimental y Teórico de Nanosistemas, GETNano, USFQ, N104-E, Quito (Ecuador); Escuela Politécnica Superior del Litoral, ESPOL, Guayaquil (Ecuador)

    2014-11-10

    Guided by the above motto (quotation), we review a broad range of issues lying at the foundations of Density Functional Theory, DFT, a theory which is currently omnipresent in our everyday computational study of atoms and molecules, solids and nano-materials, and which lies at the heart of modern many-body computational technologies. The key goal is to demonstrate that there are definitely the ways to improve DFT. We start by considering DFT in the larger context provided by reduced density matrix theory (RDMT) and natural orbital functional theory (NOFT), and examine the implications that N-representability conditions on the second-order reduced density matrix (2-RDM) have not only on RDMT and NOFT but, also, by extension, on the functionals of DFT. This examination is timely in view of the fact that necessary and sufficient N-representability conditions on the 2-RDM have recently been attained. In the second place, we review some problems appearing in the original formulation of the first Hohenberg–Kohn theorem which is still a subject of some controversy. In this vein we recall Lieb’s comment on this proof and the extension to this proof given by Pino et al. (2009), and in this context examine the conditions that must be met in order that the one-to-one correspondence between ground-state densities and external potentials remains valid for finite subspaces (namely, the subspaces where all Kohn–Sham solutions are obtained in practical applications). We also consider the issue of whether the Kohn–Sham equations can be derived from basic principles or whether they are postulated. We examine this problem in relation to ab initio DFT. The possibility of postulating arbitrary Kohn–Sham-type equations, where the effective potential is by definition some arbitrary mixture of local and non-local terms, is discussed. We also deal with the issue of whether there exists a universal functional, or whether one should advocate instead the construction of problem

  7. A Density Functional Theory Study

    KAUST Repository

    Lim, XiaoZhi

    2011-12-11

    Complexes with pincer ligand moieties have garnered much attention in the past few decades. They have been shown to be highly active catalysts in several known transition metal-catalyzed organic reactions as well as some unprecedented organic transformations. At the same time, the use of computational organometallic chemistry to aid in the understanding of the mechanisms in organometallic catalysis for the development of improved catalysts is on the rise. While it was common in earlier studies to reduce computational cost by truncating donor group substituents on complexes such as tertbutyl or isopropyl groups to hydrogen or methyl groups, recent advancements in the processing capabilities of computer clusters and codes have streamlined the time required for calculations. As the full modeling of complexes become increasingly popular, a commonly overlooked aspect, especially in the case of complexes bearing isopropyl substituents, is the conformational analysis of complexes. Isopropyl groups generate a different conformer with each 120 ° rotation (rotamer), and it has been found that each rotamer typically resides in its own potential energy well in density functional theory studies. As a result, it can be challenging to select the most appropriate structure for a theoretical study, as the adjustment of isopropyl substituents from a higher-energy rotamer to the lowest-energy rotamer usually does not occur during structure optimization. In this report, the influence of the arrangement of isopropyl substituents in pincer complexes on calculated complex structure energies as well as a case study on the mechanism of the isomerization of an iPrPCP-Fe complex is covered. It was found that as many as 324 rotamers can be generated for a single complex, as in the case of an iPrPCP-Ni formato complex, with the energy difference between the global minimum and the highest local minimum being as large as 16.5 kcalmol-1. In the isomerization of a iPrPCP-Fe complex, it was found

  8. Density functional theory and parallel processing

    International Nuclear Information System (INIS)

    Ward, R.C.; Geist, G.A.; Butler, W.H.

    1987-01-01

    The authors demonstrate a method for obtaining the ground state energies and charge densities of a system of atoms described within density functional theory using simulated annealing on a parallel computer

  9. Density functional theory in quantum chemistry

    CERN Document Server

    Tsuneda, Takao

    2014-01-01

    This book examines density functional theory based on the foundation of quantum chemistry. Unconventional in approach, it reviews basic concepts, then describes the physical meanings of state-of-the-art exchange-correlation functionals and their corrections.

  10. A Safari Through Density Functional Theory

    Science.gov (United States)

    Dreizler, Reiner M.; Lüdde, Cora S.

    Density functional theory is widely used to treat quantum many body problems in many areas of physics and related fields. A brief survey of this method covering foundations, functionals and applications is presented here.

  11. A multiconfigurational hybrid density-functional theory

    DEFF Research Database (Denmark)

    Sharkas, Kamal; Savin, Andreas; Jensen, Hans Jørgen Aagaard

    2012-01-01

    We propose a multiconfigurational hybrid density-functional theory which rigorously combines a multiconfiguration self-consistent-field calculation with a density-functional approximation based on a linear decomposition of the electron-electron interaction. This gives a straightforward extension ...

  12. Magnetic fields and density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Salsbury Jr., Freddie [Univ. of California, Berkeley, CA (United States)

    1999-02-01

    A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules.

  13. Magnetic fields and density functional theory

    International Nuclear Information System (INIS)

    Salsbury, Freddie Jr.

    1999-01-01

    A major focus of this dissertation is the development of functionals for the magnetic susceptibility and the chemical shielding within the context of magnetic field density functional theory (BDFT). These functionals depend on the electron density in the absence of the field, which is unlike any other treatment of these responses. There have been several advances made within this theory. The first of which is the development of local density functionals for chemical shieldings and magnetic susceptibilities. There are the first such functionals ever proposed. These parameters have been studied by constructing functionals for the current density and then using the Biot-Savart equations to obtain the responses. In order to examine the advantages and disadvantages of the local functionals, they were tested numerically on some small molecules

  14. Multicomponent density functional theory embedding formulation

    Energy Technology Data Exchange (ETDEWEB)

    Culpitt, Tanner; Brorsen, Kurt R.; Pak, Michael V.; Hammes-Schiffer, Sharon, E-mail: shs3@illinois.edu [Department of Chemistry, University of Illinois at Urbana-Champaign, 600 South Mathews Ave, Urbana, Illinois 61801 (United States)

    2016-07-28

    Multicomponent density functional theory (DFT) methods have been developed to treat two types of particles, such as electrons and nuclei, quantum mechanically at the same level. In the nuclear-electronic orbital (NEO) approach, all electrons and select nuclei, typically key protons, are treated quantum mechanically. For multicomponent DFT methods developed within the NEO framework, electron-proton correlation functionals based on explicitly correlated wavefunctions have been designed and used in conjunction with well-established electronic exchange-correlation functionals. Herein a general theory for multicomponent embedded DFT is developed to enable the accurate treatment of larger systems. In the general theory, the total electronic density is separated into two subsystem densities, denoted as regular and special, and different electron-proton correlation functionals are used for these two electronic densities. In the specific implementation, the special electron density is defined in terms of spatially localized Kohn-Sham electronic orbitals, and electron-proton correlation is included only for the special electron density. The electron-proton correlation functional depends on only the special electron density and the proton density, whereas the electronic exchange-correlation functional depends on the total electronic density. This scheme includes the essential electron-proton correlation, which is a relatively local effect, as well as the electronic exchange-correlation for the entire system. This multicomponent DFT-in-DFT embedding theory is applied to the HCN and FHF{sup −} molecules in conjunction with two different electron-proton correlation functionals and three different electronic exchange-correlation functionals. The results illustrate that this approach provides qualitatively accurate nuclear densities in a computationally tractable manner. The general theory is also easily extended to other types of partitioning schemes for multicomponent systems.

  15. Excited-state density functional theory

    International Nuclear Information System (INIS)

    Harbola, Manoj K; Hemanadhan, M; Shamim, Md; Samal, P

    2012-01-01

    Starting with a brief introduction to excited-state density functional theory, we present our method of constructing modified local density approximated (MLDA) energy functionals for the excited states. We show that these functionals give accurate results for kinetic energy and exchange energy compared to the ground state LDA functionals. Further, with the inclusion of GGA correction, highly accurate total energies for excited states are obtained. We conclude with a brief discussion on the further direction of research that include the construction of correlation energy functional and exchange potential for excited states.

  16. Quantal density functional theory. 2. ed.

    International Nuclear Information System (INIS)

    Sahni, Viraht

    2016-01-01

    This book is on quantal density functional theory (QDFT) which is a time-dependent local effective potential theory of the electronic structure of matter. The time-independent QDFT constitutes a special case. The 2 nd edition describes the further development of the theory, and extends it to include the presence of an external magnetostatic field. The theory is based on the 'quantal Newtonian' second and first laws for the individual electron. These laws are in terms of 'classical' fields that pervade all space, and their quantal sources. The fields are separately representative of the electron correlations that must be accounted for in local potential theory. Recent developments show that irrespective of the type of external field the electrons are subject to, the only correlations beyond those due to the Pauli exclusion principle and Coulomb repulsion that need be considered are solely of the correlation-kinetic effects. Foundational to QDFT, the book describes Schroedinger theory from the new perspective of the single electron in terms of the 'quantal Newtonian' laws. Hohenberg-Kohn density functional theory (DFT), new understandings of the theory and its extension to the presence of an external uniform magnetostatic field are described. The physical interpretation via QDFT, in terms of electron correlations, of Kohn-Sham DFT, approximations to it and Slater theory are provided.

  17. Quantal density functional theory. 2. ed.

    Energy Technology Data Exchange (ETDEWEB)

    Sahni, Viraht

    2016-07-01

    This book is on quantal density functional theory (QDFT) which is a time-dependent local effective potential theory of the electronic structure of matter. The time-independent QDFT constitutes a special case. The 2{sup nd} edition describes the further development of the theory, and extends it to include the presence of an external magnetostatic field. The theory is based on the 'quantal Newtonian' second and first laws for the individual electron. These laws are in terms of 'classical' fields that pervade all space, and their quantal sources. The fields are separately representative of the electron correlations that must be accounted for in local potential theory. Recent developments show that irrespective of the type of external field the electrons are subject to, the only correlations beyond those due to the Pauli exclusion principle and Coulomb repulsion that need be considered are solely of the correlation-kinetic effects. Foundational to QDFT, the book describes Schroedinger theory from the new perspective of the single electron in terms of the 'quantal Newtonian' laws. Hohenberg-Kohn density functional theory (DFT), new understandings of the theory and its extension to the presence of an external uniform magnetostatic field are described. The physical interpretation via QDFT, in terms of electron correlations, of Kohn-Sham DFT, approximations to it and Slater theory are provided.

  18. Density functional theory of polydisperse fluid interfaces

    International Nuclear Information System (INIS)

    Baus, M.; Bellier-Castella, L.; Xu, H.

    2002-01-01

    Most colloids usually exhibit one or several polydispersities. A natural framework for the theoretical description of polydisperse systems is provided by the extension of density functional theory to 'continuous' mixtures. This will be illustrated here by the study of both the bulk and interfacial properties of a simple van der Waals model for a polydisperse colloidal fluid. (author)

  19. Chemical hardness and density functional theory

    Indian Academy of Sciences (India)

    Unknown

    RALPH G PEARSON. Chemistry Department, University of California, Santa Barbara, CA 93106, USA. Abstract. The concept of chemical hardness is reviewed from a personal point of view. Keywords. Hardness; softness; hard & soft acids bases (HSAB); principle of maximum hardness. (PMH) density functional theory (DFT) ...

  20. Rational Density Functional Selection Using Game Theory.

    Science.gov (United States)

    McAnanama-Brereton, Suzanne; Waller, Mark P

    2018-01-22

    Theoretical chemistry has a paradox of choice due to the availability of a myriad of density functionals and basis sets. Traditionally, a particular density functional is chosen on the basis of the level of user expertise (i.e., subjective experiences). Herein we circumvent the user-centric selection procedure by describing a novel approach for objectively selecting a particular functional for a given application. We achieve this by employing game theory to identify optimal functional/basis set combinations. A three-player (accuracy, complexity, and similarity) game is devised, through which Nash equilibrium solutions can be obtained. This approach has the advantage that results can be systematically improved by enlarging the underlying knowledge base, and the deterministic selection procedure mathematically justifies the density functional and basis set selections.

  1. Teaching Density Functional Theory Through Experiential Learning

    International Nuclear Information System (INIS)

    Narasimhan, Shobhana

    2015-01-01

    Today, quantum mechanical density functional theory is often the method of choice for performing accurate calculations on atomic, molecular and condensed matter systems. Here, I share some of my experiences in teaching the necessary basics of solid state physics, as well as the theory and practice of density functional theory, in a number of workshops held in developing countries over the past two decades. I discuss the advantages of supplementing the usual mathematically formal teaching methods, characteristic of graduate courses, with the use of visual imagery and analogies. I also describe a successful experiment we carried out, which resulted in a joint publication co-authored by 67 lecturers and students participating in a summer school. (paper)

  2. The use of perturbation theory in density-functional theory

    International Nuclear Information System (INIS)

    Goerling, A.

    1996-01-01

    Perturbation theory with respect to the electron-electron interaction leads to expressions for the exchange and correlation energies and potentials in terms of Kohn-Sham orbitals and Kohn-Sham eigenvalues. An exact open-quote exchange-only close-quote procedure for solids is introduced. Results for several semiconductors are presented. Perturbation theory expansions for the hardness of molecules and the bad gap of solids are given. Density-functional exchange and correlation energies for excited states are defined and a perturbation theory based Kohn-Sham formalism to treat excited states within density-functional theory is introduced

  3. Density functional theory a practical introduction

    CERN Document Server

    Sholl, David

    2009-01-01

    Demonstrates how anyone in math, science, and engineering can master DFT calculations Density functional theory (DFT) is one of the most frequently used computational tools for studying and predicting the properties of isolated molecules, bulk solids, and material interfaces, including surfaces. Although the theoretical underpinnings of DFT are quite complicated, this book demonstrates that the basic concepts underlying the calculations are simple enough to be understood by anyone with a background in chemistry, physics, engineering, or mathematics. The authors show how the widespread availability of powerful DFT codes makes it possible for students and researchers to apply this important computational technique to a broad range of fundamental and applied problems. Density Functional Theory: A Practical Introduction offers a concise, easy-to-follow introduction to the key concepts and practical applications of DFT, focusing on plane-wave DFT. The authors have many years of experience introducing DFT to studen...

  4. Periodic subsystem density-functional theory

    International Nuclear Information System (INIS)

    Genova, Alessandro; Pavanello, Michele; Ceresoli, Davide

    2014-01-01

    By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn–Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn–Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed

  5. Periodic subsystem density-functional theory

    Science.gov (United States)

    Genova, Alessandro; Ceresoli, Davide; Pavanello, Michele

    2014-11-01

    By partitioning the electron density into subsystem contributions, the Frozen Density Embedding (FDE) formulation of subsystem Density Functional Theory (DFT) has recently emerged as a powerful tool for reducing the computational scaling of Kohn-Sham DFT. To date, however, FDE has been employed to molecular systems only. Periodic systems, such as metals, semiconductors, and other crystalline solids have been outside the applicability of FDE, mostly because of the lack of a periodic FDE implementation. To fill this gap, in this work we aim at extending FDE to treat subsystems of molecular and periodic character. This goal is achieved by a dual approach. On one side, the development of a theoretical framework for periodic subsystem DFT. On the other, the realization of the method into a parallel computer code. We find that periodic FDE is capable of reproducing total electron densities and (to a lesser extent) also interaction energies of molecular systems weakly interacting with metallic surfaces. In the pilot calculations considered, we find that FDE fails in those cases where there is appreciable density overlap between the subsystems. Conversely, we find FDE to be in semiquantitative agreement with Kohn-Sham DFT when the inter-subsystem density overlap is low. We also conclude that to make FDE a suitable method for describing molecular adsorption at surfaces, kinetic energy density functionals that go beyond the GGA level must be employed.

  6. Density functional theory, natural bond orbital and quantum theory of ...

    Indian Academy of Sciences (India)

    Density functional theory, natural bond orbital and quantum theory of atoms in molecule analyses on the hydrogen bonding interactions in tryptophan-water complexes. XIQIAN NIU, ZHENGGUO HUANG. ∗. , LINGLING MA, TINGTING SHEN and LINGFEI GUO. Tianjin Key Laboratory of Structure and Performance for ...

  7. Covariant density functional theory for nuclear matter

    Energy Technology Data Exchange (ETDEWEB)

    Badarch, U.

    2007-07-01

    The present thesis is organized as follows. In Chapter 2 we study the Nucleon-Nucleon (NN) interaction in Dirac-Brueckner (DB) approach. We start by considering the NN interaction in free-space in terms of the Bethe-Salpeter (BS) equation to the meson exchange potential model. Then we present the DB approach for nuclear matter by extending the BS equation for the in-medium NN interaction. From the solution of the three-dimensional in-medium BS equation, we derive the DB self-energies and total binding energy which are the main results of the DB approach, which we later incorporate in the field theoretical calculation of the nuclear equation of state. In Chapter 3, we introduce the basic concepts of density functional theory in the context of Quantum Hadrodynamics (QHD-I). We reach the main point of this work in Chapter 4 where we introduce the DDRH approach. In the DDRH theory, the medium dependence of the meson-nucleon vertices is expressed as functionals of the baryon field operators. Because of the complexities of the operator-valued functionals we decide to use the mean-field approximation. In Chapter 5, we contrast microscopic and phenomenological approaches to extracting density dependent meson-baryon vertices. Chapter 6 gives the results of our studies of the EOS of infinite nuclear matter in detail. Using formulas derived in Chapters 4 and 5 we calculate the properties of symmetric and asymmetric nuclear matter and pure neutron matter. (orig.)

  8. Covariant density functional theory for nuclear matter

    International Nuclear Information System (INIS)

    Badarch, U.

    2007-01-01

    The present thesis is organized as follows. In Chapter 2 we study the Nucleon-Nucleon (NN) interaction in Dirac-Brueckner (DB) approach. We start by considering the NN interaction in free-space in terms of the Bethe-Salpeter (BS) equation to the meson exchange potential model. Then we present the DB approach for nuclear matter by extending the BS equation for the in-medium NN interaction. From the solution of the three-dimensional in-medium BS equation, we derive the DB self-energies and total binding energy which are the main results of the DB approach, which we later incorporate in the field theoretical calculation of the nuclear equation of state. In Chapter 3, we introduce the basic concepts of density functional theory in the context of Quantum Hadrodynamics (QHD-I). We reach the main point of this work in Chapter 4 where we introduce the DDRH approach. In the DDRH theory, the medium dependence of the meson-nucleon vertices is expressed as functionals of the baryon field operators. Because of the complexities of the operator-valued functionals we decide to use the mean-field approximation. In Chapter 5, we contrast microscopic and phenomenological approaches to extracting density dependent meson-baryon vertices. Chapter 6 gives the results of our studies of the EOS of infinite nuclear matter in detail. Using formulas derived in Chapters 4 and 5 we calculate the properties of symmetric and asymmetric nuclear matter and pure neutron matter. (orig.)

  9. Density Functional Theory An Advanced Course

    CERN Document Server

    Dreizler, Reiner M

    2011-01-01

    Density Functional Theory (DFT) has firmly established itself as the workhorse for the atomic-level simulation of condensed matter phases, pure or composite materials and quantum chemical systems. The present book is a rigorous and detailed introduction to the foundations up to and including such advanced topics as orbital-dependent functionals and both time-dependent and relativistic DFT. Given the many ramifications of contemporary DFT, this text concentrates on the self-contained presentation of the basics of the most widely used DFT variants. This implies a thorough discussion of the corresponding existence theorems and effective single particle equations, as well as of key approximations utilized in implementations. The formal results are complemented by selected quantitative results, which primarily aim at illustrating strengths and weaknesses of a particular approach or functional. DFT for superconducting or nuclear and hadronic systems are not addressed in this work. The structure and material contain...

  10. Microhartree precision in density functional theory calculations

    Science.gov (United States)

    Gulans, Andris; Kozhevnikov, Anton; Draxl, Claudia

    2018-04-01

    To address ultimate precision in density functional theory calculations we employ the full-potential linearized augmented plane-wave + local-orbital (LAPW + lo) method and justify its usage as a benchmark method. LAPW + lo and two completely unrelated numerical approaches, the multiresolution analysis (MRA) and the linear combination of atomic orbitals, yield total energies of atoms with mean deviations of 0.9 and 0.2 μ Ha , respectively. Spectacular agreement with the MRA is reached also for total and atomization energies of the G2-1 set consisting of 55 molecules. With the example of α iron we demonstrate the capability of LAPW + lo to reach μ Ha /atom precision also for periodic systems, which allows also for the distinction between the numerical precision and the accuracy of a given functional.

  11. Stochastic density functional theory at finite temperatures

    Science.gov (United States)

    Cytter, Yael; Rabani, Eran; Neuhauser, Daniel; Baer, Roi

    2018-03-01

    Simulations in the warm dense matter regime using finite temperature Kohn-Sham density functional theory (FT-KS-DFT), while frequently used, are computationally expensive due to the partial occupation of a very large number of high-energy KS eigenstates which are obtained from subspace diagonalization. We have developed a stochastic method for applying FT-KS-DFT, that overcomes the bottleneck of calculating the occupied KS orbitals by directly obtaining the density from the KS Hamiltonian. The proposed algorithm scales as O (" close=")N3T3)">N T-1 and is compared with the high-temperature limit scaling O density approximation (LDA); we demonstrate its efficiency, statistical errors, and bias in the estimation of the free energy per electron for a diamond structure silicon. The bias is small compared to the fluctuations and is independent of system size. In addition to calculating the free energy itself, one can also use the method to calculate its derivatives and obtain the equations of state.

  12. Time-dependent quantum fluid density functional theory of hydrogen ...

    Indian Academy of Sciences (India)

    WINTEC

    density functional theory; quantum fluid dynamics. 1. Introduction ... dynamics of strongly non-linear interaction of atoms with intense ... theory and quantum fluid dynamics in real space. .... clear evidence of bond softening since density in the.

  13. Locality of correlation in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Burke, Kieron [Department of Chemistry, University of California, Irvine, California 92697 (United States); Cancio, Antonio [Department of Physics and Astronomy, Ball State University, Muncie, Indiana 47306 (United States); Gould, Tim [Qld Micro- and Nanotechnology Centre, Griffith University, Nathan, Qld 4111 (Australia); Pittalis, Stefano [CNR-Istituto di Nanoscienze, Via Campi 213A, I-41125 Modena (Italy)

    2016-08-07

    The Hohenberg-Kohn density functional was long ago shown to reduce to the Thomas-Fermi (TF) approximation in the non-relativistic semiclassical (or large-Z) limit for all matter, i.e., the kinetic energy becomes local. Exchange also becomes local in this limit. Numerical data on the correlation energy of atoms support the conjecture that this is also true for correlation, but much less relevant to atoms. We illustrate how expansions around a large particle number are equivalent to local density approximations and their strong relevance to density functional approximations. Analyzing highly accurate atomic correlation energies, we show that E{sub C} → −A{sub C} ZlnZ + B{sub C}Z as Z → ∞, where Z is the atomic number, A{sub C} is known, and we estimate B{sub C} to be about 37 mhartree. The local density approximation yields A{sub C} exactly, but a very incorrect value for B{sub C}, showing that the local approximation is less relevant for the correlation alone. This limit is a benchmark for the non-empirical construction of density functional approximations. We conjecture that, beyond atoms, the leading correction to the local density approximation in the large-Z limit generally takes this form, but with B{sub C} a functional of the TF density for the system. The implications for the construction of approximate density functionals are discussed.

  14. Spectral function from Reduced Density Matrix Functional Theory

    Science.gov (United States)

    Romaniello, Pina; di Sabatino, Stefano; Berger, Jan A.; Reining, Lucia

    2015-03-01

    In this work we focus on the calculation of the spectral function, which determines, for example, photoemission spectra, from reduced density matrix functional theory. Starting from its definition in terms of the one-body Green's function we derive an expression for the spectral function that depends on the natural occupation numbers and on an effective energy which accounts for all the charged excitations. This effective energy depends on the two-body as well as higher-order density matrices. Various approximations to this expression are explored by using the exactly solvable Hubbard chains.

  15. Synthesis, Crystal Structure, Density Function Theory, Molecular ...

    African Journals Online (AJOL)

    Tropical Journal of Pharmaceutical Research February 2016; 15 (2): 385-392 ... tested for its antimicrobial activities and computational studies including density function test (DFT) and docking ... agonists [4], selective dopamine D3 and D4 ...

  16. Functional development in density functional theory for superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Sanna, Antonio; Gross, E.K.U.; Essenberger, Frank [Max Planck Institute of Microstructure Physics, Halle (Saale) (Germany)

    2015-07-01

    Density functional theory for superconductors (SCDFT) is a fully parameter-free approach to superconductivity that allows for accurate predictions of critical temperature and properties of superconductors. We report on the most recent extensions of the method, in particular the development of new functionals to: (1) incorporate in a correct fashion Migdal's theorem; (2) compute the excitation spectrum; (3) include spin-fluctuation mediated pairing Applications and predictions are shown for a set of materials, including conventional and unconventional superconductors.

  17. Multicomponent density-functional theory for time-dependent systems

    NARCIS (Netherlands)

    Butriy, O.; Ebadi, H.; de Boeij, P. L.; van Leeuwen, R.; Gross, E. K. U.

    2007-01-01

    We derive the basic formalism of density functional theory for time-dependent electron-nuclear systems. The basic variables of this theory are the electron density in body-fixed frame coordinates and the diagonal of the nuclear N-body density matrix. The body-fixed frame transformation is carried

  18. Dynamical density functional theory for dense atomic liquids

    International Nuclear Information System (INIS)

    Archer, A J

    2006-01-01

    Starting from Newton's equations of motion, we derive a dynamical density functional theory (DDFT) applicable to atomic liquids. The theory has the feature that it requires as input the Helmholtz free energy functional from equilibrium density functional theory. This means that, given a reliable equilibrium free energy functional, the correct equilibrium fluid density profile is guaranteed. We show that when the isothermal compressibility is small, the DDFT generates the correct value for the speed of sound in a dense liquid. We also interpret the theory as a dynamical equation for a coarse grained fluid density and show that the theory can be used (making further approximations) to derive the standard mode coupling theory that is used to describe the glass transition. The present theory should provide a useful starting point for describing the dynamics of inhomogeneous atomic fluids

  19. Extended screened exchange functional derived from transcorrelated density functional theory.

    Science.gov (United States)

    Umezawa, Naoto

    2017-09-14

    We propose a new formulation of the correlation energy functional derived from the transcorrelated method in use in density functional theory (TC-DFT). An effective Hamiltonian, H TC , is introduced by a similarity transformation of a many-body Hamiltonian, H, with respect to a complex function F: H TC =1FHF. It is proved that an expectation value of H TC for a normalized single Slater determinant, D n , corresponds to the total energy: E[n] = ⟨Ψ n |H|Ψ n ⟩/⟨Ψ n |Ψ n ⟩ = ⟨D n |H TC |D n ⟩ under the two assumptions: (1) The electron density nr associated with a trial wave function Ψ n = D n F is v-representable and (2) Ψ n and D n give rise to the same electron density nr. This formulation, therefore, provides an alternative expression of the total energy that is useful for the development of novel correlation energy functionals. By substituting a specific function for F, we successfully derived a model correlation energy functional, which resembles the functional form of the screened exchange method. The proposed functional, named the extended screened exchange (ESX) functional, is described within two-body integrals and is parametrized for a numerically exact correlation energy of the homogeneous electron gas. The ESX functional does not contain any ingredients of (semi-)local functionals and thus is totally free from self-interactions. The computational cost for solving the self-consistent-field equation is comparable to that of the Hartree-Fock method. We apply the ESX functional to electronic structure calculations for a solid silicon, H - ion, and small atoms. The results demonstrate that the TC-DFT formulation is promising for the systematic improvement of the correlation energy functional.

  20. Spin theory of the density functional: reduced matrices and density functions

    International Nuclear Information System (INIS)

    Pavlov, R.; Delchev, Y.; Pavlova, K.; Maruani, J.

    1993-01-01

    Expressions for the reduced matrices and density functions of N-fermion systems of arbitrary order s (1<=s<=N) are derived within the frame of rigorous spin approach to the density functional theory (DFT). Using the local-scale transformation method and taking into account the particle spin it is shown that the reduced matrices and density functions are functionals of the total one-fermion density. Similar dependence is found for the distribution density of s-particle aggregates. Generalization and applicability of DFT to the case of s-particle ensembles and aggregates is discussed. 14 refs

  1. Density functional theory for polymeric systems in 2D

    International Nuclear Information System (INIS)

    Słyk, Edyta; Bryk, Paweł; Roth, Roland

    2016-01-01

    We propose density functional theory for polymeric fluids in two dimensions. The approach is based on Wertheim’s first order thermodynamic perturbation theory (TPT) and closely follows density functional theory for polymers proposed by Yu and Wu (2002 J. Chem. Phys . 117 2368). As a simple application we evaluate the density profiles of tangent hard-disk polymers at hard walls. The theoretical predictions are compared against the results of the Monte Carlo simulations. We find that for short chain lengths the theoretical density profiles are in an excellent agreement with the Monte Carlo data. The agreement is less satisfactory for longer chains. The performance of the theory can be improved by recasting the approach using the self-consistent field theory formalism. When the self-avoiding chain statistics is used, the theory yields a marked improvement in the low density limit. Further improvements for long chains could be reached by going beyond the first order of TPT. (paper)

  2. Density-functional theory for internal magnetic fields

    Science.gov (United States)

    Tellgren, Erik I.

    2018-01-01

    A density-functional theory is developed based on the Maxwell-Schrödinger equation with an internal magnetic field in addition to the external electromagnetic potentials. The basic variables of this theory are the electron density and the total magnetic field, which can equivalently be represented as a physical current density. Hence, the theory can be regarded as a physical current density-functional theory and an alternative to the paramagnetic current density-functional theory due to Vignale and Rasolt. The energy functional has strong enough convexity properties to allow a formulation that generalizes Lieb's convex analysis formulation of standard density-functional theory. Several variational principles as well as a Hohenberg-Kohn-like mapping between potentials and ground-state densities follow from the underlying convex structure. Moreover, the energy functional can be regarded as the result of a standard approximation technique (Moreau-Yosida regularization) applied to the conventional Schrödinger ground-state energy, which imposes limits on the maximum curvature of the energy (with respect to the magnetic field) and enables construction of a (Fréchet) differentiable universal density functional.

  3. Constructive definition of functional derivatives in density-functional theory

    International Nuclear Information System (INIS)

    Luo Ji

    2006-01-01

    It is shown that the functional derivatives in density-functional theory (DFT) can be explicitly defined within the domain of electron densities restricted by the electron number, and a constructive definition of such restricted derivatives is suggested. With this definition, Kohn-Sham (KS) equations can be established for an N-electron system without extending the functional domain and introducing a Lagrange multiplier. This may clarify some of the fundamental questions raised by Nesbet (1998 Phys. Rev. A 58 R12). The definition naturally leads to the fact that the KS effective potential is determined only to within an additive constant, thus the KS levels can shift freely and the relation between the highest occupied molecular orbital (HOMO) energy and the ionization potential of the system depends on the choice of the constant. On the other hand, if the domain of functionals is indeed extended beyond the electron number restriction, conclusions depend on whether the extended functionals have unrestricted derivatives or not. It is shown that the ensemble extension of DFT to open systems of mixed states (Perdew et al 1982 Phys. Rev. Lett. 49 1691) leads to an energy functional which has no unrestricted derivative at integer electron numbers. Hence after this extension, the relation between the HOMO energy and the ionization potential for an N-electron system is still uncertain. Besides, there are different extensions of the energy functional to a domain of densities unrestricted by the integer electron number, resulting in different unrestricted derivatives and electron systems with different chemical potentials. Even for the exact exchange-correlation potential, there is still an undetermined constant, whether it is a restricted or unrestricted derivative

  4. Density functional theory and multiscale materials modeling

    Indian Academy of Sciences (India)

    One of the vital ingredients in the theoretical tools useful in materials modeling at all the length scales of interest is the concept of density. In the microscopic length scale, it is the electron density that has played a major role in providing a deeper understanding of chemical binding in atoms, molecules and solids.

  5. Density functional theory calculations of charge transport properties ...

    Indian Academy of Sciences (India)

    ZIRAN CHEN

    2017-08-04

    Aug 4, 2017 ... properties of 'plate-like' coronene topological structures ... Keywords. Organic semiconductors; density functional theory; charge carrier mobility; ambipolar transport; ..... nology Department of Sichuan Province (Grant Number.

  6. Synthesis, Crystal Structure, Density Function Theory, Molecular ...

    African Journals Online (AJOL)

    Tropical Journal of Pharmaceutical Research ... Purpose: To determine the exact structure and antimicrobial activity of 2-(3-(4 phenylpiperazin-1-yl) ... Besides HOMO– LUMO energy gap was performed at B3LYP/6-31G (d,p) level of theory.

  7. Rationale for switching to nonlocal functionals in density functional theory.

    Science.gov (United States)

    Lazić, P; Atodiresei, N; Caciuc, V; Brako, R; Gumhalter, B; Blügel, S

    2012-10-24

    Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

  8. Rationale for switching to nonlocal functionals in density functional theory

    International Nuclear Information System (INIS)

    Lazić, P; Atodiresei, N; Caciuc, V; Blügel, S; Brako, R; Gumhalter, B

    2012-01-01

    Density functional theory (DFT) has been steadily improving over the past few decades, becoming the standard tool for electronic structure calculations. The early local functionals (LDA) were eventually replaced by more accurate semilocal functionals (GGA) which are in use today. A major persisting drawback is the lack of the nonlocal correlation which is at the core of dispersive (van der Waals) forces, so that a large and important class of systems remains outside the scope of DFT. The vdW-DF correlation functional of Langreth and Lundqvist, published in 2004, was the first nonlocal functional which could be easily implemented. Beyond expectations, the nonlocal functional has brought significant improvement to systems that were believed not to be sensitive to nonlocal correlations. In this paper, we use the example of graphene nanodomes growing on the Ir(111) surface, where with an increase of the size of the graphene islands the character of the bonding changes from strong chemisorption towards almost pure physisorption. We demonstrate how the seamless character of the vdW-DF functionals makes it possible to treat all regimes self-consistently, proving to be a systematic and consistent improvement of DFT regardless of the nature of bonding. We also discuss the typical surface science example of CO adsorption on (111) surfaces of metals, which shows that the nonlocal correlation may also be crucial for strongly chemisorbed systems. We briefly discuss open questions, in particular the choice of the most appropriate exchange part of the functional. As the vdW-DF begins to appear implemented self-consistently in a number of popular DFT codes, with numerical costs close to the GGA calculations, we draw the attention of the DFT community to the advantages and benefits of the adoption of this new class of functionals.

  9. Self-Interaction Error in Density Functional Theory: An Appraisal.

    Science.gov (United States)

    Bao, Junwei Lucas; Gagliardi, Laura; Truhlar, Donald G

    2018-05-03

    Self-interaction error (SIE) is considered to be one of the major sources of error in most approximate exchange-correlation functionals for Kohn-Sham density-functional theory (KS-DFT), and it is large with all local exchange-correlation functionals and with some hybrid functionals. In this work, we consider systems conventionally considered to be dominated by SIE. For these systems, we demonstrate that by using multiconfiguration pair-density functional theory (MC-PDFT), the error of a translated local density-functional approximation is significantly reduced (by a factor of 3) when using an MCSCF density and on-top density, as compared to using KS-DFT with the parent functional; the error in MC-PDFT with local on-top functionals is even lower than the error in some popular KS-DFT hybrid functionals. Density-functional theory, either in MC-PDFT form with local on-top functionals or in KS-DFT form with some functionals having 50% or more nonlocal exchange, has smaller errors for SIE-prone systems than does CASSCF, which has no SIE.

  10. Correlation functional in screened-exchange density functional theory procedures.

    Science.gov (United States)

    Chan, Bun; Kawashima, Yukio; Hirao, Kimihiko

    2017-10-15

    In the present study, we have explored several prospects for the further development of screened-exchange density functional theory (SX-DFT) procedures. Using the performance of HSE06 as our measure, we find that the use of alternative correlation functionals (as oppose to PBEc in HSE06) also yields adequate results for a diverse set of thermochemical properties. We have further examined the performance of new SX-DFT procedures (termed HSEB-type methods) that comprise the HSEx exchange and a (near-optimal) reparametrized B97c (c OS,0  = c SS,0  = 1, c OS,1  = -1.5, c OS,2  = -0.644, c SS,1  = -0.5, and c SS,2  = 1.10) correlation functionals. The different variants of HSEB all perform comparably to or slightly better than the original HSE-type procedures. These results, together with our fundamental analysis of correlation functionals, point toward various directions for advancing SX-DFT methods. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  11. The problem of the universal density functional and the density matrix functional theory

    International Nuclear Information System (INIS)

    Bobrov, V. B.; Trigger, S. A.

    2013-01-01

    The analysis in this paper shows that the Hohenberg-Kohn theorem is the constellation of two statements: (i) the mathematically rigorous Hohenberg-Kohn lemma, which demonstrates that the same ground-state density cannot correspond to two different potentials of an external field, and (ii) the hypothesis of the existence of the universal density functional. Based on the obtained explicit expression for the nonrel-ativistic particle energy in a local external field, we prove that the energy of the system of more than two non-interacting electrons cannot be a functional of the inhomogeneous density. This result is generalized to the system of interacting electrons. It means that the Hohenberg-Kohn lemma cannot provide justification of the universal density functional for fermions. At the same time, statements of the density functional theory remain valid when considering any number of noninteracting ground-state bosons due to the Bose condensation effect. In the framework of the density matrix functional theory, the hypothesis of the existence of the universal density matrix functional corresponds to the cases of noninteracting particles and to interaction in the Hartree-Fock approximation.

  12. Spin-Density Functionals from Current-Density Functional Theory and Vice Versa: A Road towards New Approximations

    International Nuclear Information System (INIS)

    Capelle, K.; Gross, E.

    1997-01-01

    It is shown that the exchange-correlation functional of spin-density functional theory is identical, on a certain set of densities, with the exchange-correlation functional of current-density functional theory. This rigorous connection is used to construct new approximations of the exchange-correlation functionals. These include a conceptually new generalized-gradient spin-density functional and a nonlocal current-density functional. copyright 1997 The American Physical Society

  13. A density functional theory-based chemical potential equalisation

    Indian Academy of Sciences (India)

    A chemical potential equalisation scheme is proposed for the calculation of these quantities and hence the dipole polarizability within the framework of density functional theory based linear response theory. The resulting polarizability is expressed in terms of the contributions from individual atoms in the molecule. A few ...

  14. Benchmark density functional theory calculations for nanoscale conductance

    DEFF Research Database (Denmark)

    Strange, Mikkel; Bækgaard, Iben Sig Buur; Thygesen, Kristian Sommer

    2008-01-01

    We present a set of benchmark calculations for the Kohn-Sham elastic transmission function of five representative single-molecule junctions. The transmission functions are calculated using two different density functional theory methods, namely an ultrasoft pseudopotential plane-wave code...

  15. Uniform magnetic fields in density-functional theory

    Science.gov (United States)

    Tellgren, Erik I.; Laestadius, Andre; Helgaker, Trygve; Kvaal, Simen; Teale, Andrew M.

    2018-01-01

    We construct a density-functional formalism adapted to uniform external magnetic fields that is intermediate between conventional density functional theory and Current-Density Functional Theory (CDFT). In the intermediate theory, which we term linear vector potential-DFT (LDFT), the basic variables are the density, the canonical momentum, and the paramagnetic contribution to the magnetic moment. Both a constrained-search formulation and a convex formulation in terms of Legendre-Fenchel transformations are constructed. Many theoretical issues in CDFT find simplified analogs in LDFT. We prove results concerning N-representability, Hohenberg-Kohn-like mappings, existence of minimizers in the constrained-search expression, and a restricted analog to gauge invariance. The issue of additivity of the energy over non-interacting subsystems, which is qualitatively different in LDFT and CDFT, is also discussed.

  16. Quantal density functional theory II. Approximation methods and applications

    International Nuclear Information System (INIS)

    Sahni, Viraht

    2010-01-01

    This book is on approximation methods and applications of Quantal Density Functional Theory (QDFT), a new local effective-potential-energy theory of electronic structure. What distinguishes the theory from traditional density functional theory is that the electron correlations due to the Pauli exclusion principle, Coulomb repulsion, and the correlation contribution to the kinetic energy -- the Correlation-Kinetic effects -- are separately and explicitly defined. As such it is possible to study each property of interest as a function of the different electron correlations. Approximations methods based on the incorporation of different electron correlations, as well as a many-body perturbation theory within the context of QDFT, are developed. The applications are to the few-electron inhomogeneous electron gas systems in atoms and molecules, as well as to the many-electron inhomogeneity at metallic surfaces. (orig.)

  17. A classical density functional theory of ionic liquids.

    Science.gov (United States)

    Forsman, Jan; Woodward, Clifford E; Trulsson, Martin

    2011-04-28

    We present a simple, classical density functional approach to the study of simple models of room temperature ionic liquids. Dispersion attractions as well as ion correlation effects and excluded volume packing are taken into account. The oligomeric structure, common to many ionic liquid molecules, is handled by a polymer density functional treatment. The theory is evaluated by comparisons with simulations, with an emphasis on the differential capacitance, an experimentally measurable quantity of significant practical interest.

  18. Bayesian error estimation in density-functional theory

    DEFF Research Database (Denmark)

    Mortensen, Jens Jørgen; Kaasbjerg, Kristen; Frederiksen, Søren Lund

    2005-01-01

    We present a practical scheme for performing error estimates for density-functional theory calculations. The approach, which is based on ideas from Bayesian statistics, involves creating an ensemble of exchange-correlation functionals by comparing with an experimental database of binding energies...

  19. Perspective: Fundamental aspects of time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Maitra, Neepa T. [Department of Physics and Astronomy, Hunter College and the Physics Program at the Graduate Center of the City University of New York, 695 Park Avenue, New York, New York 10065 (United States)

    2016-06-14

    In the thirty-two years since the birth of the foundational theorems, time-dependent density functional theory has had a tremendous impact on calculations of electronic spectra and dynamics in chemistry, biology, solid-state physics, and materials science. Alongside the wide-ranging applications, there has been much progress in understanding fundamental aspects of the functionals and the theory itself. This Perspective looks back to some of these developments, reports on some recent progress and current challenges for functionals, and speculates on future directions to improve the accuracy of approximations used in this relatively young theory.

  20. Open-system Kohn-Sham density functional theory.

    Science.gov (United States)

    Zhou, Yongxi; Ernzerhof, Matthias

    2012-03-07

    A simple model for electron transport through molecules is provided by the source-sink potential (SSP) method [F. Goyer, M. Ernzerhof, and M. Zhuang, J. Chem. Phys. 126, 144104 (2007)]. In SSP, the boundary conditions of having an incoming and outgoing electron current are enforced through complex potentials that are added to the Hamiltonian. Depending on the sign of the imaginary part of the potentials, current density is generated or absorbed. In this way, a finite system can be used to model infinite molecular electronic devices. The SSP has originally been developed for the Hückel method and subsequently it has been extended [F. Goyer and M. Ernzerhof, J. Chem. Phys. 134, 174101 (2011)] to the Hubbard model. Here we present a step towards its generalization for first-principles electronic structure theory methods. In particular, drawing on our earlier work, we discuss a new generalized density functional theory for complex non-Hermitian Hamiltonians. This theory enables us to combine SSP and Kohn-Sham theory to obtain a method for the description of open systems that exchange current density with their environment. Similarly, the Hartree-Fock method is extended to the realm of non-Hermitian, SSP containing Hamiltonians. As a proof of principle, we present the first applications of complex-density functional theory (CODFT) as well as non-Hermitian Hartree-Fock theory to electron transport through molecules. © 2012 American Institute of Physics

  1. Extending density functional embedding theory for covalently bonded systems.

    Science.gov (United States)

    Yu, Kuang; Carter, Emily A

    2017-12-19

    Quantum embedding theory aims to provide an efficient solution to obtain accurate electronic energies for systems too large for full-scale, high-level quantum calculations. It adopts a hierarchical approach that divides the total system into a small embedded region and a larger environment, using different levels of theory to describe each part. Previously, we developed a density-based quantum embedding theory called density functional embedding theory (DFET), which achieved considerable success in metals and semiconductors. In this work, we extend DFET into a density-matrix-based nonlocal form, enabling DFET to study the stronger quantum couplings between covalently bonded subsystems. We name this theory density-matrix functional embedding theory (DMFET), and we demonstrate its performance in several test examples that resemble various real applications in both chemistry and biochemistry. DMFET gives excellent results in all cases tested thus far, including predicting isomerization energies, proton transfer energies, and highest occupied molecular orbital-lowest unoccupied molecular orbital gaps for local chromophores. Here, we show that DMFET systematically improves the quality of the results compared with the widely used state-of-the-art methods, such as the simple capped cluster model or the widely used ONIOM method.

  2. Decay of autoionizing states in time-dependent density functional and reduced density matrix functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Varun; Brics, Martins; Bauer, Dieter [Institut fuer Physik, Universitaet Rostock, 18051 Rostock (Germany)

    2013-07-01

    Autoionizing states are inaccessible to time-dependent density functional theory (TDDFT) using known, adiabatic Kohn-Sham (KS) potentials. We determine the exact KS potential for a numerically exactly solvable model Helium atom interacting with a laser field that is populating an autoionizing state. The exact single-particle density of the population in the autoionizing state corresponds to that of the energetically lowest quasi-stationary state in the exact KS potential. We describe how this exact potential controls the decay by a barrier whose height and width allows for the density to tunnel out and decay with the same rate as in the ab initio time-dependent Schroedinger calculation. However, devising a useful exchange-correlation potential that is capable of governing such a scenario in general and in more complex systems is hopeless. As an improvement over TDDFT, time-dependent reduced density matrix functional theory has been proposed. We are able to obtain for the above described autoionization process the exact time-dependent natural orbitals (i.e., the eigenfunctions of the exact, time-dependent one-body reduced density matrix) and study the potentials that appear in the equations of motion for the natural orbitals and the structure of the two-body density matrix expanded in them.

  3. Density functional theory in surface science and heterogeneous catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Scheffler, M.; Toulhoat, H.

    2006-01-01

    Solid surfaces are used extensively as catalysts throughout the chemical industry, in the energy sector, and in environmental protection. Recently, density functional theory has started providing new insight into the atomic-scale mechanisms of heterogeneous catalysis, helping to interpret the large...

  4. Applications of Density Functional Theory in Soft Condensed Matter

    Science.gov (United States)

    Löwen, Hartmut

    Applications of classical density functional theory (DFT) to soft matter systems like colloids, liquid crystals and polymer solutions are discussed with a focus on the freezing transition and on nonequilibrium Brownian dynamics. First, after a brief reminder of equilibrium density functional theory, DFT is applied to the freezing transition of liquids into crystalline lattices. In particular, spherical particles with radially symmetric pair potentials will be treated (like hard spheres, the classical one-component plasma or Gaussian-core particles). Second, the DFT will be generalized towards Brownian dynamics in order to tackle nonequilibrium problems. After a general introduction to Brownian dynamics using the complementary Smoluchowski and Langevin pictures appropriate for the dynamics of colloidal suspensions, the dynamical density functional theory (DDFT) will be derived from the Smoluchowski equation. This will be done first for spherical particles (e.g. hard spheres or Gaussian-cores) without hydrodynamic interactions. Then we show how to incorporate hydrodynamic interactions between the colloidal particles into the DDFT framework and compare to Brownian dynamics computer simulations. Third orientational degrees of freedom (rod-like particles) will be considered as well. In the latter case, the stability of intermediate liquid crystalline phases (isotropic, nematic, smectic-A, plastic crystals etc) can be predicted. Finally, the corresponding dynamical extension of density functional theory towards orientational degrees of freedom is proposed and the collective behaviour of "active" (self-propelled) Brownian particles is briefly discussed.

  5. Time-dependent quantum fluid density functional theory of hydrogen ...

    Indian Academy of Sciences (India)

    A time-dependent generalized non-linear Schrödinger equation (GNLSE) of motion was earlier derived in our laboratory by combining density functional theory and quantum fluid dynamics in threedimensional space. In continuation of the work reported previously, the GNLSE is applied to provide additional knowledge on ...

  6. Basic concepts of Density Functional Theory: Electronic structure calculation

    International Nuclear Information System (INIS)

    Sharma, B. Indrajit

    2016-01-01

    We are looking for a material which possesses the required properties as demanded for technological applications. For this we have to repeat the preparation of the appropriate materials and its characterizations. So, before proceeding to experiments, one can study on computer generated structure and predict the properties of the desired material. To do this, a concept of Density Functional Theory comes out. (paper)

  7. Density-functional theory of atoms and molecules

    CERN Document Server

    Parr, Robert G

    1995-01-01

    Provides an account of the fundamental principles of the density-functional theory of the electronic structure of matter and its applications to atoms and molecules. This book contains a discussion of the chemical potential and its derivatives. It is intended for physicists, chemists, and advanced students in chemistry.

  8. Derivation of the density functional theory from the cluster expansion.

    Science.gov (United States)

    Hsu, J Y

    2003-09-26

    The density functional theory is derived from a cluster expansion by truncating the higher-order correlations in one and only one term in the kinetic energy. The formulation allows self-consistent calculation of the exchange correlation effect without imposing additional assumptions to generalize the local density approximation. The pair correlation is described as a two-body collision of bound-state electrons, and modifies the electron- electron interaction energy as well as the kinetic energy. The theory admits excited states, and has no self-interaction energy.

  9. Orbital functionals in density-matrix- and current-density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Helbig, N

    2006-05-15

    Density-Functional Theory (DFT), although widely used and very successful in the calculation of several observables, fails to correctly describe strongly correlated materials. In the first part of this work we, therefore, introduce reduced-densitymatrix- functional theory (RDMFT) which is one possible way to treat electron correlation beyond DFT. Within this theory the one-body reduced density matrix (1- RDM) is used as the basic variable. Our main interest is the calculation of the fundamental gap which proves very problematic within DFT. In order to calculate the fundamental gap we generalize RDMFT to fractional particle numbers M by describing the system as an ensemble of an N and an N+1 particle system (with N{<=}M{<=}N+1). For each fixed particle number, M, the total energy is minimized with respect to the natural orbitals and their occupation numbers. This leads to the total energy as a function of M. The derivative of this function with respect to the particle number has a discontinuity at integer particle number which is identical to the gap. In addition, we investigate the necessary and sufficient conditions for the 1- RDM of a system with fractional particle number to be N-representable. Numerical results are presented for alkali atoms, small molecules, and periodic systems. Another problem within DFT is the description of non-relativistic many-electron systems in the presence of magnetic fields. It requires the paramagnetic current density and the spin magnetization to be used as basic variables besides the electron density. However, electron-gas-based functionals of current-spin-density-functional Theory (CSDFT) exhibit derivative discontinuities as a function of the magnetic field whenever a new Landau level is occupied, which makes them difficult to use in practice. Since the appearance of Landau levels is, intrinsically, an orbital effect it is appealing to use orbital-dependent functionals. We have developed a CSDFT version of the optimized

  10. Benchmarks for electronically excited states: Time-dependent density functional theory and density functional theory based multireference configuration interaction

    DEFF Research Database (Denmark)

    Silva-Junior, Mario R.; Schreiber, Marko; Sauer, Stephan P. A.

    2008-01-01

    Time-dependent density functional theory (TD-DFT) and DFT-based multireference configuration interaction (DFT/MRCI) calculations are reported for a recently proposed benchmark set of 28 medium-sized organic molecules. Vertical excitation energies, oscillator strengths, and excited-state dipole...

  11. Density Functional Theory and Materials Modeling at Atomistic Length Scales

    Directory of Open Access Journals (Sweden)

    Swapan K. Ghosh

    2002-04-01

    Full Text Available Abstract: We discuss the basic concepts of density functional theory (DFT as applied to materials modeling in the microscopic, mesoscopic and macroscopic length scales. The picture that emerges is that of a single unified framework for the study of both quantum and classical systems. While for quantum DFT, the central equation is a one-particle Schrodinger-like Kohn-Sham equation, the classical DFT consists of Boltzmann type distributions, both corresponding to a system of noninteracting particles in the field of a density-dependent effective potential, the exact functional form of which is unknown. One therefore approximates the exchange-correlation potential for quantum systems and the excess free energy density functional or the direct correlation functions for classical systems. Illustrative applications of quantum DFT to microscopic modeling of molecular interaction and that of classical DFT to a mesoscopic modeling of soft condensed matter systems are highlighted.

  12. Density functional and many-body theories of Hydrogen plasmas

    International Nuclear Information System (INIS)

    Perrot, F.; Dharma-Wardana, M.W.C.

    1983-11-01

    This work is an attempt to go beyond the standard description of hot condensed matter using the well-known ''average atom model''. The first part describes a static model using ''Density functional theory'' to calculate self-consistent coupled electron and ion density profiles of the plasma not restricted to a single average atomic sphere. In a second part, the results are used as ingredients for a many-body approach to electronic properties: the one-particle Green-function self-energy is calculated, from which shifted levels, populations and level-widths are deduced. Results for the Hydrogen plasma are reported, with emphasis on the 1s bound state

  13. Comments on the locality in density-functional theory

    International Nuclear Information System (INIS)

    Lindgren, Ingvar; Salomonson, Sten

    2003-01-01

    The 'locality hypothesis' in density-functional theory (DFT), implying that the functional derivative is equivalent to a multiplicative local function, forms the basis of models of Kohn-Sham type. This has been generally accepted by the community since the advent of the model, and has later been formally proved for a large class of functionals. The hypothesis has recently been questioned by Nesbet [Phys. Rev. A 58, R12 (1998) and Phys. Rev. A 65, 010502 (2001)], who claims that it fails for the kinetic-energy functional for a system with more than two noninteracting electrons with a nondegenerate ground state. This conclusion has been questioned by Gal [Phys. Rev. A 62, 044501 (2000)] and by Holas and March [Phys. Rev. A 64, 016501 (2001)]. We claim that the arguments of Nesbet are incorrect, since the orbital functional used for the kinetic energy is not a unique functional of the total density in the domain of unnormalized orbitals. We have demonstrated that with a proper definition of the kinetic energy, which is a unique density functional also in the unnormalized region, the derivative can be represented by a single local multiplicative function for all v-representable densities. Therefore, we consider the controversy connected with the issue raised by Nesbet as resolved. We believe that the proof of the differentiability given here can be extended to larger groups of DFT functionals, and works along these lines are in progress

  14. Rydberg energies using excited state density functional theory

    International Nuclear Information System (INIS)

    Cheng, C.-L.; Wu Qin; Van Voorhis, Troy

    2008-01-01

    We utilize excited state density functional theory (eDFT) to study Rydberg states in atoms. We show both analytically and numerically that semilocal functionals can give quite reasonable Rydberg energies from eDFT, even in cases where time dependent density functional theory (TDDFT) fails catastrophically. We trace these findings to the fact that in eDFT the Kohn-Sham potential for each state is computed using the appropriate excited state density. Unlike the ground state potential, which typically falls off exponentially, the sequence of excited state potentials has a component that falls off polynomially with distance, leading to a Rydberg-type series. We also address the rigorous basis of eDFT for these systems. Perdew and Levy have shown using the constrained search formalism that every stationary density corresponds, in principle, to an exact stationary state of the full many-body Hamiltonian. In the present context, this means that the excited state DFT solutions are rigorous as long as they deliver the minimum noninteracting kinetic energy for the given density. We use optimized effective potential techniques to show that, in some cases, the eDFT Rydberg solutions appear to deliver the minimum kinetic energy because the associated density is not pure state v-representable. We thus find that eDFT plays a complementary role to constrained DFT: The former works only if the excited state density is not the ground state of some potential while the latter applies only when the density is a ground state density.

  15. Local density approximation for exchange in excited-state density functional theory

    OpenAIRE

    Harbola, Manoj K.; Samal, Prasanjit

    2004-01-01

    Local density approximation for the exchange energy is made for treatment of excited-states in density-functional theory. It is shown that taking care of the state-dependence of the LDA exchange energy functional leads to accurate excitation energies.

  16. A pair density functional theory utilizing the correlated wave function

    International Nuclear Information System (INIS)

    Higuchi, M; Higuchi, K

    2009-01-01

    We propose a practical scheme for calculating the ground-state pair density (PD) by utilizing the correlated wave function. As the correlated wave function, we adopt a linear combination of the single Slater determinants that are constructed from the solutions of the initial scheme [Higuchi M and Higuchi K 2007 Physica B 387, 117]. The single-particle equation is derived by performing the variational principle within the set of PDs that are constructed from such correlated wave functions. Since the search region of the PD is substantially extended as compared with the initial scheme, it is expected that the present scheme can cover more correlation effects. The single-particle equation is practical, and may be easily applied to actual calculations.

  17. Covariant density functional theory: The role of the pion

    International Nuclear Information System (INIS)

    Lalazissis, G. A.; Karatzikos, S.; Serra, M.; Otsuka, T.; Ring, P.

    2009-01-01

    We investigate the role of the pion in covariant density functional theory. Starting from conventional relativistic mean field (RMF) theory with a nonlinear coupling of the σ meson and without exchange terms we add pions with a pseudovector coupling to the nucleons in relativistic Hartree-Fock approximation. In order to take into account the change of the pion field in the nuclear medium the effective coupling constant of the pion is treated as a free parameter. It is found that the inclusion of the pion to this sort of density functionals does not destroy the overall description of the bulk properties by RMF. On the other hand, the noncentral contribution of the pion (tensor coupling) does have effects on single particle energies and on binding energies of certain nuclei.

  18. Buckled graphene: A model study based on density functional theory

    KAUST Repository

    Khan, Yasser

    2010-09-01

    We make use of ab initio calculations within density functional theory to investigate the influence of buckling on the electronic structure of single layer graphene. Our systematic study addresses a wide range of bond length and bond angle variations in order to obtain insights into the energy scale associated with the formation of ripples in a graphene sheet. © 2010 Elsevier B.V. All rights reserved.

  19. Buckled graphene: A model study based on density functional theory

    KAUST Repository

    Khan, Yasser; Mukaddam, Mohsin Ahmed; Schwingenschlö gl, Udo

    2010-01-01

    We make use of ab initio calculations within density functional theory to investigate the influence of buckling on the electronic structure of single layer graphene. Our systematic study addresses a wide range of bond length and bond angle variations in order to obtain insights into the energy scale associated with the formation of ripples in a graphene sheet. © 2010 Elsevier B.V. All rights reserved.

  20. Magnetic behavior study of samarium nitride using density functional theory

    Science.gov (United States)

    Som, Narayan N.; Mankad, Venu H.; Dabhi, Shweta D.; Patel, Anjali; Jha, Prafulla K.

    2018-02-01

    In this work, the state-of-art density functional theory is employed to study the structural, electronic and magnetic properties of samarium nitride (SmN). We have performed calculation for both ferromagnetic and antiferromagnetic states in rock-salt phase. The calculated results of optimized lattice parameter and magnetic moment agree well with the available experimental and theoretical values. From energy band diagram and electronic density of states, we observe a half-metallic behaviour in FM phase of rock salt SmN in while metallicity in AFM I and AFM III phases. We present and discuss our current understanding of the possible half-metallicity together with the magnetic ordering in SmN. The calculated phonon dispersion curves shows dynamical stability of the considered structures. The phonon density of states and Eliashberg functional have also been analysed to understand the superconductivity in SmN.

  1. Efficient molecular density functional theory using generalized spherical harmonics expansions.

    Science.gov (United States)

    Ding, Lu; Levesque, Maximilien; Borgis, Daniel; Belloni, Luc

    2017-09-07

    We show that generalized spherical harmonics are well suited for representing the space and orientation molecular density in the resolution of the molecular density functional theory. We consider the common system made of a rigid solute of arbitrary complexity immersed in a molecular solvent, both represented by molecules with interacting atomic sites and classical force fields. The molecular solvent density ρ(r,Ω) around the solute is a function of the position r≡(x,y,z) and of the three Euler angles Ω≡(θ,ϕ,ψ) describing the solvent orientation. The standard density functional, equivalent to the hypernetted-chain closure for the solute-solvent correlations in the liquid theory, is minimized with respect to ρ(r,Ω). The up-to-now very expensive angular convolution products are advantageously replaced by simple products between projections onto generalized spherical harmonics. The dramatic gain in speed of resolution enables to explore in a systematic way molecular solutes of up to nanometric sizes in arbitrary solvents and to calculate their solvation free energy and associated microscopic solvent structure in at most a few minutes. We finally illustrate the formalism by tackling the solvation of molecules of various complexities in water.

  2. What Density Functional Theory could do for Quantum Information

    Science.gov (United States)

    Mattsson, Ann

    2015-03-01

    The Hohenberg-Kohn theorem of Density Functional Theory (DFT), and extensions thereof, tells us that all properties of a system of electrons can be determined through their density, which uniquely determines the many-body wave-function. Given access to the appropriate, universal, functionals of the density we would, in theory, be able to determine all observables of any electronic system, without explicit reference to the wave-function. On the other hand, the wave-function is at the core of Quantum Information (QI), with the wave-function of a set of qubits being the central computational resource in a quantum computer. While there is seemingly little overlap between DFT and QI, reliance upon observables form a key connection. Though the time-evolution of the wave-function and associated phase information is fundamental to quantum computation, the initial and final states of a quantum computer are characterized by observables of the system. While observables can be extracted directly from a system's wave-function, DFT tells us that we may be able to intuit a method for extracting them from its density. In this talk, I will review the fundamentals of DFT and how these principles connect to the world of QI. This will range from DFT's utility in the engineering of physical qubits, to the possibility of using it to efficiently (but approximately) simulate Hamiltonians at the logical level. The apparent paradox of describing algorithms based on the quantum mechanical many-body wave-function with a DFT-like theory based on observables will remain a focus throughout. The ultimate goal of this talk is to initiate a dialog about what DFT could do for QI, in theory and in practice. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  3. Reduced density matrix functional theory at finite temperature

    Energy Technology Data Exchange (ETDEWEB)

    Baldsiefen, Tim

    2012-10-15

    Density functional theory (DFT) is highly successful in many fields of research. There are, however, areas in which its performance is rather limited. An important example is the description of thermodynamical variables of a quantum system in thermodynamical equilibrium. Although the finite-temperature version of DFT (FT-DFT) rests on a firm theoretical basis and is only one year younger than its brother, groundstate DFT, it has been successfully applied to only a few problems. Because FT-DFT, like DFT, is in principle exact, these shortcomings can be attributed to the difficulties of deriving valuable functionals for FT-DFT. In this thesis, we are going to present an alternative theoretical description of quantum systems in thermal equilibrium. It is based on the 1-reduced density matrix (1RDM) of the system, rather than on its density and will rather cumbersomly be called finite-temperature reduced density matrix functional theory (FT-RDMFT). Its zero-temperature counterpart (RDMFT) proved to be successful in several fields, formerly difficult to address via DFT. These fields include, for example, the calculation of dissociation energies or the calculation of the fundamental gap, also for Mott insulators. This success is mainly due to the fact that the 1RDM carries more directly accessible ''manybody'' information than the density alone, leading for example to an exact description of the kinetic energy functional. This sparks the hope that a description of thermodynamical systems employing the 1RDM via FT-RDMFT can yield an improvement over FT-DFT. Giving a short review of RDMFT and pointing out difficulties when describing spin-polarized systems initiates our work. We then lay the theoretical framework for FT-RDMFT by proving the required Hohenberg-Kohn-like theorems, investigating and determining the domain of FT-RDMFT functionals and by deriving several properties of the exact functional. Subsequently, we present a perturbative method to

  4. Reduced density matrix functional theory at finite temperature

    International Nuclear Information System (INIS)

    Baldsiefen, Tim

    2012-10-01

    Density functional theory (DFT) is highly successful in many fields of research. There are, however, areas in which its performance is rather limited. An important example is the description of thermodynamical variables of a quantum system in thermodynamical equilibrium. Although the finite-temperature version of DFT (FT-DFT) rests on a firm theoretical basis and is only one year younger than its brother, groundstate DFT, it has been successfully applied to only a few problems. Because FT-DFT, like DFT, is in principle exact, these shortcomings can be attributed to the difficulties of deriving valuable functionals for FT-DFT. In this thesis, we are going to present an alternative theoretical description of quantum systems in thermal equilibrium. It is based on the 1-reduced density matrix (1RDM) of the system, rather than on its density and will rather cumbersomly be called finite-temperature reduced density matrix functional theory (FT-RDMFT). Its zero-temperature counterpart (RDMFT) proved to be successful in several fields, formerly difficult to address via DFT. These fields include, for example, the calculation of dissociation energies or the calculation of the fundamental gap, also for Mott insulators. This success is mainly due to the fact that the 1RDM carries more directly accessible ''manybody'' information than the density alone, leading for example to an exact description of the kinetic energy functional. This sparks the hope that a description of thermodynamical systems employing the 1RDM via FT-RDMFT can yield an improvement over FT-DFT. Giving a short review of RDMFT and pointing out difficulties when describing spin-polarized systems initiates our work. We then lay the theoretical framework for FT-RDMFT by proving the required Hohenberg-Kohn-like theorems, investigating and determining the domain of FT-RDMFT functionals and by deriving several properties of the exact functional. Subsequently, we present a perturbative method to iteratively construct

  5. Describing a Strongly Correlated Model System with Density Functional Theory.

    Science.gov (United States)

    Kong, Jing; Proynov, Emil; Yu, Jianguo; Pachter, Ruth

    2017-07-06

    The linear chain of hydrogen atoms, a basic prototype for the transition from a metal to Mott insulator, is studied with a recent density functional theory model functional for nondynamic and strong correlation. The computed cohesive energy curve for the transition agrees well with accurate literature results. The variation of the electronic structure in this transition is characterized with a density functional descriptor that yields the atomic population of effectively localized electrons. These new methods are also applied to the study of the Peierls dimerization of the stretched even-spaced Mott insulator to a chain of H 2 molecules, a different insulator. The transitions among the two insulating states and the metallic state of the hydrogen chain system are depicted in a semiquantitative phase diagram. Overall, we demonstrate the capability of studying strongly correlated materials with a mean-field model at the fundamental level, in contrast to the general pessimistic view on such a feasibility.

  6. Plato: A localised orbital based density functional theory code

    Science.gov (United States)

    Kenny, S. D.; Horsfield, A. P.

    2009-12-01

    The Plato package allows both orthogonal and non-orthogonal tight-binding as well as density functional theory (DFT) calculations to be performed within a single framework. The package also provides extensive tools for analysing the results of simulations as well as a number of tools for creating input files. The code is based upon the ideas first discussed in Sankey and Niklewski (1989) [1] with extensions to allow high-quality DFT calculations to be performed. DFT calculations can utilise either the local density approximation or the generalised gradient approximation. Basis sets from minimal basis through to ones containing multiple radial functions per angular momenta and polarisation functions can be used. Illustrations of how the package has been employed are given along with instructions for its utilisation. Program summaryProgram title: Plato Catalogue identifier: AEFC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEFC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 219 974 No. of bytes in distributed program, including test data, etc.: 1 821 493 Distribution format: tar.gz Programming language: C/MPI and PERL Computer: Apple Macintosh, PC, Unix machines Operating system: Unix, Linux and Mac OS X Has the code been vectorised or parallelised?: Yes, up to 256 processors tested RAM: Up to 2 Gbytes per processor Classification: 7.3 External routines: LAPACK, BLAS and optionally ScaLAPACK, BLACS, PBLAS, FFTW Nature of problem: Density functional theory study of electronic structure and total energies of molecules, crystals and surfaces. Solution method: Localised orbital based density functional theory. Restrictions: Tight-binding and density functional theory only, no exact exchange. Unusual features: Both atom centred and uniform meshes available

  7. JDFTx: Software for joint density-functional theory

    Directory of Open Access Journals (Sweden)

    Ravishankar Sundararaman

    2017-01-01

    Full Text Available Density-functional theory (DFT has revolutionized computational prediction of atomic-scale properties from first principles in physics, chemistry and materials science. Continuing development of new methods is necessary for accurate predictions of new classes of materials and properties, and for connecting to nano- and mesoscale properties using coarse-grained theories. JDFTx is a fully-featured open-source electronic DFT software designed specifically to facilitate rapid development of new theories, models and algorithms. Using an algebraic formulation as an abstraction layer, compact C++11 code automatically performs well on diverse hardware including GPUs (Graphics Processing Units. This code hosts the development of joint density-functional theory (JDFT that combines electronic DFT with classical DFT and continuum models of liquids for first-principles calculations of solvated and electrochemical systems. In addition, the modular nature of the code makes it easy to extend and interface with, facilitating the development of multi-scale toolkits that connect to ab initio calculations, e.g. photo-excited carrier dynamics combining electron and phonon calculations with electromagnetic simulations.

  8. Time-dependent density-functional theory concepts and applications

    CERN Document Server

    Ullrich, Carsten A

    2011-01-01

    Time-dependent density-functional theory (TDDFT) describes the quantum dynamics of interacting electronic many-body systems formally exactly and in a practical and efficient manner. TDDFT has become the leading method for calculating excitation energies and optical properties of large molecules, with accuracies that rival traditional wave-function based methods, but at a fraction of the computational cost.This book is the first graduate-level text on the concepts and applications of TDDFT, including many examples and exercises, and extensive coverage of the literature. The book begins with a s

  9. Formation energies of rutile metal dioxides using density functional theory

    DEFF Research Database (Denmark)

    Martinez, Jose Ignacio; Hansen, Heine Anton; Rossmeisl, Jan

    2009-01-01

    We apply standard density functional theory at the generalized gradient approximation (GGA) level to study the stability of rutile metal oxides. It is well known that standard GGA exchange and correlation in some cases is not sufficient to address reduction and oxidation reactions. Especially...... and due to a more accurate description of exchange for this particular GGA functional compared to PBE. Furthermore, we would expect the self-interaction problem to be largest for the most localized d orbitals; that means the late 3d metals and since Co, Fe, Ni, and Cu do not form rutile oxides...

  10. General framework for fluctuating dynamic density functional theory

    Science.gov (United States)

    Durán-Olivencia, Miguel A.; Yatsyshin, Peter; Goddard, Benjamin D.; Kalliadasis, Serafim

    2017-12-01

    We introduce a versatile bottom-up derivation of a formal theoretical framework to describe (passive) soft-matter systems out of equilibrium subject to fluctuations. We provide a unique connection between the constituent-particle dynamics of real systems and the time evolution equation of their measurable (coarse-grained) quantities, such as local density and velocity. The starting point is the full Hamiltonian description of a system of colloidal particles immersed in a fluid of identical bath particles. Then, we average out the bath via Zwanzig’s projection-operator techniques and obtain the stochastic Langevin equations governing the colloidal-particle dynamics. Introducing the appropriate definition of the local number and momentum density fields yields a generalisation of the Dean-Kawasaki (DK) model, which resembles the stochastic Navier-Stokes description of a fluid. Nevertheless, the DK equation still contains all the microscopic information and, for that reason, does not represent the dynamical law of observable quantities. We address this controversial feature of the DK description by carrying out a nonequilibrium ensemble average. Adopting a natural decomposition into local-equilibrium and nonequilibrium contribution, where the former is related to a generalised version of the canonical distribution, we finally obtain the fluctuating-hydrodynamic equation governing the time-evolution of the mesoscopic density and momentum fields. Along the way, we outline the connection between the ad hoc energy functional introduced in previous DK derivations and the free-energy functional from classical density-functional theory. The resultant equation has the structure of a dynamical density-functional theory (DDFT) with an additional fluctuating force coming from the random interactions with the bath. We show that our fluctuating DDFT formalism corresponds to a particular version of the fluctuating Navier-Stokes equations, originally derived by Landau and Lifshitz

  11. Computational complexity of time-dependent density functional theory

    International Nuclear Information System (INIS)

    Whitfield, J D; Yung, M-H; Tempel, D G; Aspuru-Guzik, A; Boixo, S

    2014-01-01

    Time-dependent density functional theory (TDDFT) is rapidly emerging as a premier method for solving dynamical many-body problems in physics and chemistry. The mathematical foundations of TDDFT are established through the formal existence of a fictitious non-interacting system (known as the Kohn–Sham system), which can reproduce the one-electron reduced probability density of the actual system. We build upon these works and show that on the interior of the domain of existence, the Kohn–Sham system can be efficiently obtained given the time-dependent density. We introduce a V-representability parameter which diverges at the boundary of the existence domain and serves to quantify the numerical difficulty of constructing the Kohn-Sham potential. For bounded values of V-representability, we present a polynomial time quantum algorithm to generate the time-dependent Kohn–Sham potential with controllable error bounds. (paper)

  12. Fundamentals of time-dependent density functional theory

    International Nuclear Information System (INIS)

    Marques, Miguel A.L.; Rubio, Angel

    2012-01-01

    There have been many significant advances in time-dependent density functional theory over recent years, both in enlightening the fundamental theoretical basis of the theory, as well as in computational algorithms and applications. This book, as successor to the highly successful volume Time-Dependent Density Functional Theory (Lect. Notes Phys. 706, 2006) brings together for the first time all recent developments in a systematic and coherent way. First, a thorough pedagogical presentation of the fundamental theory is given, clarifying aspects of the original proofs and theorems, as well as presenting fresh developments that extend the theory into new realms such as alternative proofs of the original Runge-Gross theorem, open quantum systems, and dispersion forces to name but a few. Next, all of the basic concepts are introduced sequentially and building in complexity, eventually reaching the level of open problems of interest. Contemporary applications of the theory are discussed, from real-time coupled-electron-ion dynamics, to excited-state dynamics and molecular transport. Last but not least, the authors introduce and review recent advances in computational implementation, including massively parallel architectures and graphical processing units. Special care has been taken in editing this volume as a multi-author textbook, following a coherent line of thought, and making all the relevant connections between chapters and concepts consistent throughout. As such it will prove to be the text of reference in this field, both for beginners as well as expert researchers and lecturers teaching advanced quantum mechanical methods to model complex physical systems, from molecules to nanostructures, from biocomplexes to surfaces, solids and liquids. (orig.)

  13. A J matrix engine for density functional theory calculations

    International Nuclear Information System (INIS)

    White, C.A.; Head-Gordon, M.

    1996-01-01

    We introduce a new method for the formation of the J matrix (Coulomb interaction matrix) within a basis of Cartesian Gaussian functions, as needed in density functional theory and Hartree endash Fock calculations. By summing the density matrix into the underlying Gaussian integral formulas, we have developed a J matrix open-quote open-quote engine close-quote close-quote which forms the exact J matrix without explicitly forming the full set of two electron integral intermediates. Several precomputable quantities have been identified, substantially reducing the number of floating point operations and memory accesses needed in a J matrix calculation. Initial timings indicate a speedup of greater than four times for the (pp parallel pp) class of integrals with speedups increasing to over ten times for (ff parallel ff) integrals. copyright 1996 American Institute of Physics

  14. Inclusion of Dispersion Effects in Density Functional Theory

    DEFF Research Database (Denmark)

    Møgelhøj, Andreas

    on fitting to high-level ab initio and experimental results. The fitting scheme, based on Baysian theory, focuses on the three aspects: a) model space, b) datasets, and c) model selection. The model space consists of a flexible expansion of the exchange enhancement factor in the generalized gradient......In this thesis, applications and development will be presented within the field of van der Waals interactions in density functional theory. The thesis is based on the three projects: i) van der Waals interactions effect on the structure of liquid water at ambient conditions, ii) development......-range van der Waals interactions is essential to describe the adsorption/desorption process and commonly used generalized gradient approximation functionals are seen to be incapable of this....

  15. Nitrotyrosine adsorption on carbon nanotube: a density functional theory study

    Science.gov (United States)

    Majidi, R.; Karami, A. R.

    2014-05-01

    We have studied the effect of nitrotyrosine on electronic properties of different single-wall carbon nanotubes by density functional theory. Optimal adsorption configurations of nitrotyrosine adsorbed on carbon nanotube have been determined by calculation of adsorption energy. Adsorption energies indicate that nitrotyrosine is chemisorbed on carbon nanotubes. It is found that the nitrotyrosine adsorption modifies the electronic properties of the semiconducting carbon nanotubes significantly and these nanotubes become n-type semiconductors, while the effect of nitrotyrosine on metallic carbon nanotubes is not considerable and these nanotubes remain metallic. Results clarify sensitivity of carbon nanotubes to nitrotyrosine adsorption and suggest the possibility of using carbon nanotubes as biosensor for nitrotyrosine detection.

  16. The density functional theory and the charged fluid molecular dynamics

    International Nuclear Information System (INIS)

    Hansen, J.P.; Zerah, G.

    1993-01-01

    Car and Parrinello had the idea of combining the density functional theory (Hohenberg, Kohn and Sham) to the 'molecular dynamics' numerical modelling method, in order to simulate metallic or co-valent solids and liquids from the first principles. The objective of this paper is to present a simplified version of this method ab initio, applicable to classical and quantal charged systems. The method is illustrated with recent results on charged colloidal suspensions and highly correlated electron-proton plasmas. 1 fig., 21 refs

  17. Density functional theory for hydrogen storage materials: successes and opportunities

    International Nuclear Information System (INIS)

    Hector, L G Jr; Herbst, J F

    2008-01-01

    Solid state systems for hydrogen storage continue to be the focus of considerable international research, driven to a large extent by technological demands, especially for mobile applications. Density functional theory (DFT) has become a valuable tool in this effort. It has greatly expanded our understanding of the properties of known hydrides, including electronic structure, hydrogen bonding character, enthalpy of formation, elastic behavior, and vibrational energetics. Moreover, DFT holds substantial promise for guiding the discovery of new materials. In this paper we discuss, within the context of results from our own work, some successes and a few shortcomings of state-of-the-art DFT as applied to hydrogen storage materials

  18. Use of density functional theory in drug metabolism studies

    DEFF Research Database (Denmark)

    Rydberg, Patrik; Jørgensen, Flemming Steen; Olsen, Lars

    2014-01-01

    INTRODUCTION: The cytochrome P450 enzymes (CYPs) metabolize many drug compounds. They catalyze a wide variety of reactions, and potentially, a large number of different metabolites can be generated. Density functional theory (DFT) has, over the past decade, been shown to be a powerful tool...... isoforms. This is probably due to the fact that the binding of the substrates is not the major determinant. When binding of the substrate plays a significant role, the well-known issue of determining the free energy of binding is the challenge. How approaches taking the protein environment into account...

  19. Multiconfiguration Pair-Density Functional Theory Outperforms Kohn-Sham Density Functional Theory and Multireference Perturbation Theory for Ground-State and Excited-State Charge Transfer.

    Science.gov (United States)

    Ghosh, Soumen; Sonnenberger, Andrew L; Hoyer, Chad E; Truhlar, Donald G; Gagliardi, Laura

    2015-08-11

    The correct description of charge transfer in ground and excited states is very important for molecular interactions, photochemistry, electrochemistry, and charge transport, but it is very challenging for Kohn-Sham (KS) density functional theory (DFT). KS-DFT exchange-correlation functionals without nonlocal exchange fail to describe both ground- and excited-state charge transfer properly. We have recently proposed a theory called multiconfiguration pair-density functional theory (MC-PDFT), which is based on a combination of multiconfiguration wave function theory with a new type of density functional called an on-top density functional. Here we have used MC-PDFT to study challenging ground- and excited-state charge-transfer processes by using on-top density functionals obtained by translating KS exchange-correlation functionals. For ground-state charge transfer, MC-PDFT performs better than either the PBE exchange-correlation functional or CASPT2 wave function theory. For excited-state charge transfer, MC-PDFT (unlike KS-DFT) shows qualitatively correct behavior at long-range with great improvement in predicted excitation energies.

  20. Dynamic density functional theory of solid tumor growth: Preliminary models

    Directory of Open Access Journals (Sweden)

    Arnaud Chauviere

    2012-03-01

    Full Text Available Cancer is a disease that can be seen as a complex system whose dynamics and growth result from nonlinear processes coupled across wide ranges of spatio-temporal scales. The current mathematical modeling literature addresses issues at various scales but the development of theoretical methodologies capable of bridging gaps across scales needs further study. We present a new theoretical framework based on Dynamic Density Functional Theory (DDFT extended, for the first time, to the dynamics of living tissues by accounting for cell density correlations, different cell types, phenotypes and cell birth/death processes, in order to provide a biophysically consistent description of processes across the scales. We present an application of this approach to tumor growth.

  1. Descriptions of carbon isotopes within the energy density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Ismail, Atef [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak, Malaysia and Department of Physics, Al-Azhar University, 71524 Assiut (Egypt); Cheong, Lee Yen; Yahya, Noorhana [Fundamental and Applied Sciences Department, Universiti Teknologi PETRONAS, Bandar Seri Iskandar, 31750 Tronoh, Perak (Malaysia); Tammam, M. [Department of Physics, Al-Azhar University, 71524 Assiut (Egypt)

    2014-10-24

    Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in {sup 15}C, {sup 17}C and {sup 19}C, and the two-neutron halo structures in {sup 16}C and {sup 22}C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations.

  2. Descriptions of carbon isotopes within the energy density functional theory

    International Nuclear Information System (INIS)

    Ismail, Atef; Cheong, Lee Yen; Yahya, Noorhana; Tammam, M.

    2014-01-01

    Within the energy density functional (EDF) theory, the structure properties of Carbon isotopes are systematically studied. The shell model calculations are done for both even-A and odd-A nuclei, to study the structure of rich-neutron Carbon isotopes. The EDF theory indicates the single-neutron halo structures in 15 C, 17 C and 19 C, and the two-neutron halo structures in 16 C and 22 C nuclei. It is also found that close to the neutron drip-line, there exist amazing increase in the neutron radii and decrease on the binding energies BE, which are tightly related with the blocking effect and correspondingly the blocking effect plays a significant role in the shell model configurations

  3. Thermodynamics as a Foundation for Density Functional Theory

    International Nuclear Information System (INIS)

    Argaman, Nathan

    2014-01-01

    Density Functional Theory (DFT) is the method of choice for an ever increasing number of electronic structure computations (recently reaching 30,000 publications per year). It was founded in the sixties on the basis of the Hohenberg-Kohn theorem and the Kohn-Sham equations, which were originally proved and derived for electronic ground states. Alternatively, one may use thermodynamics to derive DFT for finite-temperature ensembles, with the ground-state theory recovered in the zero temperature limit. Specifically, the transformation from chemical potential µ to electron number N as a free variable may be directly generalized to clarify how DFT uses the density distribution n(r), rather than the external potential v(r), to specify a particular inhomogeneous electronic system. Relating interacting and non-interacting systems with the same n(r) distribution, one recovers not only the Kohn-Sham formulation, but also the so-called adiabatic connection theorem, which gives an explicit expression for the exchange-correlation energy in terms of the 'exchangecorrelation hole.' This derivation has the advantage of being constructive, rather than being based on a reductio ad absurdum argument. It thus serves as an excellent basis for a discussion of the approximations which are inevitably introduced, including the Local Density Approximation (LDA) and the Generalized Gradient Approximation (GGA)

  4. Single-particle energies and density of states in density functional theory

    Science.gov (United States)

    van Aggelen, H.; Chan, G. K.-L.

    2015-07-01

    Time-dependent density functional theory (TD-DFT) is commonly used as the foundation to obtain neutral excited states and transition weights in DFT, but does not allow direct access to density of states and single-particle energies, i.e. ionisation energies and electron affinities. Here we show that by extending TD-DFT to a superfluid formulation, which involves operators that break particle-number symmetry, we can obtain the density of states and single-particle energies from the poles of an appropriate superfluid response function. The standard Kohn- Sham eigenvalues emerge as the adiabatic limit of the superfluid response under the assumption that the exchange- correlation functional has no dependence on the superfluid density. The Kohn- Sham eigenvalues can thus be interpreted as approximations to the ionisation energies and electron affinities. Beyond this approximation, the formalism provides an incentive for creating a new class of density functionals specifically targeted at accurate single-particle eigenvalues and bandgaps.

  5. Density-functional theory simulation of large quantum dots

    Science.gov (United States)

    Jiang, Hong; Baranger, Harold U.; Yang, Weitao

    2003-10-01

    Kohn-Sham spin-density functional theory provides an efficient and accurate model to study electron-electron interaction effects in quantum dots, but its application to large systems is a challenge. Here an efficient method for the simulation of quantum dots using density-function theory is developed; it includes the particle-in-the-box representation of the Kohn-Sham orbitals, an efficient conjugate-gradient method to directly minimize the total energy, a Fourier convolution approach for the calculation of the Hartree potential, and a simplified multigrid technique to accelerate the convergence. We test the methodology in a two-dimensional model system and show that numerical studies of large quantum dots with several hundred electrons become computationally affordable. In the noninteracting limit, the classical dynamics of the system we study can be continuously varied from integrable to fully chaotic. The qualitative difference in the noninteracting classical dynamics has an effect on the quantum properties of the interacting system: integrable classical dynamics leads to higher-spin states and a broader distribution of spacing between Coulomb blockade peaks.

  6. The force distribution probability function for simple fluids by density functional theory.

    Science.gov (United States)

    Rickayzen, G; Heyes, D M

    2013-02-28

    Classical density functional theory (DFT) is used to derive a formula for the probability density distribution function, P(F), and probability distribution function, W(F), for simple fluids, where F is the net force on a particle. The final formula for P(F) ∝ exp(-AF(2)), where A depends on the fluid density, the temperature, and the Fourier transform of the pair potential. The form of the DFT theory used is only applicable to bounded potential fluids. When combined with the hypernetted chain closure of the Ornstein-Zernike equation, the DFT theory for W(F) agrees with molecular dynamics computer simulations for the Gaussian and bounded soft sphere at high density. The Gaussian form for P(F) is still accurate at lower densities (but not too low density) for the two potentials, but with a smaller value for the constant, A, than that predicted by the DFT theory.

  7. Geometry-based density functional theory an overview

    CERN Document Server

    Schmidt, M

    2003-01-01

    An overview of recent developments and applications of a specific density functional approach that originates from Rosenfeld's fundamental measure theory for hard spheres is given. Model systems that were treated include penetrable spheres that interact with a step function pair potential, the Widom-Rowlinson model, the Asakura-Oosawa colloid-polymer mixture, ternary mixtures of spheres, needles, and globular polymers, hard-body amphiphilic mixtures, fluids in porous media, and random sequential adsorption that describes non-equilibrium processes such as colloidal deposition and random car parking. In these systems various physical phenomena were studied, such as correlations in liquids, freezing and demixing phase behaviour, the properties of fluid interfaces with and without orientational order, and wetting and layering phenomena at walls.

  8. Geometry-based density functional theory: an overview

    Science.gov (United States)

    Schmidt, Matthias

    2003-01-01

    An overview of recent developments and applications of a specific density functional approach that originates from Rosenfeld's fundamental measure theory for hard spheres is given. Model systems that were treated include penetrable spheres that interact with a step function pair potential, the Widom-Rowlinson model, the Asakura-Oosawa colloid-polymer mixture, ternary mixtures of spheres, needles, and globular polymers, hard-body amphiphilic mixtures, fluids in porous media, and random sequential adsorption that describes non-equilibrium processes such as colloidal deposition and random car parking. In these systems various physical phenomena were studied, such as correlations in liquids, freezing and demixing phase behaviour, the properties of fluid interfaces with and without orientational order, and wetting and layering phenomena at walls.

  9. Geometry-based density functional theory: an overview

    International Nuclear Information System (INIS)

    Schmidt, Matthias

    2003-01-01

    An overview of recent developments and applications of a specific density functional approach that originates from Rosenfeld's fundamental measure theory for hard spheres is given. Model systems that were treated include penetrable spheres that interact with a step function pair potential, the Widom-Rowlinson model, the Asakura-Oosawa colloid-polymer mixture, ternary mixtures of spheres, needles, and globular polymers, hard-body amphiphilic mixtures, fluids in porous media, and random sequential adsorption that describes non-equilibrium processes such as colloidal deposition and random car parking. In these systems various physical phenomena were studied, such as correlations in liquids, freezing and demixing phase behaviour, the properties of fluid interfaces with and without orientational order, and wetting and layering phenomena at walls

  10. Density functional theory studies of transition metal nanoparticles in catalysis

    DEFF Research Database (Denmark)

    Greeley, Jeffrey Philip; Rankin, Rees; Zeng, Zhenhua

    2013-01-01

    Periodic Density Functional Theory calculations are capable of providing powerful insights into the structural, energetics, and electronic phenomena that underlie heterogeneous catalysis on transition metal nanoparticles. Such calculations are now routinely applied to single crystal metal surfaces...... and to subnanometer metal clusters. Descriptions of catalysis on truly nanosized structures, however, are generally not as well developed. In this talk, I will illustrate different approaches to analyzing nanocatalytic phenomena with DFT calculations. I will describe case studies from heterogeneous catalysis...... and electrocatalysis, in which single crystal models are combined with Wulff construction-based ideas to produce descriptions of average nanocatalyst behavior. Then, I will proceed to describe explicitly DFT-based descriptions of catalysis on truly nanosized particles (

  11. Nitrotyrosine adsorption on defective graphene: A density functional theory study

    Science.gov (United States)

    Majidi, R.; Karami, A. R.

    2015-06-01

    We have applied density functional theory to study adsorption of nitrotyrosine on perfect and defective graphene sheets. The graphene sheets with Stone-Wales (SW) defect, pentagon-nonagon (5-9) single vacancy, and pentagon-octagon-pentagon (5-8-5) double vacancy were considered. The calculations of adsorption energy showed that nitrotyrosine presents a more strong interaction with defective graphene rather than with perfect graphene sheet. The order of interaction strength is: SW>5-9>5-8-5>perfect graphene. It is found that the electronic properties of perfect and defective graphene are sensitive to the presence of nitrotyrosine. Hence, graphene sheets can be considered as a good sensor for detection of nitrotyrosine molecule which is observed in connection with several human disorders, such as Parkinson's and Alzheimer's disease.

  12. Oenin and Quercetin Copigmentation: Highlights From Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Yunkui Li

    2018-06-01

    Full Text Available Making use of anthocyanin copigmentation, it is possible to effectively improve color quality and stability of red wines and other foods. This can be done by selecting strong copigments, but a 1-fold experimental screening usually entails a high cost and a low efficiency. The aim of this work is to show how a theoretical model based on density functional theory can be useful for an accurate and rapid prediction of copigmentation ability of a copigment. The present study, concerning the copigmentation between oenin and quercetin under the framework of implicit solvent, indicates that, in these conditions, the intermolecular hydrogen bonds play an important role in the system stabilization. The dispersion interaction slightly affects the structure, energies and UV-Vis spectral properties of the copigmentation complex.

  13. Density functional theory study of Al-doped hematite

    International Nuclear Information System (INIS)

    Rivera, Richard; Stashans, Arvids; Piedra, Lorena; Pinto, Henry P

    2012-01-01

    Using first-principles density functional theory calculations within the generalized gradient approximation (GGA) as well as the GGA+U approach, we study Al-doped α-Fe 2 O 3 crystals. Structural, electronic, magnetic and optical properties due to impurity incorporation have been investigated and discussed in detail. Atomic displacements and Bader charges on atoms have been computed, showing that Al dopant converts the chemical bonding in its neighbourhood into a more ionic one. This work enhances our knowledge about how a crystalline lattice reacts in the presence of an Al impurity. It was found that Al incorporation produces some local changes in the band structure of the material without the creation of local energy levels within the band gap. The results provide evidence for changes in the magnetic moments in the vicinity of a defect, which means that α-Fe 2 O 3 doped with aluminum might not act as an antiferromagnetic substance.

  14. Strong Correlation in Kohn-Sham Density Functional Theory

    NARCIS (Netherlands)

    Malet, F.; Gori Giorgi, P.

    2012-01-01

    We use the exact strong-interaction limit of the Hohenberg-Kohn energy density functional to approximate the exchange-correlation energy of the restricted Kohn-Sham scheme. Our approximation corresponds to a highly nonlocal density functional whose functional derivative can be easily constructed,

  15. Multiscale time-dependent density functional theory: Demonstration for plasmons.

    Science.gov (United States)

    Jiang, Jiajian; Abi Mansour, Andrew; Ortoleva, Peter J

    2017-08-07

    Plasmon properties are of significant interest in pure and applied nanoscience. While time-dependent density functional theory (TDDFT) can be used to study plasmons, it becomes impractical for elucidating the effect of size, geometric arrangement, and dimensionality in complex nanosystems. In this study, a new multiscale formalism that addresses this challenge is proposed. This formalism is based on Trotter factorization and the explicit introduction of a coarse-grained (CG) structure function constructed as the Weierstrass transform of the electron wavefunction. This CG structure function is shown to vary on a time scale much longer than that of the latter. A multiscale propagator that coevolves both the CG structure function and the electron wavefunction is shown to bring substantial efficiency over classical propagators used in TDDFT. This efficiency follows from the enhanced numerical stability of the multiscale method and the consequence of larger time steps that can be used in a discrete time evolution. The multiscale algorithm is demonstrated for plasmons in a group of interacting sodium nanoparticles (15-240 atoms), and it achieves improved efficiency over TDDFT without significant loss of accuracy or space-time resolution.

  16. Reduced density-matrix functional theory: Correlation and spectroscopy.

    Science.gov (United States)

    Di Sabatino, S; Berger, J A; Reining, L; Romaniello, P

    2015-07-14

    In this work, we explore the performance of approximations to electron correlation in reduced density-matrix functional theory (RDMFT) and of approximations to the observables calculated within this theory. Our analysis focuses on the calculation of total energies, occupation numbers, removal/addition energies, and spectral functions. We use the exactly solvable Hubbard dimer at 1/4 and 1/2 fillings as test systems. This allows us to analyze the underlying physics and to elucidate the origin of the observed trends. For comparison, we also report the results of the GW approximation, where the self-energy functional is approximated, but no further hypothesis is made concerning the approximations of the observables. In particular, we focus on the atomic limit, where the two sites of the dimer are pulled apart and electrons localize on either site with equal probability, unless a small perturbation is present: this is the regime of strong electron correlation. In this limit, using the Hubbard dimer at 1/2 filling with or without a spin-symmetry-broken ground state allows us to explore how degeneracies and spin-symmetry breaking are treated in RDMFT. We find that, within the used approximations, neither in RDMFT nor in GW, the signature of strong correlation is present, when looking at the removal/addition energies and spectral function from the spin-singlet ground state, whereas both give the exact result for the spin-symmetry broken case. Moreover, we show how the spectroscopic properties change from one spin structure to the other.

  17. Explicit polarization (X-Pol) potential using ab initio molecular orbital theory and density functional theory.

    Science.gov (United States)

    Song, Lingchun; Han, Jaebeom; Lin, Yen-lin; Xie, Wangshen; Gao, Jiali

    2009-10-29

    The explicit polarization (X-Pol) method has been examined using ab initio molecular orbital theory and density functional theory. The X-Pol potential was designed to provide a novel theoretical framework for developing next-generation force fields for biomolecular simulations. Importantly, the X-Pol potential is a general method, which can be employed with any level of electronic structure theory. The present study illustrates the implementation of the X-Pol method using ab initio Hartree-Fock theory and hybrid density functional theory. The computational results are illustrated by considering a set of bimolecular complexes of small organic molecules and ions with water. The computed interaction energies and hydrogen bond geometries are in good accord with CCSD(T) calculations and B3LYP/aug-cc-pVDZ optimizations.

  18. Reduced density matrix functional theory via a wave function based approach

    Energy Technology Data Exchange (ETDEWEB)

    Schade, Robert; Bloechl, Peter [Institute for Theoretical Physics, Clausthal University of Technology, Clausthal (Germany); Pruschke, Thomas [Institute for Theoretical Physics, University of Goettingen, Goettingen (Germany)

    2016-07-01

    We propose a new method for the calculation of the electronic and atomic structure of correlated electron systems based on reduced density matrix functional theory (rDMFT). The density-matrix functional is evaluated on the fly using Levy's constrained search formalism. The present implementation rests on a local approximation of the interaction reminiscent to that of dynamical mean field theory (DMFT). We focus here on additional approximations to the exact density-matrix functional in the local approximation and evaluate their performance.

  19. Modeling charged defects inside density functional theory band gaps

    International Nuclear Information System (INIS)

    Schultz, Peter A.; Edwards, Arthur H.

    2014-01-01

    Density functional theory (DFT) has emerged as an important tool to probe microscopic behavior in materials. The fundamental band gap defines the energy scale for charge transition energy levels of point defects in ionic and covalent materials. The eigenvalue gap between occupied and unoccupied states in conventional DFT, the Kohn–Sham gap, is often half or less of the experimental band gap, seemingly precluding quantitative studies of charged defects. Applying explicit and rigorous control of charge boundary conditions in supercells, we find that calculations of defect energy levels derived from total energy differences give accurate predictions of charge transition energy levels in Si and GaAs, unhampered by a band gap problem. The GaAs system provides a good theoretical laboratory for investigating band gap effects in defect level calculations: depending on the functional and pseudopotential, the Kohn–Sham gap can be as large as 1.1 eV or as small as 0.1 eV. We find that the effective defect band gap, the computed range in defect levels, is mostly insensitive to the Kohn–Sham gap, demonstrating it is often possible to use conventional DFT for quantitative studies of defect chemistry governing interesting materials behavior in semiconductors and oxides despite a band gap problem

  20. Self-interaction corrections in density functional theory

    International Nuclear Information System (INIS)

    Tsuneda, Takao; Hirao, Kimihiko

    2014-01-01

    Self-interaction corrections for Kohn-Sham density functional theory are reviewed for their physical meanings, formulations, and applications. The self-interaction corrections get rid of the self-interaction error, which is the sum of the Coulomb and exchange self-interactions that remains because of the use of an approximate exchange functional. The most frequently used self-interaction correction is the Perdew-Zunger correction. However, this correction leads to instabilities in the electronic state calculations of molecules. To avoid these instabilities, several self-interaction corrections have been developed on the basis of the characteristic behaviors of self-interacting electrons, which have no two-electron interactions. These include the von Weizsäcker kinetic energy and long-range (far-from-nucleus) asymptotic correction. Applications of self-interaction corrections have shown that the self-interaction error has a serious effect on the states of core electrons, but it has a smaller than expected effect on valence electrons. This finding is supported by the fact that the distribution of self-interacting electrons indicates that they are near atomic nuclei rather than in chemical bonds

  1. Relationship of Quantum Entanglement to Density Functional Theory

    OpenAIRE

    Rajagopal, A. K.; Rendell, R. W.

    2005-01-01

    The maximum von Neumann entropy principle subject to given constraints of mean values of some physical observables determines the density matrix. Similarly the stationary action principle in the case of time-dependent (dissipative) situations under similar constraints yields the density matrix. The free energy and measures of entanglement are expressed in terms of such a density matrix and thus define respective functionals of the mean values. In the light of several model calculations, it is...

  2. Quantum Crystallography: Density Matrix-Density Functional Theory and the X-Ray Diffraction Experiment

    Science.gov (United States)

    Soirat, Arnaud J. A.

    Density Matrix Theory is a Quantum Mechanical formalism in which the wavefunction is eliminated and its role taken over by reduced density matrices. The interest of this is that, it allows one, in principle, to calculate any electronic property of a physical system, without having to solve the Schrodinger equation, using only two entities much simpler than an N-body wavefunction: first and second -order reduced density matrices. In practice, though, this very promising possibility faces the tremendous theoretical problem of N-representability, which has been solved for the former, but, until now, voids any hope of theoretically determining the latter. However, it has been shown that single determinant reduced density matrices of any order may be recovered from coherent X-ray diffraction data, if one provides a proper Quantum Mechanical description of the Crystallography experiment. A deeper investigation of this method is the purpose of this work, where we, first, further study the calculation of X-ray reduced density matrices N-representable by a single Slater determinant. In this context, we independently derive necessary and sufficient conditions for the uniqueness of the method. We then show how to account for electron correlation in this model. For the first time, indeed, we derive highly accurate, yet practical, density matrices approximately N-representable by correlated-determinant wavefunctions. The interest of such a result lies in the Quantum Mechanical validity of these density matrices, their property of being entirely obtainable from X-ray coherent diffraction data, their very high accuracy conferred by this known property of the N-representing wavefunction, as well as their definition as explicit functionals of the density. All of these properties are finally used in both a theoretical and a numerical application: in the former, we show that these density matrices may be used in the context of Density Functional Theory to highly accurately determine

  3. Transport through correlated systems with density functional theory.

    Science.gov (United States)

    Kurth, S; Stefanucci, G

    2017-10-18

    We present recent advances in density functional theory (DFT) for applications in the field of quantum transport, with particular emphasis on transport through strongly correlated systems. We review the foundations of the popular Landauer-Büttiker(LB)  +  DFT approach. This formalism, when using approximations to the exchange-correlation (xc) potential with steps at integer occupation, correctly captures the Kondo plateau in the zero bias conductance at zero temperature but completely fails to capture the transition to the Coulomb blockade (CB) regime as the temperature increases. To overcome the limitations of LB  +  DFT, the quantum transport problem is treated from a time-dependent (TD) perspective using TDDFT, an exact framework to deal with nonequilibrium situations. The steady-state limit of TDDFT shows that in addition to an xc potential in the junction, there also exists an xc correction to the applied bias. Open shell molecules in the CB regime provide the most striking examples of the importance of the xc bias correction. Using the Anderson model as guidance we estimate these corrections in the limit of zero bias. For the general case we put forward a steady-state DFT which is based on one-to-one correspondence between the pair of basic variables, steady density on and steady current across the junction and the pair local potential on and bias across the junction. Like TDDFT, this framework also leads to both an xc potential in the junction and an xc correction to the bias. Unlike TDDFT, these potentials are independent of history. We highlight the universal features of both xc potential and xc bias corrections for junctions in the CB regime and provide an accurate parametrization for the Anderson model at arbitrary temperatures and interaction strengths, thus providing a unified DFT description for both Kondo and CB regimes and the transition between them.

  4. Density Functional Theory for Phase-Ordering Transitions

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jianzhong [Univ. of California, Riverside, CA (United States)

    2016-03-30

    Colloids display astonishing structural and dynamic properties that can be dramatically altered by modest changes in the solution condition or an external field. This complex behavior stems from a subtle balance of colloidal forces and intriguing mesoscopic and macroscopic phase transitions that are sensitive to the processing conditions and the dispersing environment. Whereas the knowledge on the microscopic structure and phase behavior of colloidal systems at equilibrium is now well-advanced, quantitative predictions of the dynamic properties and the kinetics of phase-ordering transitions in colloids are not always realized. Many important mesoscopic and off-equilibrium colloidal states remain poorly understood. The proposed research aims to develop a new, unifying approach to describe colloidal dynamics and the kinetics of phase-ordering transitions based on accomplishments from previous work for the equilibrium properties of both uniform and inhomogeneous systems and on novel concepts from the state-of-the-art dynamic density functional theory. In addition to theoretical developments, computational research is designed to address a number of fundamental questions on phase-ordering transitions in colloids, in particular those pertinent to a competition of the dynamic pathways leading to various mesoscopic structures, off-equilibrium states, and crystalline phases. By providing a generic theoretical framework to describe equilibrium, metastable as well as non-ergodic phase transitions concurrent with the colloidal self-assembly processes, accomplishments from this work will have major impacts on both fundamental research and technological applications.

  5. Quantum Drude friction for time-dependent density functional theory

    Science.gov (United States)

    Neuhauser, Daniel; Lopata, Kenneth

    2008-10-01

    way to very simple finite grid description of scattering and multistage conductance using time-dependent density functional theory away from the linear regime, just as absorbing potentials and self-energies are useful for noninteracting systems and leads.

  6. Dispersion correction derived from first principles for density functional theory and Hartree-Fock theory.

    Science.gov (United States)

    Guidez, Emilie B; Gordon, Mark S

    2015-03-12

    The modeling of dispersion interactions in density functional theory (DFT) is commonly performed using an energy correction that involves empirically fitted parameters for all atom pairs of the system investigated. In this study, the first-principles-derived dispersion energy from the effective fragment potential (EFP) method is implemented for the density functional theory (DFT-D(EFP)) and Hartree-Fock (HF-D(EFP)) energies. Overall, DFT-D(EFP) performs similarly to the semiempirical DFT-D corrections for the test cases investigated in this work. HF-D(EFP) tends to underestimate binding energies and overestimate intermolecular equilibrium distances, relative to coupled cluster theory, most likely due to incomplete accounting for electron correlation. Overall, this first-principles dispersion correction yields results that are in good agreement with coupled-cluster calculations at a low computational cost.

  7. Global and local curvature in density functional theory.

    Science.gov (United States)

    Zhao, Qing; Ioannidis, Efthymios I; Kulik, Heather J

    2016-08-07

    Piecewise linearity of the energy with respect to fractional electron removal or addition is a requirement of an electronic structure method that necessitates the presence of a derivative discontinuity at integer electron occupation. Semi-local exchange-correlation (xc) approximations within density functional theory (DFT) fail to reproduce this behavior, giving rise to deviations from linearity with a convex global curvature that is evidence of many-electron, self-interaction error and electron delocalization. Popular functional tuning strategies focus on reproducing piecewise linearity, especially to improve predictions of optical properties. In a divergent approach, Hubbard U-augmented DFT (i.e., DFT+U) treats self-interaction errors by reducing the local curvature of the energy with respect to electron removal or addition from one localized subshell to the surrounding system. Although it has been suggested that DFT+U should simultaneously alleviate global and local curvature in the atomic limit, no detailed study on real systems has been carried out to probe the validity of this statement. In this work, we show when DFT+U should minimize deviations from linearity and demonstrate that a "+U" correction will never worsen the deviation from linearity of the underlying xc approximation. However, we explain varying degrees of efficiency of the approach over 27 octahedral transition metal complexes with respect to transition metal (Sc-Cu) and ligand strength (CO, NH3, and H2O) and investigate select pathological cases where the delocalization error is invisible to DFT+U within an atomic projection framework. Finally, we demonstrate that the global and local curvatures represent different quantities that show opposing behavior with increasing ligand field strength, and we identify where these two may still coincide.

  8. Central depression in nucleonic densities: Trend analysis in the nuclear density functional theory approach

    Science.gov (United States)

    Schuetrumpf, B.; Nazarewicz, W.; Reinhard, P.-G.

    2017-08-01

    Background: The central depression of nucleonic density, i.e., a reduction of density in the nuclear interior, has been attributed to many factors. For instance, bubble structures in superheavy nuclei are believed to be due to the electrostatic repulsion. In light nuclei, the mechanism behind the density reduction in the interior has been discussed in terms of shell effects associated with occupations of s orbits. Purpose: The main objective of this work is to reveal mechanisms behind the formation of central depression in nucleonic densities in light and heavy nuclei. To this end, we introduce several measures of the internal nucleonic density. Through the statistical analysis, we study the information content of these measures with respect to nuclear matter properties. Method: We apply nuclear density functional theory with Skyrme functionals. Using the statistical tools of linear least square regression, we inspect correlations between various measures of central depression and model parameters, including nuclear matter properties. We study bivariate correlations with selected quantities as well as multiple correlations with groups of parameters. Detailed correlation analysis is carried out for 34Si for which a bubble structure has been reported recently, 48Ca, and N =82 , 126, and 184 isotonic chains. Results: We show that the central depression in medium-mass nuclei is very sensitive to shell effects, whereas for superheavy systems it is firmly driven by the electrostatic repulsion. An appreciable semibubble structure in proton density is predicted for 294Og, which is currently the heaviest nucleus known experimentally. Conclusion: Our correlation analysis reveals that the central density indicators in nuclei below 208Pb carry little information on parameters of nuclear matter; they are predominantly driven by shell structure. On the other hand, in the superheavy nuclei there exists a clear relationship between the central nucleonic density and symmetry energy.

  9. Recent developments in LIBXC - A comprehensive library of functionals for density functional theory

    Science.gov (United States)

    Lehtola, Susi; Steigemann, Conrad; Oliveira, Micael J. T.; Marques, Miguel A. L.

    2018-01-01

    LIBXC is a library of exchange-correlation functionals for density-functional theory. We are concerned with semi-local functionals (or the semi-local part of hybrid functionals), namely local-density approximations, generalized-gradient approximations, and meta-generalized-gradient approximations. Currently we include around 400 functionals for the exchange, correlation, and the kinetic energy, spanning more than 50 years of research. Moreover, LIBXC is by now used by more than 20 codes, not only from the atomic, molecular, and solid-state physics, but also from the quantum chemistry communities.

  10. Antioxidant Properties of Kynurenines: Density Functional Theory Calculations

    Science.gov (United States)

    2016-01-01

    Kynurenines, the main products of tryptophan catabolism, possess both prooxidant and anioxidant effects. Having multiple neuroactive properties, kynurenines are implicated in the development of neurological and cognitive disorders, such as Alzheimer's, Parkinson's, and Huntington's diseases. Autoxidation of 3-hydroxykynurenine (3HOK) and its derivatives, 3-hydroxyanthranilic acid (3HAA) and xanthommatin (XAN), leads to the hyperproduction of reactive oxygen species (ROS) which damage cell structures. At the same time, 3HOK and 3HAA have been shown to be powerful ROS scavengers. Their ability to quench free radicals is believed to result from the presence of the aromatic hydroxyl group which is able to easily abstract an electron and H-atom. In this study, the redox properties for kynurenines and several natural and synthetic antioxidants have been calculated at different levels of density functional theory in the gas phase and water solution. Hydroxyl bond dissociation enthalpy (BDE) and ionization potential (IP) for 3HOK and 3HAA appear to be lower than for xanthurenic acid (XAA), several phenolic antioxidants, and ascorbic acid. BDE and IP for the compounds with aromatic hydroxyl group are lower than for their precursors without hydroxyl group. The reaction rate for H donation to *O-atom of phenoxyl radical (Ph-O*) and methyl peroxy radical (Met-OO*) decreases in the following rankings: 3HOK ~ 3HAA > XAAOXO > XAAENOL. The enthalpy absolute value for Met-OO* addition to the aromatic ring of the antioxidant radical increases in the following rankings: 3HAA* < 3HOK* < XAAOXO* < XAAENOL*. Thus, the high free radical scavenging activity of 3HAA and 3HOK can be explained by the easiness of H-atom abstraction and transfer to O-atom of the free radical, rather than by Met-OO* addition to the kynurenine radical. PMID:27861556

  11. Functional renormalization group and Kohn-Sham scheme in density functional theory

    Science.gov (United States)

    Liang, Haozhao; Niu, Yifei; Hatsuda, Tetsuo

    2018-04-01

    Deriving accurate energy density functional is one of the central problems in condensed matter physics, nuclear physics, and quantum chemistry. We propose a novel method to deduce the energy density functional by combining the idea of the functional renormalization group and the Kohn-Sham scheme in density functional theory. The key idea is to solve the renormalization group flow for the effective action decomposed into the mean-field part and the correlation part. Also, we propose a simple practical method to quantify the uncertainty associated with the truncation of the correlation part. By taking the φ4 theory in zero dimension as a benchmark, we demonstrate that our method shows extremely fast convergence to the exact result even for the highly strong coupling regime.

  12. Subsystem density functional theory with meta-generalized gradient approximation exchange-correlation functionals.

    Science.gov (United States)

    Śmiga, Szymon; Fabiano, Eduardo; Laricchia, Savio; Constantin, Lucian A; Della Sala, Fabio

    2015-04-21

    We analyze the methodology and the performance of subsystem density functional theory (DFT) with meta-generalized gradient approximation (meta-GGA) exchange-correlation functionals for non-bonded molecular systems. Meta-GGA functionals depend on the Kohn-Sham kinetic energy density (KED), which is not known as an explicit functional of the density. Therefore, they cannot be directly applied in subsystem DFT calculations. We propose a Laplacian-level approximation to the KED which overcomes this limitation and provides a simple and accurate way to apply meta-GGA exchange-correlation functionals in subsystem DFT calculations. The so obtained density and energy errors, with respect to the corresponding supermolecular calculations, are comparable with conventional approaches, depending almost exclusively on the approximations in the non-additive kinetic embedding term. An embedding energy error decomposition explains the accuracy of our method.

  13. Zinc surface complexes on birnessite: A density functional theory study

    Energy Technology Data Exchange (ETDEWEB)

    Kwon, Kideok D.; Refson, Keith; Sposito, Garrison

    2009-01-05

    Biogeochemical cycling of zinc is strongly influenced by sorption on birnessite minerals (layer-type MnO2), which are found in diverse terrestrial and aquatic environments. Zinc has been observed to form both tetrahedral (Zn{sup IV}) and octahedral (Zn{sup VI}) triple-corner-sharing surface complexes (TCS) at Mn(IV) vacancy sites in hexagonal birnessite. The octahedral complex is expected to be similar to that of Zn in the Mn oxide mineral, chalcophanite (ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O), but the reason for the occurrence of the four-coordinate Zn surface species remains unclear. We address this issue computationally using spin-polarized Density Functional Theory (DFT) to examine the Zn{sub IV}-TCS and Zn{sup VI}-TCS species. Structural parameters obtained by DFT geometry optimization were in excellent agreement with available experimental data on Zn-birnessites. Total energy, magnetic moments, and electron-overlap populations obtained by DFT for isolated Zn{sup IV}-TCS revealed that this species is stable in birnessite without a need for Mn(III) substitution in the octahedral sheet and that it is more effective in reducing undersaturation of surface O at a Mn vacancy than is Zn{sub VI}-TCS. Comparison between geometry-optimized ZnMn{sub 3}O{sub 7} {center_dot} 3H{sub 2}O (chalcophanite) and the hypothetical monohydrate mineral, ZnMn{sub 3}O{sub 7} {center_dot} H{sub 2}O, which contains only tetrahedral Zn, showed that the hydration state of Zn significantly affects birnessite structural stability. Finally, our study also revealed that, relative to their positions in an ideal vacancy-free MnO{sub 2}, Mn nearest to Zn in a TCS surface complex move toward the vacancy by 0.08-0.11 {angstrom}, while surface O bordering the vacancy move away from it by 0.16-0.21 {angstrom}, in agreement with recent X-ray absorption spectroscopic analyses.

  14. Density Functional Theory Modeling of Ferrihydrite Nanoparticle Adsorption Behavior

    Science.gov (United States)

    Kubicki, J.

    2016-12-01

    Ferrihydrite is a critical substrate for adsorption of oxyanion species in the environment1. The nanoparticulate nature of ferrihydrite is inherent to its formation, and hence it has been called a "nano-mineral"2. The nano-scale size and unusual composition of ferrihydrite has made structural determination of this phase problematic. Michel et al.3 have proposed an atomic structure for ferrihydrite, but this model has been controversial4,5. Recent work has shown that the Michel et al.3 model structure may be reasonably accurate despite some deficiencies6-8. An alternative model has been proposed by Manceau9. This work utilizes density functional theory (DFT) calculations to model both the structure of ferrihydrite nanoparticles based on the Michel et al. 3 model as refined in Hiemstra8 and the modified akdalaite model of Manceau9. Adsorption energies of carbonate, phosphate, sulfate, chromate, arsenite and arsenate are calculated. Periodic projector-augmented planewave calculations were performed with the Vienna Ab-initio Simulation Package (VASP10) on an approximately 1.7 nm diameter Michel nanoparticle (Fe38O112H110) and on a 2 nm Manceau nanoparticle (Fe38O95H76). After energy minimization of the surface H and O atoms. The model will be used to assess the possible configurations of adsorbed oxyanions on the model nanoparticles. Brown G.E. Jr. and Calas G. (2012) Geochemical Perspectives, 1, 483-742. Hochella M.F. and Madden A.S. (2005) Elements, 1, 199-203. Michel, F.M., Ehm, L., Antao, S.M., Lee, P.L., Chupas, P.J., Liu, G., Strongin, D.R., Schoonen, M.A.A., Phillips, B.L., and Parise, J.B., 2007, Science, 316, 1726-1729. Rancourt, D.G., and Meunier, J.F., 2008, American Mineralogist, 93, 1412-1417. Manceau, A., 2011, American Mineralogist, 96, 521-533. Maillot, F., Morin, G., Wang, Y., Bonnin, D., Ildefonse, P., Chaneac, C., Calas, G., 2011, Geochimica et Cosmochimica Acta, 75, 2708-2720. Pinney, N., Kubicki, J.D., Middlemiss, D.S., Grey, C.P., and Morgan, D

  15. Comparison of exact-exchange calculations for solids in current-spin-density- and spin-density-functional theory

    DEFF Research Database (Denmark)

    Sharma, S.; Pittalis, S.; Kurth, S.

    2007-01-01

    The relative merits of current-spin-density- and spin-density-functional theory are investigated for solids treated within the exact-exchange-only approximation. Spin-orbit splittings and orbital magnetic moments are determined at zero external magnetic field. We find that for magnetic (Fe, Co......, and Ni) and nonmagnetic (Si and Ge) solids, the exact-exchange current-spin-density functional approach does not significantly improve the accuracy of the corresponding spin-density functional results....

  16. A density functional theory study on redox reaction of uranium

    International Nuclear Information System (INIS)

    Toraishi, T.; Kawaguchi, M.; Tsuneda, T.; Tanaka, S.; Nagasaki, S.

    2005-01-01

    Full text of publication follows: Redox reactions are key issues for predicting the migration behavior of actinides in the geosphere, and therefore the chemical processes have to be profoundly understood. However, redox reactions basically involve several elemental processes, and in many cases only limited chemical information can be obtained experimentally. A theoretical approach gives further information which never can be obtained by experiments, such as precise thermodynamic data or reaction pathways of very rapid charge transfer reactions. For this reason, ab initio MO calculations have been applied in the last 5-6 years to the elucidation of redox processes in the U(VI)-Fe(II) or U(VI)-U(IV) system [1- 3]. Those studies provided extremely important chemical information. Nevertheless, the 'huge' calculation costs of ab initio MO techniques now interfere with the extension of the calculation to the 'real' size system: In order to deal with the practically important chemical reactions such as the reduction of actinides at solid surfaces, a large chemical system involving many atoms (electrons) has to be treated. Present ab initio MO techniques at CASSCF, CASPT2 or MRCI level, however, do not allow to handle such a large systems because of the high calculation costs. Density functional theory (DFT) calculations should be also feasible for such systems. Nevertheless, there are very few reports on redox processes of actinides calculated by DFT. This fact was based on the argument that DFT could not treat charge transfer phenomena accurately since the two-electron exchange integral term is not explicitly involved [1-3]. However this is no longer correct: the long-range corrected (LC) energy function was recently developed, and now the charge transfer reaction can safely be calculated by DFT [4]. In the present work, we employ the DFT technique to treat the reduction of U(VI) to U(V) by Fe(II) via the bi-nuclear complex system, and confirm the applicability of the

  17. Ionization Potentials of Chemical Warfare Agents and Related Compounds Determined with Density Functional Theory

    National Research Council Canada - National Science Library

    Wright, J

    2000-01-01

    ...) agents at contaminated sites. Reported herein are theoretical ionization potentials for CW agents and their related compounds calculated using density functional theory at the B3LYP/6-311+G(2d,p) level of theory...

  18. Solvation in atomic liquids: connection between Gaussian field theory and density functional theory

    Directory of Open Access Journals (Sweden)

    V. Sergiievskyi

    2017-12-01

    Full Text Available For the problem of molecular solvation, formulated as a liquid submitted to the external potential field created by a molecular solute of arbitrary shape dissolved in that solvent, we draw a connection between the Gaussian field theory derived by David Chandler [Phys. Rev. E, 1993, 48, 2898] and classical density functional theory. We show that Chandler's results concerning the solvation of a hard core of arbitrary shape can be recovered by either minimising a linearised HNC functional using an auxiliary Lagrange multiplier field to impose a vanishing density inside the core, or by minimising this functional directly outside the core — indeed a simpler procedure. Those equivalent approaches are compared to two other variants of DFT, either in the HNC, or partially linearised HNC approximation, for the solvation of a Lennard-Jones solute of increasing size in a Lennard-Jones solvent. Compared to Monte-Carlo simulations, all those theories give acceptable results for the inhomogeneous solvent structure, but are completely out-of-range for the solvation free-energies. This can be fixed in DFT by adding a hard-sphere bridge correction to the HNC functional.

  19. Local and linear chemical reactivity response functions at finite temperature in density functional theory

    International Nuclear Information System (INIS)

    Franco-Pérez, Marco; Ayers, Paul W.; Gázquez, José L.; Vela, Alberto

    2015-01-01

    We explore the local and nonlocal response functions of the grand canonical potential density functional at nonzero temperature. In analogy to the zero-temperature treatment, local (e.g., the average electron density and the local softness) and nonlocal (e.g., the softness kernel) intrinsic response functions are defined as partial derivatives of the grand canonical potential with respect to its thermodynamic variables (i.e., the chemical potential of the electron reservoir and the external potential generated by the atomic nuclei). To define the local and nonlocal response functions of the electron density (e.g., the Fukui function, the linear density response function, and the dual descriptor), we differentiate with respect to the average electron number and the external potential. The well-known mathematical relationships between the intrinsic response functions and the electron-density responses are generalized to nonzero temperature, and we prove that in the zero-temperature limit, our results recover well-known identities from the density functional theory of chemical reactivity. Specific working equations and numerical results are provided for the 3-state ensemble model

  20. Many-body theory and Energy Density Functionals

    Energy Technology Data Exchange (ETDEWEB)

    Baldo, M. [INFN, Catania (Italy)

    2016-07-15

    In this paper a method is first presented to construct an Energy Density Functional on a microscopic basis. The approach is based on the Kohn-Sham method, where one introduces explicitly the Nuclear Matter Equation of State, which can be obtained by an accurate many-body calculation. In this way it connects the functional to the bare nucleon-nucleon interaction. It is shown that the resulting functional can be performing as the best Gogny force functional. In the second part of the paper it is shown how one can go beyond the mean-field level and the difficulty that can appear. The method is based on the particle-vibration coupling scheme and a formalism is presented that can handle the correct use of the vibrational degrees of freedom within a microscopic approach. (orig.)

  1. Density functional theory: Its origins, rise to prominence, and future

    Science.gov (United States)

    Jones, R. O.

    2015-07-01

    In little more than 20 years, the number of applications of the density functional (DF) formalism in chemistry and materials science has grown in an astonishing fashion. The number of publications alone shows that DF calculations make up a huge success story, and many younger colleagues are surprised to learn that the widespread application of density functional methods, particularly in chemistry, began only after 1990. This is indeed unexpected, because the origins are usually traced to the papers of Hohenberg, Kohn, and Sham more than a quarter of a century earlier. The DF formalism, its applications, and prospects were reviewed for this journal in 1989. About the same time, the combination of DF calculations with molecular dynamics promised to provide an efficient way to study structures and reactions in molecules and extended systems. This paper reviews the development of density-related methods back to the early years of quantum mechanics and follows the breakthrough in their application after 1990. The two examples from biochemistry and materials science are among the many current applications that were simply far beyond expectations in 1990. The reasons why—50 years after its modern formulation and after two decades of rapid expansion—some of the most cited practitioners in the field are concerned about its future are discussed.

  2. Density functional theory of the electrical double layer: the RFD functional

    International Nuclear Information System (INIS)

    Gillespie, Dirk; Valisko, Monika; Boda, Dezso

    2005-01-01

    Density functional theory (DFT) of electrolytes is applied to the electrical double layer under a wide range of conditions. The ions are charged, hard spheres of different size and valence, and the wall creating the double layer is uncharged, weakly charged, and strongly charged. Under all conditions, the density and electrostatic potential profiles calculated using the recently proposed RFD electrostatic functional (Gillespie et al 2002 J. Phys.: Condens. Matter 14 12129; 2003 Phys. Rev. E 68 031503) compare well to Monte Carlo simulations. When the wall is strongly charged, the RFD functional results agree with the results of a simpler perturbative electrostatic DFT, but the two functionals' results qualitatively disagree when the wall is uncharged or weakly charged. The RFD functional reproduces these phenomena of weakly charged double layers. It also reproduces bulk thermodynamic quantities calculated from pair correlation functions

  3. Microscopic aspects of wetting using classical density functional theory

    Science.gov (United States)

    Yatsyshin, P.; Durán-Olivencia, M.-A.; Kalliadasis, S.

    2018-07-01

    Wetting is a rather efficient mechanism for nucleation of a phase (typically liquid) on the interface between two other phases (typically solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid–fluid and fluid–substrate intermolecular interactions brings about an entire ‘zoo’ of possible fluid configurations, such as liquid films with a thickness of a few nanometers, liquid nanodrops and liquid bridges. These fluid configurations are often associated with phase transitions occurring at the solid–gas interface and at lengths of just several molecular diameters away from the substrate. In this special issue article, we demonstrate how a fully microscopic classical density-functional framework can be applied to the efficient, rational and systematic exploration of the rich phase space of wetting phenomena. We consider a number of model prototype systems such as wetting on a planar wall, a chemically patterned wall and a wedge. Through density-functional computations we demonstrate that for these simply structured substrates the behaviour of the solid–gas interface is already highly complex and non-trivial.

  4. Ground-state densities from the Rayleigh-Ritz variation principle and from density-functional theory.

    Science.gov (United States)

    Kvaal, Simen; Helgaker, Trygve

    2015-11-14

    The relationship between the densities of ground-state wave functions (i.e., the minimizers of the Rayleigh-Ritz variation principle) and the ground-state densities in density-functional theory (i.e., the minimizers of the Hohenberg-Kohn variation principle) is studied within the framework of convex conjugation, in a generic setting covering molecular systems, solid-state systems, and more. Having introduced admissible density functionals as functionals that produce the exact ground-state energy for a given external potential by minimizing over densities in the Hohenberg-Kohn variation principle, necessary and sufficient conditions on such functionals are established to ensure that the Rayleigh-Ritz ground-state densities and the Hohenberg-Kohn ground-state densities are identical. We apply the results to molecular systems in the Born-Oppenheimer approximation. For any given potential v ∈ L(3/2)(ℝ(3)) + L(∞)(ℝ(3)), we establish a one-to-one correspondence between the mixed ground-state densities of the Rayleigh-Ritz variation principle and the mixed ground-state densities of the Hohenberg-Kohn variation principle when the Lieb density-matrix constrained-search universal density functional is taken as the admissible functional. A similar one-to-one correspondence is established between the pure ground-state densities of the Rayleigh-Ritz variation principle and the pure ground-state densities obtained using the Hohenberg-Kohn variation principle with the Levy-Lieb pure-state constrained-search functional. In other words, all physical ground-state densities (pure or mixed) are recovered with these functionals and no false densities (i.e., minimizing densities that are not physical) exist. The importance of topology (i.e., choice of Banach space of densities and potentials) is emphasized and illustrated. The relevance of these results for current-density-functional theory is examined.

  5. Density Functional Theory (DFT Study of Edaravone Derivatives as Antioxidants

    Directory of Open Access Journals (Sweden)

    Walace G. Leal

    2012-06-01

    Full Text Available Quantum chemical calculations at the B3LYP/6–31G* level of theory were employed for the structure-activity relationship and prediction of the antioxidant activity of edaravone and structurally related derivatives using energy (E, ionization potential (IP, bond dissociation energy (BDE, and stabilization energies (∆Eiso. Spin density calculations were also performed for the proposed antioxidant activity mechanism. The electron abstraction is related to electron-donating groups (EDG at position 3, decreasing the IP when compared to substitution at position 4. The hydrogen abstraction is related to electron-withdrawing groups (EDG at position 4, decreasing the BDECH when compared to other substitutions, resulting in a better antioxidant activity. The unpaired electron formed by the hydrogen abstraction from the C–H group of the pyrazole ring is localized at 2, 4, and 6 positions. The highest scavenging activity prediction is related to the lowest contribution at the carbon atom. The likely mechanism is related to hydrogen transfer. It was found that antioxidant activity depends on the presence of EDG at the C2 and C4 positions and there is a correlation between IP and BDE. Our results identified three different classes of new derivatives more potent than edaravone.

  6. The problem of the universal density functional and the density matrix functional theory

    NARCIS (Netherlands)

    Bobrov, V.B.; Trigger, S.A.

    2013-01-01

    The analysis in this paper shows that the Hohenberg-Kohn theorem is the constellation of two statements: (i) the mathematically rigorous Hohenberg-Kohn lemma, which demonstrates that the same ground-state density cannot correspond to two different potentials of an external field, and (ii) the

  7. Antisites in III-V semiconductors: Density functional theory calculations

    KAUST Repository

    Chroneos, A.

    2014-07-14

    Density functional based simulation, corrected for finite size effects, is used to investigate systematically the formation of antisite defects in III-V semiconductors (III=Al, Ga, and In and V=P, As, and Sb). Different charge states are modelled as a function of the Fermi level and under different growth conditions. The formation energies of group III antisites (III V q) decrease with increasing covalent radius of the group V atom though not group III radius, whereas group V antisites (V I I I q) show a consistent decrease in formation energies with increase in group III and group V covalent radii. In general, III V q defects dominate under III-rich conditions and V I I I q under V-rich conditions. Comparison with equivalent vacancy formation energy simulations shows that while antisite concentrations are always dominant under stoichiometric conditions, modest variation in growth or doping conditions can lead to a significantly higher concentration of vacancies. © 2014 AIP Publishing LLC.

  8. The QTP family of consistent functionals and potentials in Kohn-Sham density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Jin, Yifan; Bartlett, Rodney J., E-mail: bartlett@qtp.ufl.edu [Quantum Theory Project and Departments of Chemistry and Physics, University of Florida, Gainesville, Florida 32611 (United States)

    2016-07-21

    This manuscript presents the second, consistent density functional in the QTP (Quantum Theory Project) family, that is, the CAM-QTP(01). It is a new range-separated exchange-correlation functional in which the non-local exchange contribution is 100% at large separation. It follows the same basic principles of this family that the Kohn-Sham eigenvalues of the occupied orbitals approximately equal the vertical ionization energies, which is not fulfilled by most of the traditional density functional methods. This new CAM-QTP(01) functional significantly improves the accuracy of the vertical excitation energies especially for the Rydberg states in the test set. It also reproduces many other properties such as geometries, reaction barrier heights, and atomization energies.

  9. Multiconfiguration pair-density functional theory: barrier heights and main group and transition metal energetics.

    Science.gov (United States)

    Carlson, Rebecca K; Li Manni, Giovanni; Sonnenberger, Andrew L; Truhlar, Donald G; Gagliardi, Laura

    2015-01-13

    Kohn-Sham density functional theory, resting on the representation of the electronic density and kinetic energy by a single Slater determinant, has revolutionized chemistry, but for open-shell systems, the Kohn-Sham Slater determinant has the wrong symmetry properties as compared to an accurate wave function. We have recently proposed a theory, called multiconfiguration pair-density functional theory (MC-PDFT), in which the electronic kinetic energy and classical Coulomb energy are calculated from a multiconfiguration wave function with the correct symmetry properties, and the rest of the energy is calculated from a density functional, called the on-top density functional, that depends on the density and the on-top pair density calculated from this wave function. We also proposed a simple way to approximate the on-top density functional by translation of Kohn-Sham exchange-correlation functionals. The method is much less expensive than other post-SCF methods for calculating the dynamical correlation energy starting with a multiconfiguration self-consistent-field wave function as the reference wave function, and initial tests of the theory were quite encouraging. Here, we provide a broader test of the theory by applying it to bond energies of main-group molecules and transition metal complexes, barrier heights and reaction energies for diverse chemical reactions, proton affinities, and the water dimerization energy. Averaged over 56 data points, the mean unsigned error is 3.2 kcal/mol for MC-PDFT, as compared to 6.9 kcal/mol for Kohn-Sham theory with a comparable density functional. MC-PDFT is more accurate on average than complete active space second-order perturbation theory (CASPT2) for main-group small-molecule bond energies, alkyl bond dissociation energies, transition-metal-ligand bond energies, proton affinities, and the water dimerization energy.

  10. Vibrational Spectroscopic Studies of Tenofovir Using Density Functional Theory Method

    Directory of Open Access Journals (Sweden)

    G. R. Ramkumaar

    2013-01-01

    Full Text Available A systematic vibrational spectroscopic assignment and analysis of tenofovir has been carried out by using FTIR and FT-Raman spectral data. The vibrational analysis was aided by electronic structure calculations—hybrid density functional methods (B3LYP/6-311++G(d,p, B3LYP/6-31G(d,p, and B3PW91/6-31G(d,p. Molecular equilibrium geometries, electronic energies, IR intensities, and harmonic vibrational frequencies have been computed. The assignments proposed based on the experimental IR and Raman spectra have been reviewed and complete assignment of the observed spectra have been proposed. UV-visible spectrum of the compound was also recorded and the electronic properties such as HOMO and LUMO energies and were determined by time-dependent DFT (TD-DFT method. The geometrical, thermodynamical parameters, and absorption wavelengths were compared with the experimental data. The B3LYP/6-311++G(d,p-, B3LYP/6-31G(d,p-, and B3PW91/6-31G(d,p-based NMR calculation procedure was also done. It was used to assign the 13C and 1H NMR chemical shift of tenofovir.

  11. Current Density Functional Theory Using Meta-Generalized Gradient Exchange-Correlation Functionals.

    Science.gov (United States)

    Furness, James W; Verbeke, Joachim; Tellgren, Erik I; Stopkowicz, Stella; Ekström, Ulf; Helgaker, Trygve; Teale, Andrew M

    2015-09-08

    We present the self-consistent implementation of current-dependent (hybrid) meta-generalized gradient approximation (mGGA) density functionals using London atomic orbitals. A previously proposed generalized kinetic energy density is utilized to implement mGGAs in the framework of Kohn-Sham current density functional theory (KS-CDFT). A unique feature of the nonperturbative implementation of these functionals is the ability to seamlessly explore a wide range of magnetic fields up to 1 au (∼235 kT) in strength. CDFT functionals based on the TPSS and B98 forms are investigated, and their performance is assessed by comparison with accurate coupled-cluster singles, doubles, and perturbative triples (CCSD(T)) data. In the weak field regime, magnetic properties such as magnetizabilities and nuclear magnetic resonance shielding constants show modest but systematic improvements over generalized gradient approximations (GGA). However, in the strong field regime, the mGGA-based forms lead to a significantly improved description of the recently proposed perpendicular paramagnetic bonding mechanism, comparing well with CCSD(T) data. In contrast to functionals based on the vorticity, these forms are found to be numerically stable, and their accuracy at high field suggests that the extension of mGGAs to CDFT via the generalized kinetic energy density should provide a useful starting point for further development of CDFT approximations.

  12. Approximate self-consistent potentials for density-functional-theory exchange-correlation functionals

    International Nuclear Information System (INIS)

    Cafiero, Mauricio; Gonzalez, Carlos

    2005-01-01

    We show that potentials for exchange-correlation functionals within the Kohn-Sham density-functional-theory framework may be written as potentials for simpler functionals multiplied by a factor close to unity, and in a self-consistent field calculation, these effective potentials find the correct self-consistent solutions. This simple theory is demonstrated with self-consistent exchange-only calculations of the atomization energies of some small molecules using the Perdew-Kurth-Zupan-Blaha (PKZB) meta-generalized-gradient-approximation (meta-GGA) exchange functional. The atomization energies obtained with our method agree with or surpass previous meta-GGA calculations performed in a non-self-consistent manner. The results of this work suggest the utility of this simple theory to approximate exchange-correlation potentials corresponding to energy functionals too complicated to generate closed forms for their potentials. We hope that this method will encourage the development of complex functionals which have correct boundary conditions and are free of self-interaction errors without the worry that the functionals are too complex to differentiate to obtain potentials

  13. Tuning electronic properties in graphene quantum dots by chemical functionalization: Density functional theory calculations

    Science.gov (United States)

    Abdelsalam, Hazem; Elhaes, Hanan; Ibrahim, Medhat A.

    2018-03-01

    The energy gap and dipole moment of chemically functionalized graphene quantum dots are investigated by density functional theory. The energy gap can be tuned through edge passivation by different elements or groups. Edge passivation by oxygen considerably decreases the energy gap in hexagonal nanodots. Edge states in triangular quantum dots can also be manipulated by passivation with fluorine. The dipole moment depends on: (a) shape and edge termination of the quantum dot, (b) attached group, and (c) position to which the groups are attached. Depending on the position of attached groups, the total dipole can be increased, decreased, or eliminated.

  14. The spin polarized linear response from density functional theory: Theory and application to atoms

    Energy Technology Data Exchange (ETDEWEB)

    Fias, Stijn, E-mail: sfias@vub.ac.be; Boisdenghien, Zino; De Proft, Frank; Geerlings, Paul [General Chemistry (ALGC), Vrije Universiteit Brussel (Free University Brussels – VUB), Pleinlaan 2, 1050 Brussels (Belgium)

    2014-11-14

    Within the context of spin polarized conceptual density functional theory, the spin polarized linear response functions are introduced both in the [N, N{sub s}] and [N{sub α}, N{sub β}] representations. The mathematical relations between the spin polarized linear response functions in both representations are examined and an analytical expression for the spin polarized linear response functions in the [N{sub α}, N{sub β}] representation is derived. The spin polarized linear response functions were calculated for all atoms up to and including argon. To simplify the plotting of our results, we integrated χ(r, r′) to a quantity χ(r, r{sup ′}), circumventing the θ and ϕ dependence. This allows us to plot and to investigate the periodicity throughout the first three rows in the periodic table within the two different representations. For the first time, χ{sub αβ}(r, r{sup ′}), χ{sub βα}(r, r{sup ′}), and χ{sub SS}(r, r{sup ′}) plots have been calculated and discussed. By integration of the spin polarized linear response functions, different components to the polarisability, α{sub αα}, α{sub αβ}, α{sub βα}, and α{sub ββ} have been calculated.

  15. Energy landscapes of nucleophilic substitution reactions: a comparison of density functional theory and coupled cluster methods

    NARCIS (Netherlands)

    Swart, M.; Sola, M.; Bickelhaupt, F.M.

    2007-01-01

    We have carried out a detailed evaluation of the performance of all classes of density functional theory (DFT) for describing the potential energy surface (PES) of a wide range of nucleophilic substitution (S

  16. Conjugation-promoted reaction of open-cage fullerene: A density functional theory study

    KAUST Repository

    Guo, Yong; Yan, Jingjing; Khashab, Niveen M.

    2012-01-01

    Density functional theory calculations are performed to study the addition mechanism of e-rich moieties such as triethyl phosphite to a carbonyl group on the rim of a fullerene orifice. Three possible reaction channels have been investigated

  17. Time dependent – density functional theory characterization of organic dyes for dye-sensitized solar cells

    KAUST Repository

    Hilal, Rifaat; Aziz, Saadullah G.; Osman, Osman I.; Bredas, Jean-Luc

    2017-01-01

    We aim at providing better insight into the parameters that govern the intramolecular charge transfer (ICT) and photo-injection processes in dyes for dye-sensitised solar cells (DSSC). Density functional theory (DFT) and time-dependent DFT (TD

  18. Time-dependent density functional theory for multi-component systems

    International Nuclear Information System (INIS)

    Tiecheng Li; Peiqing Tong

    1985-10-01

    The Runge-Gross version of Hohenberg-Kohn-Sham's density functional theory is generalized to multi-component systems, both for arbitrary time-dependent pure states and for arbitrary time-dependent ensembles. (author)

  19. G-centers in irradiated silicon revisited: A screened hybrid density functional theory approach

    KAUST Repository

    Wang, H.; Chroneos, A.; Londos, C. A.; Sgourou, E. N.; Schwingenschlö gl, Udo

    2014-01-01

    Electronic structure calculations employing screened hybrid density functional theory are used to gain fundamental insight into the interaction of carbon interstitial (Ci) and substitutional (Cs) atoms forming the CiCs defect known as G

  20. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben; Zhu, Zhiyong; Al-Kassab, Talaat; Schwingenschlö gl, Udo

    2012-01-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations

  1. Optical properties of Al nanostructures from time dependent density functional theory

    KAUST Repository

    Mokkath, Junais Habeeb; Schwingenschlö gl, Udo

    2016-01-01

    The optical properties of Al nanostructures are investigated by means of time dependent density functional theory, considering chains of varying length and ladders/stripes of varying aspect ratio. The absorption spectra show redshifting

  2. Discontinuities of Green functions in field theory at finite temperature and density

    International Nuclear Information System (INIS)

    Kobes, R.L.; Semenoff, G.W.

    1985-01-01

    We derive systematic rules for calculating the imaginary parts of Minkowski space Green functions in quantum field theory at finite temperature and density. Self-energy corrections are used as an example of the application of these rules. (orig.)

  3. Patching the Exchange-Correlation Potential in Density Functional Theory.

    Science.gov (United States)

    Huang, Chen

    2016-05-10

    A method for directly patching exchange-correlation (XC) potentials in materials is derived. The electron density of a system is partitioned into subsystem densities by dividing its Kohn-Sham (KS) potential among the subsystems. Inside each subsystem, its projected KS potential is required to become the total system's KS potential. This requirement, together with the nearsightedness principle of electronic matters, ensures that the electronic structures inside subsystems can be good approximations to the total system's electronic structure. The nearsightedness principle also ensures that subsystem densities could be well localized in their regions, making it possible to use high-level methods to invert the XC potentials for subsystem densities. Two XC patching methods are developed. In the local XC patching method, the total system's XC potential is improved in the cluster region. We show that the coupling between a cluster and its environment is important for achieving a fast convergence of the electronic structure in the cluster region. In the global XC patching method, we discuss how to patch the subsystem XC potentials to construct the XC potential in the total system, aiming to scale up high-level quantum mechanics simulations of materials. Proof-of-principle examples are given.

  4. Density functional theory study of structure, electronic and magnetic ...

    Indian Academy of Sciences (India)

    ABHIJIT DUTTA

    2018-01-30

    Jan 30, 2018 ... magnetic properties of non-metal (Group 13) doped stable. Rhn(n = 2−8) ... Deformed electron density was found to be higher in the case of Rh5B, Rh4Al, Rh7Al and ...... systems: Modeling of surface alloys and alloy surfaces.

  5. Density functional theory in surface chemistry and catalysis

    DEFF Research Database (Denmark)

    Nørskov, Jens Kehlet; Abild-Pedersen, Frank; Studt, Felix

    2011-01-01

    Recent advances in the understanding of reactivity trends for chemistry at transition-metal surfaces have enabled in silico design of heterogeneous catalysts in a few cases. The current status of the field is discussed with an emphasis on the role of coupling theory and experiment and future...

  6. Performance of density functional theory methods to describe ...

    Indian Academy of Sciences (India)

    Fukui function shows a small dependence with both the exchange and correlation functional and the basis set. Evolution of the Fukui function along the reaction path describes important changes in the basic sites of the corresponding molecules. These results are in agreement with the chemical behavior of those species.

  7. Towards a Density Functional Theory Exchange-Correlation Functional able to describe localization/delocalization

    Science.gov (United States)

    Mattsson, Ann E.; Wills, John M.

    2013-03-01

    The inability to computationally describe the physics governing the properties of actinides and their alloys is the poster child of failure of existing Density Functional Theory exchange-correlation functionals. The intricate competition between localization and delocalization of the electrons, present in these materials, exposes the limitations of functionals only designed to properly describe one or the other situation. We will discuss the manifestation of this competition in real materials and propositions on how to construct a functional able to accurately describe properties of these materials. I addition we will discuss both the importance of using the Dirac equation to describe the relativistic effects in these materials, and the connection to the physics of transition metal oxides. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  8. Existence of time-dependent density-functional theory for open electronic systems: time-dependent holographic electron density theorem.

    Science.gov (United States)

    Zheng, Xiao; Yam, ChiYung; Wang, Fan; Chen, GuanHua

    2011-08-28

    We present the time-dependent holographic electron density theorem (TD-HEDT), which lays the foundation of time-dependent density-functional theory (TDDFT) for open electronic systems. For any finite electronic system, the TD-HEDT formally establishes a one-to-one correspondence between the electron density inside any finite subsystem and the time-dependent external potential. As a result, any electronic property of an open system in principle can be determined uniquely by the electron density function inside the open region. Implications of the TD-HEDT on the practicality of TDDFT are also discussed.

  9. Local thermodynamic mapping for effective liquid density-functional theory

    Science.gov (United States)

    Kyrlidis, Agathagelos; Brown, Robert A.

    1992-01-01

    The structural-mapping approximation introduced by Lutsko and Baus (1990) in the generalized effective-liquid approximation is extended to include a local thermodynamic mapping based on a spatially dependent effective density for approximating the solid phase in terms of the uniform liquid. This latter approximation, called the local generalized effective-liquid approximation (LGELA) yields excellent predictions for the free energy of hard-sphere solids and for the conditions of coexistence of a hard-sphere fcc solid with a liquid. Moreover, the predicted free energy remains single valued for calculations with more loosely packed crystalline structures, such as the diamond lattice. The spatial dependence of the weighted density makes the LGELA useful in the study of inhomogeneous solids.

  10. A density functional theory study of new boron nanotubes

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Zhao-Hua [Shijiazhuang Institute of Technology, Shijiazhuang (China); Xie, Zun [Hebei Normal Univ., Shijiazhuang (China). College of Physics Science and Information Engineering and Hebei Advanced Thin Films Lab.

    2017-07-01

    Using first-principles calculations, a series of new boron nanotubes (BNTs), which show various electronic properties, were theoretically predicted. Stable nanotubes with various chiral vectors and diameters can be formed by rolling up the boron sheet with relative stability [H. Tang and S. I. Beigi, Phys. Rev. B 82, 115412 (2010).]. By increasing the diameter for BNT, the stability is enhanced. The calculated density of states and band structures demonstrate that all the predicted BNTs are metallic, regardless of their diameter and chirality. The multicentre chemical bonds of the relatively stable boron sheet and BNTs are analysed using the deformation electron density. Within our study, the BNTs all have metallic conductive characteristics, in addition to having a low effective quality and high carrier concentration, which are very good nanoconductive material properties and could be combined to form high-power electrodes for lithium-ion batteries such as those used in many modern electronics.

  11. Energy expressions in density-functional theory using line integrals.

    NARCIS (Netherlands)

    van Leeuwen, R.; Baerends, E.J.

    1995-01-01

    In this paper we will address the question of how to obtain energies from functionals when only the functional derivative is given. It is shown that one can obtain explicit expressions for the exchange-correlation energy from approximate exchange-correlation potentials using line integrals along

  12. Diverse carrier mobility of monolayer BNCx: A combined density functional theory and Boltzmann transport theory study.

    Science.gov (United States)

    Wu, Tao; Deng, Kaiming; Deng, Wei-Qiao; Lu, Ruifeng

    2017-09-19

    BNCX monolayer as a kind of two-dimensional material has numerous chemical atomic ratios and arrangements with different electronic structures. Via calculations on the basis of density functional theory and Boltzmann transport theory under deformation potential approximation, the band structures and carrier mobilities of BNCX (x=1,2,3,4) nanosheets are systematically investigated. The calculated results show that BNC2-1 is a material with very small band gap (0.02 eV) among all the structures while other BNCX monolayers are semiconductors with band gap ranging from 0.51 to 1.32 eV. The carrier mobility of BNCX varies considerably from tens to millions of cm2 V-1 s-1. For BNC2-1, the hole mobility and electron mobility along both x and y directions can reach 105 orders of magnitude, which is similar to the carrier mobility of graphene. Besides, all studied BNCX monolayers obviously have anisotropic hole mobility and electron mobility. In particular, for semiconductor BNC4, its hole mobility along y direction and electron mobility along x direction unexpectedly reach 106 orders of magnitude, even higher than that of graphene. Our findings suggest that BNCX layered materials with proper ratio and arrangement of carbon atoms will possess desirable charge transport properties, exhibiting potential applications in nanoelectronic devices. © 2017 IOP Publishing Ltd.

  13. Density-functional theory in one dimension for contact-interacting fermions

    International Nuclear Information System (INIS)

    Magyar, R.J.; Burke, K.

    2004-01-01

    A density-functional theory is developed for fermions in one dimension, interacting via a δ function. Such systems provide a natural testing ground for questions of principle, as the local-density approximation should be highly accurate since for this interaction type the exchange contribution to the local-density approximation is intrinsically self-interaction-free. The exact-exchange contribution to the total energy is a local functional of the density. A local-density approximation for correlation is obtained using perturbation theory and Bethe ansatz results for the one-dimensional contact-interacting uniform Fermi gas. The ground-state energies are calculated for two finite systems, the analogs of helium and of Hooke's atom. The local-density approximation is shown to be excellent as expected

  14. Antisites in III-V semiconductors: Density functional theory calculations

    KAUST Repository

    Chroneos, A.; Tahini, Hassan Ali; Schwingenschlö gl, Udo; Grimes, R. W.

    2014-01-01

    as a function of the Fermi level and under different growth conditions. The formation energies of group III antisites (III V q) decrease with increasing covalent radius of the group V atom though not group III radius, whereas group V antisites (V I I I

  15. Density functional theory studies of screw dislocation core structures in bcc metals

    DEFF Research Database (Denmark)

    Frederiksen, Søren Lund; Jacobsen, Karsten Wedel

    2003-01-01

    The core structures of (I 11) screw dislocations in bee metals are studied using density functional theory in the local-density approximation. For Mo and Fe, direct calculations of the core structures show the cores to be symmetric with respect to 180degrees rotations around an axis perpendicular...... to symmetric core structures for all the studied metals....

  16. Introduction to Density Functional Theory: Calculations by Hand on the Helium Atom

    Science.gov (United States)

    Baseden, Kyle A.; Tye, Jesse W.

    2014-01-01

    Density functional theory (DFT) is a type of electronic structure calculation that has rapidly gained popularity. In this article, we provide a step-by-step demonstration of a DFT calculation by hand on the helium atom using Slater's X-Alpha exchange functional on a single Gaussian-type orbital to represent the atomic wave function. This DFT…

  17. Theoretical investigation of cyromazine tautomerism using density functional theory and Møller–Plesset perturbation theory methods

    Science.gov (United States)

    A computational chemistry analysis of six unique tautomers of cyromazine, a pesticide used for fly control, was performed with density functional theory (DFT) and canonical second order Møller–Plesset perturbation theory (MP2) methods to gain insight into the contributions of molecular structure to ...

  18. Electrocatalytic Activity and Selectivity - a Density Functional Theory Study

    DEFF Research Database (Denmark)

    Karamad, Mohammadreza

    -catalysts towards two appealing electrochemical reactions: 1)electroreduction of CO2 to hydrocarbons and alcohols, and 2) electrochemical production of hydrogen peroxide, i.e. H2O2, from its elements i.e. H2 and O2. The thesis is divided into three parts: In the first part, electro-catalytic activity of different...... metallic and functionalized graphene catalysts. Secondly, we considered CO2 reduction on RuO2, which has a distinctive catalytic activity and selectivity compared to Cu to get insight into mechanistic pathway of the CO2 reduction. Finally, in the last part, we have taken advantage of the isolated active...

  19. Isomers of Cu6 cluster: a density function theory study

    International Nuclear Information System (INIS)

    Jia Yanhui; Wang Shanshan; Li Gongping

    2008-01-01

    The possible structure of Cu 6 cluster has been given with the GaussView that is a graphical user interface software. The structure optimization was performed on the B3LYP functional and SDD basic set of the quantum computational software of Gaussian03. And eight isomers of Cu 6 cluster were calculated. The binding energy and the structure of eight isomers have been investigated in detail. The result showed that the value of the binding energy was in reasonable agreement with available experimental data, as well as with other theoretical results, and the most stable structure was the triangle of plane. Three new isomers of the Cu 6 cluster have been got in our work, which would be the valuable data for the further theoretical and experimental study. (authors)

  20. Time-dependent density functional theory for many-electron systems interacting with cavity photons.

    Science.gov (United States)

    Tokatly, I V

    2013-06-07

    Time-dependent (current) density functional theory for many-electron systems strongly coupled to quantized electromagnetic modes of a microcavity is proposed. It is shown that the electron-photon wave function is a unique functional of the electronic (current) density and the expectation values of photonic coordinates. The Kohn-Sham system is constructed, which allows us to calculate the above basic variables by solving self-consistent equations for noninteracting particles. We suggest possible approximations for the exchange-correlation potentials and discuss implications of this approach for the theory of open quantum systems. In particular we show that it naturally leads to time-dependent density functional theory for systems coupled to the Caldeira-Leggett bath.

  1. Many-body perturbation theory using the density-functional concept: beyond the GW approximation.

    Science.gov (United States)

    Bruneval, Fabien; Sottile, Francesco; Olevano, Valerio; Del Sole, Rodolfo; Reining, Lucia

    2005-05-13

    We propose an alternative formulation of many-body perturbation theory that uses the density-functional concept. Instead of the usual four-point integral equation for the polarizability, we obtain a two-point one, which leads to excellent optical absorption and energy-loss spectra. The corresponding three-point vertex function and self-energy are then simply calculated via an integration, for any level of approximation. Moreover, we show the direct impact of this formulation on the time-dependent density-functional theory. Numerical results for the band gap of bulk silicon and solid argon illustrate corrections beyond the GW approximation for the self-energy.

  2. Multiconfiguration Pair-Density Functional Theory Is Free From Delocalization Error.

    Science.gov (United States)

    Bao, Junwei Lucas; Wang, Ying; He, Xiao; Gagliardi, Laura; Truhlar, Donald G

    2017-11-16

    Delocalization error has been singled out by Yang and co-workers as the dominant error in Kohn-Sham density functional theory (KS-DFT) with conventional approximate functionals. In this Letter, by computing the vertical first ionization energy for well separated He clusters, we show that multiconfiguration pair-density functional theory (MC-PDFT) is free from delocalization error. To put MC-PDFT in perspective, we also compare it with some Kohn-Sham density functionals, including both traditional and modern functionals. Whereas large delocalization errors are almost universal in KS-DFT (the only exception being the very recent corrected functionals of Yang and co-workers), delocalization error is removed by MC-PDFT, which bodes well for its future as a step forward from KS-DFT.

  3. Semiclassical neutral atom as a reference system in density functional theory.

    Science.gov (United States)

    Constantin, Lucian A; Fabiano, E; Laricchia, S; Della Sala, F

    2011-05-06

    We use the asymptotic expansions of the semiclassical neutral atom as a reference system in density functional theory to construct accurate generalized gradient approximations (GGAs) for the exchange-correlation and kinetic energies without any empiricism. These asymptotic functionals are among the most accurate GGAs for molecular systems, perform well for solid state, and overcome current GGA state of the art in frozen density embedding calculations. Our results also provide evidence for the conjointness conjecture between exchange and kinetic energies of atomic systems.

  4. Reducing Systematic Errors in Oxide Species with Density Functional Theory Calculations

    DEFF Research Database (Denmark)

    Christensen, Rune; Hummelshøj, Jens S.; Hansen, Heine Anton

    2015-01-01

    Density functional theory calculations can be used to gain valuable insight into the fundamental reaction processes in metal−oxygen systems, e.g., metal−oxygen batteries. Here, the ability of a range of different exchange-correlation functionals to reproduce experimental enthalpies of formation...

  5. On the universality of the long-/short-range separation in multiconfigurational density-functional theory

    DEFF Research Database (Denmark)

    Fromager, Emmanuel; Toulouse, Julien; Jensen, Hans Jørgen Aagaard

    2007-01-01

    In many cases, the dynamic correlation can be calculated quite accurately and at a fairly low computational cost in Kohn-Sham density-functional theory (KS-DFT), using current standard approximate functionals. However, in general, KS-DFT does not treat static correlation effects (near degeneracy...

  6. International Workshop on Electronic Density Functional Theory : Recent Progress and New Directions

    CERN Document Server

    Vignale, Giovanni; Das, Mukunda

    1998-01-01

    This book is an outcome of the International Workshop on Electronic Density Functional Theory, held at Griffith University in Brisbane, Australia, in July 1996. Density functional theory, standing as it does at the boundary between the disciplines of physics, chemistry, and materials science, is a great mixer. Invited experts from North America, Europe, and Australia mingled with students from several disciplines, rapidly taking up the informal style for which Australia is famous. A list of participants is given at the end of the book. Density functional theory (DFT) is a subtle approach to the very difficult problem of predicting the behavior of many interacting particles. A major application is the study of many-electron systems. This was the workshop theme, embracing inter alia computational chemistry and condensed matter physics. DFT circumvents the more conceptually straightforward (but more computationally intensive) approach in which one solves the many-body Schrodinger equation. It relies instead on r...

  7. Source-Free Exchange-Correlation Magnetic Fields in Density Functional Theory.

    Science.gov (United States)

    Sharma, S; Gross, E K U; Sanna, A; Dewhurst, J K

    2018-03-13

    Spin-dependent exchange-correlation energy functionals in use today depend on the charge density and the magnetization density: E xc [ρ, m]. However, it is also correct to define the functional in terms of the curl of m for physical external fields: E xc [ρ,∇ × m]. The exchange-correlation magnetic field, B xc , then becomes source-free. We study this variation of the theory by uniquely removing the source term from local and generalized gradient approximations to the functional. By doing so, the total Kohn-Sham moments are improved for a wide range of materials for both functionals. Significantly, the moments for the pnictides are now in good agreement with experiment. This source-free method is simple to implement in all existing density functional theory codes.

  8. Electronic states of aryl radical functionalized graphenes: Density functional theory study

    Science.gov (United States)

    Tachikawa, Hiroto; Kawabata, Hiroshi

    2016-06-01

    Functionalized graphenes are known as a high-performance molecular device. In the present study, the structures and electronic states of the aryl radical functionalized graphene have been investigated by the density functional theory (DFT) method to elucidate the effects of functionalization on the electronic states of graphene (GR). Also, the mechanism of aryl radical reaction with GR was investigated. The benzene, biphenyl, p-terphenyl, and p-quaterphenyl radicals [denoted by (Bz) n (n = 1-4), where n means numbers of benzene rings in aryl radical] were examined as aryl radicals. The DFT calculation of GR-(Bz) n (n = 1-4) showed that the aryl radical binds to the carbon atom of GR, and a C-C single bond was formed. The binding energies of aryl radicals to GR were calculated to be ca. 6.0 kcal mol-1 at the CAM-B3LYP/6-311G(d,p) level. It was found that the activation barrier exists in the aryl radical addition: the barrier heights were calculated to be 10.0 kcal mol-1. The electronic states of GR-(Bz) n were examined on the basis of theoretical results.

  9. Density Functional Theory and Atomic Force Microscopy Study of Oleate Functioned on Siderite Surface

    Directory of Open Access Journals (Sweden)

    Lixia Li

    2018-01-01

    Full Text Available Efficiently discovering the interaction of the collector oleate and siderite is of great significance for understanding the inherent function of siderite weakening hematite reverse flotation. For this purpose, investigation of the adsorption behavior of oleate on siderite surface was performed by density functional theory (DFT calculations associating with atomic force microscopy (AFM imaging. The siderite crystal geometry was computationally optimized via convergence tests. Calculated results of the interaction energy and the Mulliken population verified that the collector oleate adsorbed on siderite surface and the covalent bond was established as a result of electrons transferring from O1 atoms (in oleate molecule to Fe1 atoms (in siderite lattice. Therefore, valence-electrons’ configurations of Fe1 and O1 changed into 3d6.514s0.37 and 2s1.832p4.73 from 3d6.214s0.31 and 2s1.83p4.88 correspondingly. Siderite surfaces with or without oleate functioned were examined with the aid of AFM imaging in PeakForce Tapping mode, and the functioned siderite surface was found to be covered by vesicular membrane matters with the average roughness of 16.4 nm assuring the oleate adsorption. These results contributed to comprehending the interaction of oleate and siderite.

  10. Density functional theory and beyond-opportunities for quantum methods in materials modeling semiconductor technology

    International Nuclear Information System (INIS)

    Shankar, Sadasivan; Simka, Harsono; Haverty, Michael

    2008-01-01

    In the semiconductor industry, the use of new materials has been increasing with the advent of nanotechnology. As critical dimensions decrease, and the number of materials increases, the interactions between heterogeneous materials themselves and processing increase in complexity. Traditionally, applications of ab initio techniques are confined to electronic structure and band gap calculations of bulk materials, which are then used in coarse-grained models such as mesoscopic and continuum models. Density functional theory is the most widely used ab initio technique that was successfully extended to several applications. This paper illustrates applications of density functional theory to semiconductor processes and proposes further opportunities for use of such techniques in process development

  11. Strontium, nickel, cadmium, and lead substitution into calcite, studied by density functional theory

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Sakuma, Hiroshi; Stipp, Susan Louise Svane

    2014-01-01

    We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral-fluid inte......We have used density functional theory to predict the ion exchange energies for divalent cations Ni(2+), Sr(2+), Cd(2+), and Pb(2+) into a calcite {10.4} surface in equilibrium with water. Exchange energies were calculated for substitution into the topmost surface layer, at the mineral...

  12. Melting slope of MgO from molecular dynamics and density functional theory

    Science.gov (United States)

    Tangney, Paul; Scandolo, Sandro

    2009-09-01

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

  13. Optical Absorption in Molecular Crystals from Time-Dependent Density Functional Theory

    Science.gov (United States)

    2017-04-23

    Our approach represents a full solid-state calculation, allowing for polarization ef- fects while still capable of capturing inter-molecular dis...AFRL-AFOSR-UK-TR-2017-0030 Optical absorption in molecular crystals from time-dependent density functional theory Leeor Kronik WEIZMANN INSTITUTE OF...from time-dependent density functional theory 5a.  CONTRACT NUMBER 5b.  GRANT NUMBER FA9550-15-1-0290 5c.  PROGRAM ELEMENT NUMBER 61102F 6. AUTHOR(S

  14. Natural excitation orbitals from linear response theories : Time-dependent density functional theory, time-dependent Hartree-Fock, and time-dependent natural orbital functional theory

    NARCIS (Netherlands)

    Van Meer, R.; Gritsenko, O. V.; Baerends, E. J.

    2017-01-01

    Straightforward interpretation of excitations is possible if they can be described as simple single orbital-to-orbital (or double, etc.) transitions. In linear response time-dependent density functional theory (LR-TDDFT), the (ground state) Kohn-Sham orbitals prove to be such an orbital basis. In

  15. Chemical functionalization of graphene by carbene cycloaddition: A density functional theory study

    International Nuclear Information System (INIS)

    Zan, Wenyan

    2014-01-01

    Graphical abstract: - Highlights: • The reaction process of graphene functionalization with CCl 2 group in atomic scales was studied. • The potential candidate carbenes CR 2 (R = H, F, CN, NO 2 0 , NO 2 90 , CH 3 , OCH 3 , CCH, C 6 H 5 ) were separately combined with graphene. • The functionalization of graphene nanoribbon with dichlorocarbene group was investigated. • The electronic properties of graphene functionalized by carbene groups were discussed. - Abstract: In this work, we have systematically studied the structural, energetic and electronic properties of graphene functionalized with carbene groups by using density functional theory. Introducing a low concentration of CCl 2 group in graphene was studied in detail by DFT, and closed cyclopropane-like three-membered ring structure was formed, meanwhile, the potential candidate carbene groups CR 2 (R = H, F, CH 3 , CN, NO 2 , OCH 3 , CCH, C 6 H 5 ) were added to graphene sheet, and CR 2 (R = H, NO 2 , CH 3 ) groups were expected to be good reactive species to covalently modify graphene. The graphene functionalization with carbene groups above can open graphene's band gap. More CCl 2 molecules were added to graphene, and different concentrations of CCl 2 group can tune graphene's band gap. In addition, the addition of CCl 2 group to graphene edges was investigated, and the stronger binding energy was found. Multiple CCl 2 molecules preferred to be bound with the same edge of graphene nanoribbon. This work provides an insight into the detailed molecular mechanism of graphene functionalization with carbene groups

  16. Density functional theory and dynamical mean-field theory. A way to model strongly correlated systems

    International Nuclear Information System (INIS)

    Backes, Steffen

    2017-04-01

    The study of the electronic properties of correlated systems is a very diverse field and has lead to valuable insight into the physics of real materials. In these systems, the decisive factor that governs the physical properties is the ratio between the electronic kinetic energy, which promotes delocalization over the lattice, and the Coulomb interaction, which instead favours localized electronic states. Due to this competition, correlated electronic systems can show unique and interesting properties like the Metal-Insulator transition, diverse phase diagrams, strong temperature dependence and in general a high sensitivity to the environmental conditions. A theoretical description of these systems is not an easy task, since perturbative approaches that do not preserve the competition between the kinetic and interaction terms can only be applied in special limiting cases. One of the most famous approaches to obtain the electronic properties of a real material is the ab initio density functional theory (DFT) method. It allows one to obtain the ground state density of the system under investigation by mapping onto an effective non-interacting system that has to be found self-consistently. While being an exact theory, in practical implementations certain approximations have to be made to the exchange-correlation potential. The local density approximation (LDA), which approximates the exchange-correlation contribution to the total energy by that of a homogeneous electron gas with the corresponding density, has proven quite successful in many cases. Though, this approximation in general leads to an underestimation of electronic correlations and is not able to describe a metal-insulator transition due to electronic localization in the presence of strong Coulomb interaction. A different approach to the interacting electronic problem is the dynamical mean-field theory (DMFT), which is non-perturbative in the kinetic and interaction term but neglects all non

  17. Density functional theory and dynamical mean-field theory. A way to model strongly correlated systems

    Energy Technology Data Exchange (ETDEWEB)

    Backes, Steffen

    2017-04-15

    The study of the electronic properties of correlated systems is a very diverse field and has lead to valuable insight into the physics of real materials. In these systems, the decisive factor that governs the physical properties is the ratio between the electronic kinetic energy, which promotes delocalization over the lattice, and the Coulomb interaction, which instead favours localized electronic states. Due to this competition, correlated electronic systems can show unique and interesting properties like the Metal-Insulator transition, diverse phase diagrams, strong temperature dependence and in general a high sensitivity to the environmental conditions. A theoretical description of these systems is not an easy task, since perturbative approaches that do not preserve the competition between the kinetic and interaction terms can only be applied in special limiting cases. One of the most famous approaches to obtain the electronic properties of a real material is the ab initio density functional theory (DFT) method. It allows one to obtain the ground state density of the system under investigation by mapping onto an effective non-interacting system that has to be found self-consistently. While being an exact theory, in practical implementations certain approximations have to be made to the exchange-correlation potential. The local density approximation (LDA), which approximates the exchange-correlation contribution to the total energy by that of a homogeneous electron gas with the corresponding density, has proven quite successful in many cases. Though, this approximation in general leads to an underestimation of electronic correlations and is not able to describe a metal-insulator transition due to electronic localization in the presence of strong Coulomb interaction. A different approach to the interacting electronic problem is the dynamical mean-field theory (DMFT), which is non-perturbative in the kinetic and interaction term but neglects all non

  18. Multireference Density Functional Theory with Generalized Auxiliary Systems for Ground and Excited States.

    Science.gov (United States)

    Chen, Zehua; Zhang, Du; Jin, Ye; Yang, Yang; Su, Neil Qiang; Yang, Weitao

    2017-09-21

    To describe static correlation, we develop a new approach to density functional theory (DFT), which uses a generalized auxiliary system that is of a different symmetry, such as particle number or spin, from that of the physical system. The total energy of the physical system consists of two parts: the energy of the auxiliary system, which is determined with a chosen density functional approximation (DFA), and the excitation energy from an approximate linear response theory that restores the symmetry to that of the physical system, thus rigorously leading to a multideterminant description of the physical system. The electron density of the physical system is different from that of the auxiliary system and is uniquely determined from the functional derivative of the total energy with respect to the external potential. Our energy functional is thus an implicit functional of the physical system density, but an explicit functional of the auxiliary system density. We show that the total energy minimum and stationary states, describing the ground and excited states of the physical system, can be obtained by a self-consistent optimization with respect to the explicit variable, the generalized Kohn-Sham noninteracting density matrix. We have developed the generalized optimized effective potential method for the self-consistent optimization. Among options of the auxiliary system and the associated linear response theory, reformulated versions of the particle-particle random phase approximation (pp-RPA) and the spin-flip time-dependent density functional theory (SF-TDDFT) are selected for illustration of principle. Numerical results show that our multireference DFT successfully describes static correlation in bond dissociation and double bond rotation.

  19. Pressure and surface tension of solid-liquid interface using Tara zona density functional theory

    International Nuclear Information System (INIS)

    Moradi, M.; Kavosh Tehrani, M.

    2001-01-01

    The weighted density functional theory proposed by Tara zona is applied to study the solid-liquid interface. In the last two decades the weighted density functional became a useful tool to consider the properties of inhomogeneous liquids. In this theory, the role of the size of molecules or the particles of which the matter is composed, was found to be important. In this research we study a hard sphere fluid beside a hard wall. For this study the liquid is an inhomogeneous system. We use the definition of the direct correlation function as a second derivative of free energy with respect to the density. We use this definition and the definition of the weighting function, then we minimize the grand potential with respect to the density to get the Euler Lagrange equation and we obtain an integral equation to find the inhomogeneous density profile. The obtained density profile as a function of the distance from the wall, for different bulk density is pitted in three dimensions. We also calculate the pressure and compare it with the Carnahan-Starling results, and finally we obtained the surface tension at liquid-solid interface and compared it with the results of Monte Carlo simulation

  20. Pressure and surface tension of soild-liquid interface using Tarazona density functional theory

    Directory of Open Access Journals (Sweden)

    M. M.

    2000-12-01

    Full Text Available   The weighted density functional theory proposed by Tarazona is applied to study the solid-liquid interface. In the last two decades the weighted density functional became a useful tool to consider the properties of inhomogeneous liquids. In this theory, the role of the size of molecules or the particles of which the matter is composed, was found to be important. In this resarch we study a hard sphere fluid beside a hard wall. For this study the liquid is an inhomogeneous system. We use the definition of the direct correlation function as a second derivative of free energy with respect to the density. We use this definition and the definition of the weighting function, then we minimize the grand potential with respect to the density to get the Euler Lagrange equation and we obtain an integral equation to find the inhomogeneous density profile. The obtained density profile as a function of the distance from the wall, for different bulk density is plotted in three dimensions. We also calculate the pressure and compare it with the Carnahan-starling results, and finally we obtained the surface tension at liquid-solid interface and compared it with the results of Monte Carlo simulation.

  1. Joint density-functional theory and its application to systems in solution

    Science.gov (United States)

    Petrosyan, Sahak A.

    The physics of solvation, the interaction of water with solutes, plays a central role in chemistry and biochemistry, and it is essential for the very existence of life. Despite the central importance of water and the advent of the quantum theory early in the twentieth century, the link between the fundamental laws of physics and the observable properties of water remain poorly understood to this day. The central goal of this thesis is to develop a new formalism and framework to make the study of systems (solutes or surfaces) in contact with liquid water as practical and accurate as standard electronic structure calculations without the need for explicit averaging over large ensembles of configurations of water molecules. The thesis introduces a new form of density functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment. This theory rigorously joins an electron density-functional for the electrons of a solute with a classical density-functional theory for the liquid into a single variational principle for the free energy of the combined system. Using the new form of density-functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment, the thesis then presents the first detailed study of the impact of a solvent on the surface chemistry of Cr2O3, the passivating layer of stainless steel alloys. In comparison to a vacuum, we predict that the presence of water has little impact on the adsorption of chloride ions to the oxygen-terminated surface but has a dramatic effect on the binding of hydrogen to that surface. A key ingredient of a successful joint density functional theory is a good approximate functional for describing the solvent. We explore how the simplest examples of the best known class of approximate forms for the classical density functional fail when applied directly to water. The thesis then presents a computationally efficient density-functional

  2. Generalized nuclear Fukui functions in the framework of spin-polarized density-functional theory

    International Nuclear Information System (INIS)

    Chamorro, E.; Proft, F. de; Geerlings, P.

    2005-01-01

    An extension of Cohen's nuclear Fukui function is presented in the spin-polarized framework of density-functional theory (SP-DFT). The resulting new nuclear Fukui function indices Φ Nα and Φ Sα are intended to be the natural descriptors for the responses of the nuclei to changes involving charge transfer at constant multiplicity and also the spin polarization at constant number of electrons. These generalized quantities allow us to gain new insights within a perturbative scheme based on DFT. Calculations of the electronic and nuclear SP-DFT quantities are presented within a Kohn-Sham framework of chemical reactivity for a sample of molecules, including H 2 O, H 2 CO, and some simple nitrenes (NX) and phosphinidenes (PX), with X=H, Li, F, Cl, OH, SH, NH 2 , and PH 2 . Results have been interpreted in terms of chemical bonding in the context of Berlin's theorem, which provides a separation of the molecular space into binding and antibinding regions

  3. Charge Transfer Enhancement in the D-π-A Type Porphyrin Dyes: A Density Functional Theory (DFT and Time-Dependent Density Functional Theory (TD-DFT Study

    Directory of Open Access Journals (Sweden)

    Guo-Jun Kang

    2016-11-01

    Full Text Available The electronic geometries and optical properties of two D-π-A type zinc porphyrin dyes (NCH3-YD2 and TPhe-YD were systematically investigated by density functional theory (DFT and time-dependent density functional theory (TD-DFT to reveal the origin of significantly altered charge transfer enhancement by changing the electron donor of the famous porphyrin-based sensitizer YD2-o-C8. The molecular geometries and photophysical properties of dyes before and after binding to the TiO2 cluster were fully investigated. From the analyses of natural bond orbital (NBO, extended charge decomposition analysis (ECDA, and electron density variations (Δρ between the excited state and ground state, it was found that the introduction of N(CH32 and 1,1,2-triphenylethene groups enhanced the intramolecular charge-transfer (ICT character compared to YD2-o-C8. The absorption wavelength and transition possess character were significantly influenced by N(CH32 and 1,1,2-triphenylethene groups. NCH3-YD2 with N(CH32 groups in the donor part is an effective way to improve the interactions between the dyes and TiO2 surface, light having efficiency (LHE, and free energy change (ΔGinject, which is expected to be an efficient dye for use in dye-sensitized solar cells (DSSCs.

  4. Structure of solvent-free grafted nanoparticles: Molecular dynamics and density-functional theory

    KAUST Repository

    Chremos, Alexandros

    2011-01-01

    The structure of solvent-free oligomer-grafted nanoparticles has been investigated using molecular dynamics simulations and density-functional theory. At low temperatures and moderate to high oligomer lengths, the qualitative features of the core particle pair probability, structure factor, and the oligomer brush configuration obtained from the simulations can be explained by a density-functional theory that incorporates the configurational entropy of the space-filling oligomers. In particular, the structure factor at small wave numbers attains a value much smaller than the corresponding hard-sphere suspension, the first peak of the pair distribution function is enhanced due to entropic attractions among the particles, and the oligomer brush expands with decreasing particle volume fraction to fill the interstitial space. At higher temperatures, the simulations reveal effects that differ from the theory and are likely caused by steric repulsions of the expanded corona chains. © 2011 American Institute of Physics.

  5. Density functional theory study of the concerted pyrolysis mechanism for lignin models

    Science.gov (United States)

    Thomas Elder; Ariana Beste

    2014-01-01

    ABSTRACT: Studies on the pyrolysis mechanisms of lignin model compounds have largely focused on initial homolytic cleavage reactions. It has been noted, however, that concerted mechanisms may also account for observed product formation. In the current work, the latter processes are examined and compared to the former, by the application of density functional theory...

  6. The oxygen reduction reaction mechanism on Pt(111) from density functional theory calculations

    DEFF Research Database (Denmark)

    Tripkovic, Vladimir; Skulason, Egill; Siahrostami, Samira

    2010-01-01

    We study the oxygen reduction reaction (ORR) mechanism on a Pt(1 1 1) surface using density functional theory calculations We find that at low overpotentials the surface is covered with a half dissociated water layer We estimate the barrier for proton transfer to this surface and the barrier...

  7. Characterization of the nitrogen split interstitial defect in wurtzite aluminum nitride using density functional theory

    International Nuclear Information System (INIS)

    Szállás, A.; Szász, K.; Trinh, X. T.; Son, N. T.; Janzén, E.; Gali, A.

    2014-01-01

    We carried out Heyd-Scuseria-Ernzerhof hybrid density functional theory plane wave supercell calculations in wurtzite aluminum nitride in order to characterize the geometry, formation energies, transition levels, and hyperfine tensors of the nitrogen split interstitial defect. The calculated hyperfine tensors may provide useful fingerprint of this defect for electron paramagnetic resonance measurement.

  8. Time-dependent density-functional theory in the projector augmented-wave method

    DEFF Research Database (Denmark)

    Walter, Michael; Häkkinen, Hannu; Lehtovaara, Lauri

    2008-01-01

    We present the implementation of the time-dependent density-functional theory both in linear-response and in time-propagation formalisms using the projector augmented-wave method in real-space grids. The two technically very different methods are compared in the linear-response regime where we...

  9. Solving large nonlinear generalized eigenvalue problems from Density Functional Theory calculations in parallel

    DEFF Research Database (Denmark)

    Bendtsen, Claus; Nielsen, Ole Holm; Hansen, Lars Bruno

    2001-01-01

    The quantum mechanical ground state of electrons is described by Density Functional Theory, which leads to large minimization problems. An efficient minimization method uses a self-consistent field (SCF) solution of large eigenvalue problems. The iterative Davidson algorithm is often used, and we...

  10. Electronic zero-point oscillations in the strong-interaction limit of density functional theory

    NARCIS (Netherlands)

    Gori Giorgi, P.; Vignale, G.; Seidl, M.

    2009-01-01

    The exchange-correlation energy in Kohn-Sham density functional theory can be expressed exactly in terms of the change in the expectation of the electron-electron repulsion operator when, in the many-electron Hamiltonian, this same operator is multiplied by a real parameter λ varying between 0

  11. Characterization of the nitrogen split interstitial defect in wurtzite aluminum nitride using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Szállás, A., E-mail: szallas.attila@wigner.mta.hu [Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Szász, K. [Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Institute of Physics, Eötvös University, Pázmány Péter sétány 1/A, H-1117 Budapest (Hungary); Trinh, X. T.; Son, N. T.; Janzén, E. [Department of Physics, Chemistry and Biology, Linköping University, SE-581 83 Linköping (Sweden); Gali, A., E-mail: gali.adam@wigner.mta.hu [Institute for Solid State Physics and Optics, Wigner Research Centre for Physics, Hungarian Academy of Sciences, P.O. Box 49, H-1525 Budapest (Hungary); Department of Atomic Physics, Budapest University of Technology and Economics, Budafoki út 8, H-1111 Budapest (Hungary)

    2014-09-21

    We carried out Heyd-Scuseria-Ernzerhof hybrid density functional theory plane wave supercell calculations in wurtzite aluminum nitride in order to characterize the geometry, formation energies, transition levels, and hyperfine tensors of the nitrogen split interstitial defect. The calculated hyperfine tensors may provide useful fingerprint of this defect for electron paramagnetic resonance measurement.

  12. Exchange coupling interactions in a Fe6 complex: A theoretical study using density functional theory

    International Nuclear Information System (INIS)

    Cauchy, Thomas; Ruiz, Eliseo; Alvarez, Santiago

    2006-01-01

    Theoretical methods based on density functional theory have been employed to analyze the exchange interactions in an Fe 6 complex. The calculated exchange coupling constants are consistent with an S=5 ground state and agree well with those reported previously for other Fe III polynuclear complexes. Ferromagnetic interactions may appear through exchange pathways formed by two bridging hydroxo or oxo ligands

  13. A density functional theory study of arsenic immobilization by the Al(III)-modified zeolite clinoptilolite

    NARCIS (Netherlands)

    Awuah, Joel B.; Dzade, N.Y.; Tia, Richard; Adei, Evans; Kwakye-Awuah, Bright; Catlow, C. Richard A.; de Leeuw, Nora H.

    2016-01-01

    We present density functional theory calculations of the adsorption of arsenic acid (AsO(OH)3) and arsenous acid (As(OH)3) on the Al(III)-modified natural zeolite clinoptilolite under anhydrous and hydrated conditions. From our calculated adsorption energies, we show that adsorption of both arsenic

  14. Analysis of the photophysical properties of zearalenone using density functional theory

    Science.gov (United States)

    The intrinsic photophysical properties of the resorcylic acid moiety of zearalenone offer a convenient label free method to determine zearalenone levels in contaminated agricultural products. Density functional theory and steady-state fluorescence methods were applied to investigate the role of stru...

  15. 2nd derivatives of the electronic energy in density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Dam, H. van

    2001-08-01

    This document details the equations needed to implement the calculation of vibrational frequencies within the density functional formalism of electronic structure theory. This functionality has been incorporated into the CCP1 DFT module and the required changes to the application programmers interface are outlined. Throughout it is assumed that an implementation of Hartree-Fock vibrational frequencies is available that can be modified to incorporate the density functional formalism. Employing GAMESS-UK as an example the required changes to the Hartree-Fock code are outlined. (author)

  16. Time-dependent density functional theory for open quantum systems with unitary propagation.

    Science.gov (United States)

    Yuen-Zhou, Joel; Tempel, David G; Rodríguez-Rosario, César A; Aspuru-Guzik, Alán

    2010-01-29

    We extend the Runge-Gross theorem for a very general class of open quantum systems under weak assumptions about the nature of the bath and its coupling to the system. We show that for Kohn-Sham (KS) time-dependent density functional theory, it is possible to rigorously include the effects of the environment within a bath functional in the KS potential. A Markovian bath functional inspired by the theory of nonlinear Schrödinger equations is suggested, which can be readily implemented in currently existing real-time codes. Finally, calculations on a helium model system are presented.

  17. Layered interfaces between immiscible liquids studied by density-functional theory and molecular-dynamics simulations.

    Science.gov (United States)

    Geysermans, P; Elyeznasni, N; Russier, V

    2005-11-22

    We present a study of the structure in the interface between two immiscible liquids by density-functional theory and molecular-dynamics calculations. The liquids are modeled by Lennard-Jones potentials, which achieve immiscibility by suppressing the attractive interaction between unlike particles. The density profiles of the liquids display oscillations only in a limited part of the simple liquid-phase diagram (rho,T). When approaching the liquid-vapor coexistence, a significant depletion appears while the layering behavior of the density profile vanishes. By analogy with the liquid-vapor interface and the analysis of the adsorption this behavior is suggested to be strongly related to the drying transition.

  18. Density functional theory of simple polymers in a slit pore. III. Surface tension

    International Nuclear Information System (INIS)

    Hooper, Justin B.; McCoy, John D.; Curro, John G.; Swol, Frank van

    2000-01-01

    In a previous study of tangent hard-site chains near a surface, the inhomogeneous density profiles were found through density functional theory. In the current study, the surface tensions of these systems are found from the results of the previous study through a thermodynamic integration. The calculated surface tensions are then compared to those found directly through computer simulation. Both the surface tension and surface excess for polymeric systems are shown to differ qualitatively from those of atomic systems, although certain similarities are seen at high densities. (c) 2000 American Institute of Physics

  19. Hot-electron-assisted femtochemistry at surfaces: A time-dependent density functional theory approach

    DEFF Research Database (Denmark)

    Gavnholt, Jeppe; Rubio, Angel; Olsen, Thomas

    2009-01-01

    Using time-evolution time-dependent density functional theory (TDDFT) within the adiabatic local-density approximation, we study the interactions between single electrons and molecular resonances at surfaces. Our system is a nitrogen molecule adsorbed on a ruthenium surface. The surface is modele...... resonance and the lowering of the resonance energy due to an image charge effect. Finally we apply the TDDFT procedure to only consider the decay of molecular excitations and find that it agrees quite well with the width of the projected density of Kohn-Sham states....

  20. Classical density functional theory & simulations on a coarse-grained model of aromatic ionic liquids.

    Science.gov (United States)

    Turesson, Martin; Szparaga, Ryan; Ma, Ke; Woodward, Clifford E; Forsman, Jan

    2014-05-14

    A new classical density functional approach is developed to accurately treat a coarse-grained model of room temperature aromatic ionic liquids. Our major innovation is the introduction of charge-charge correlations, which are treated in a simple phenomenological way. We test this theory on a generic coarse-grained model for aromatic RTILs with oligomeric forms for both cations and anions, approximating 1-alkyl-3-methyl imidazoliums and BF₄⁻, respectively. We find that predictions by the new density functional theory for fluid structures at charged surfaces are very accurate, as compared with molecular dynamics simulations, across a range of surface charge densities and lengths of the alkyl chain. Predictions of interactions between charged surfaces are also presented.

  1. Time dependent density functional theory of light absorption in dense plasmas: application to iron-plasma

    International Nuclear Information System (INIS)

    Grimaldi, F.; Grimaldi-Lecourt, A.; Dharma-Wardana, M.W.C.

    1986-10-01

    The objective of this paper is to present a simple time-dependent calculation of the light absorption cross section for a strongly coupled partially degenerate plasma so as to transcend the usual single-particle picture. This is achieved within the density functional theory (DFT) of plasmas by generalizing the method given by Zangwill and Soven for atomic calculations at zero temperature. The essential feature of the time dependent DFT is the correct treatment of the relaxation of the system under the external field. Exploratory calculations for a Fe-plasma at 100 eV show new features in the absorption cross section which are absent in the usual single particle theory. These arise from inter-shell correlations, channel mixing and self-energy effects. These many-body effects introduce significant modifications to the radiative properties of plasmas and are shown to be efficiently calculable by time dependent density functional theory (TD-DFT)

  2. Time dependent density functional theory of light absorption in dense plasmas: application to iron-plasma

    International Nuclear Information System (INIS)

    Grimaldi, F.; Grimaldi-Lecourt, A.; Dharma-Wardana, M.W.C.

    1985-02-01

    The objective of this paper is to present a simple time-dependent calculation of the light absorption cross section for a strongly coupled partially degenerate plasma so as to transcend the usual single-particle picture. This is achieved within the density functional theory (DFT) of plasmas by generalizing the method given by Zangwill and Soven for atomic calculations at zero temperature. The essential feature of the time dependent DFT is the correct treatment of the relaxation of the system under the external field. Exploratory calculations for an Fe-plasma at 100 eV show new features in the absorption cross section which are absent in the usual single particle theory. These arise from inter-shell correlations, channel mixing and self-energy effects. These many-body effects introduce significant modifications to the radiative properties of plasma and are shown to be efficiently calculable by time dependent density functional theory (TD-DFT)

  3. Applications of the Conceptual Density Functional Theory Indices to Organic Chemistry Reactivity.

    Science.gov (United States)

    Domingo, Luis R; Ríos-Gutiérrez, Mar; Pérez, Patricia

    2016-06-09

    Theoretical reactivity indices based on the conceptual Density Functional Theory (DFT) have become a powerful tool for the semiquantitative study of organic reactivity. A large number of reactivity indices have been proposed in the literature. Herein, global quantities like the electronic chemical potential μ, the electrophilicity ω and the nucleophilicity N indices, and local condensed indices like the electrophilic P k + and nucleophilic P k - Parr functions, as the most relevant indices for the study of organic reactivity, are discussed.

  4. Hartree and Exchange in Ensemble Density Functional Theory: Avoiding the Nonuniqueness Disaster.

    Science.gov (United States)

    Gould, Tim; Pittalis, Stefano

    2017-12-15

    Ensemble density functional theory is a promising method for the efficient and accurate calculation of excitations of quantum systems, at least if useful functionals can be developed to broaden its domain of practical applicability. Here, we introduce a guaranteed single-valued "Hartree-exchange" ensemble density functional, E_{Hx}[n], in terms of the right derivative of the universal ensemble density functional with respect to the coupling constant at vanishing interaction. We show that E_{Hx}[n] is straightforwardly expressible using block eigenvalues of a simple matrix [Eq. (14)]. Specialized expressions for E_{Hx}[n] from the literature, including those involving superpositions of Slater determinants, can now be regarded as originating from the unifying picture presented here. We thus establish a clear and practical description for Hartree and exchange in ensemble systems.

  5. A-centers in silicon studied with hybrid density functional theory

    KAUST Repository

    Wang, Hao; Chroneos, Alexander; Londos, C. A.; Schwingenschlö gl, Udo; Sgourou, E. N.

    2013-01-01

    Density functional theory employing hybrid functional is used to gain fundamental insight into the interaction of vacancies with oxygen interstitials to form defects known as A-centers in silicon. We calculate the formation energy of the defect with respect to the Fermi energy for all possible charge states. It is found that the neutral and doubly negatively charged A-centers dominate. The findings are analyzed in terms of the density of states and discussed in view of previous experimental and theoretical studies.

  6. Multi-configuration time-dependent density-functional theory based on range separation

    DEFF Research Database (Denmark)

    Fromager, E.; Knecht, S.; Jensen, Hans Jørgen Aagaard

    2013-01-01

    Multi-configuration range-separated density-functional theory is extended to the time-dependent regime. An exact variational formulation is derived. The approximation, which consists in combining a long-range Multi-Configuration- Self-Consistent Field (MCSCF) treatment with an adiabatic short...... (srGGA) approximations. As expected, when modeling long-range interactions with the MCSCF model instead of the adiabatic Buijse-Baerends density-matrix functional as recently proposed by Pernal [J. Chem. Phys. 136, 184105 (2012)10.1063/1.4712019], the description of both the 1D doubly-excited state...

  7. A-centers in silicon studied with hybrid density functional theory

    KAUST Repository

    Wang, Hao

    2013-07-29

    Density functional theory employing hybrid functional is used to gain fundamental insight into the interaction of vacancies with oxygen interstitials to form defects known as A-centers in silicon. We calculate the formation energy of the defect with respect to the Fermi energy for all possible charge states. It is found that the neutral and doubly negatively charged A-centers dominate. The findings are analyzed in terms of the density of states and discussed in view of previous experimental and theoretical studies.

  8. Computational Benchmarking for Ultrafast Electron Dynamics: Wave Function Methods vs Density Functional Theory.

    Science.gov (United States)

    Oliveira, Micael J T; Mignolet, Benoit; Kus, Tomasz; Papadopoulos, Theodoros A; Remacle, F; Verstraete, Matthieu J

    2015-05-12

    Attosecond electron dynamics in small- and medium-sized molecules, induced by an ultrashort strong optical pulse, is studied computationally for a frozen nuclear geometry. The importance of exchange and correlation effects on the nonequilibrium electron dynamics induced by the interaction of the molecule with the strong optical pulse is analyzed by comparing the solution of the time-dependent Schrödinger equation based on the correlated field-free stationary electronic states computed with the equationof-motion coupled cluster singles and doubles and the complete active space multi-configurational self-consistent field methodologies on one hand, and various functionals in real-time time-dependent density functional theory (TDDFT) on the other. We aim to evaluate the performance of the latter approach, which is very widely used for nonlinear absorption processes and whose computational cost has a more favorable scaling with the system size. We focus on LiH as a toy model for a nontrivial molecule and show that our conclusions carry over to larger molecules, exemplified by ABCU (C10H19N). The molecules are probed with IR and UV pulses whose intensities are not strong enough to significantly ionize the system. By comparing the evolution of the time-dependent field-free electronic dipole moment, as well as its Fourier power spectrum, we show that TD-DFT performs qualitatively well in most cases. Contrary to previous studies, we find almost no changes in the TD-DFT excitation energies when excited states are populated. Transitions between states of different symmetries are induced using pulses polarized in different directions. We observe that the performance of TD-DFT does not depend on the symmetry of the states involved in the transition.

  9. Hole trapping at Al impurities in silica: A challenge for density functional theories

    DEFF Research Database (Denmark)

    Lægsgaard, Jesper; Stokbro, Kurt

    2001-01-01

    The atomic geometry and electronic structure around a neutral substitutional Al impurity in silica is investigated using either the unrestricted Hartree-Fock (UHF) approximation, or Beckes three-parameter hybrid functional (B3LYP). It is found that the B3LYP functional fails to describe...... the structural distortions around the Al impurity, while the UHF results are consistent with experimental information. We argue that the failure of the B3LYP functional is caused by the incomplete self-interaction cancellation usually present in density functional theories....

  10. Studying the varied shapes of gold clusters by an elegant optimization algorithm that hybridizes the density functional tight-binding theory and the density functional theory

    Science.gov (United States)

    Yen, Tsung-Wen; Lim, Thong-Leng; Yoon, Tiem-Leong; Lai, S. K.

    2017-11-01

    We combined a new parametrized density functional tight-binding (DFTB) theory (Fihey et al. 2015) with an unbiased modified basin hopping (MBH) optimization algorithm (Yen and Lai 2015) and applied it to calculate the lowest energy structures of Au clusters. From the calculated topologies and their conformational changes, we find that this DFTB/MBH method is a necessary procedure for a systematic study of the structural development of Au clusters but is somewhat insufficient for a quantitative study. As a result, we propose an extended hybridized algorithm. This improved algorithm proceeds in two steps. In the first step, the DFTB theory is employed to calculate the total energy of the cluster and this step (through running DFTB/MBH optimization for given Monte-Carlo steps) is meant to efficiently bring the Au cluster near to the region of the lowest energy minimum since the cluster as a whole has explicitly considered the interactions of valence electrons with ions, albeit semi-quantitatively. Then, in the second succeeding step, the energy-minimum searching process will continue with a skilledly replacement of the energy function calculated by the DFTB theory in the first step by one calculated in the full density functional theory (DFT). In these subsequent calculations, we couple the DFT energy also with the MBH strategy and proceed with the DFT/MBH optimization until the lowest energy value is found. We checked that this extended hybridized algorithm successfully predicts the twisted pyramidal structure for the Au40 cluster and correctly confirms also the linear shape of C8 which our previous DFTB/MBH method failed to do so. Perhaps more remarkable is the topological growth of Aun: it changes from a planar (n =3-11) → an oblate-like cage (n =12-15) → a hollow-shape cage (n =16-18) and finally a pyramidal-like cage (n =19, 20). These varied forms of the cluster's shapes are consistent with those reported in the literature.

  11. FDE-vdW: A van der Waals inclusive subsystem density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kevorkyants, Ruslan; Pavanello, Michele, E-mail: m.pavanello@rutgers.edu [Department of Chemistry, Rutgers University, Newark, New Jersey 07102 (United States); Eshuis, Henk [Department of Chemistry and Biochemistry, Montclair State University, Montclair, New Jersey 07043 (United States)

    2014-07-28

    We present a formally exact van der Waals inclusive electronic structure theory, called FDE-vdW, based on the Frozen Density Embedding formulation of subsystem Density-Functional Theory. In subsystem DFT, the energy functional is composed of subsystem additive and non-additive terms. We show that an appropriate definition of the long-range correlation energy is given by the value of the non-additive correlation functional. This functional is evaluated using the fluctuation–dissipation theorem aided by a formally exact decomposition of the response functions into subsystem contributions. FDE-vdW is derived in detail and several approximate schemes are proposed, which lead to practical implementations of the method. We show that FDE-vdW is Casimir-Polder consistent, i.e., it reduces to the generalized Casimir-Polder formula for asymptotic inter-subsystems separations. Pilot calculations of binding energies of 13 weakly bound complexes singled out from the S22 set show a dramatic improvement upon semilocal subsystem DFT, provided that an appropriate exchange functional is employed. The convergence of FDE-vdW with basis set size is discussed, as well as its dependence on the choice of associated density functional approximant.

  12. Unsupervised Learning and Pattern Recognition of Biological Data Structures with Density Functional Theory and Machine Learning.

    Science.gov (United States)

    Chen, Chien-Chang; Juan, Hung-Hui; Tsai, Meng-Yuan; Lu, Henry Horng-Shing

    2018-01-11

    By introducing the methods of machine learning into the density functional theory, we made a detour for the construction of the most probable density function, which can be estimated by learning relevant features from the system of interest. Using the properties of universal functional, the vital core of density functional theory, the most probable cluster numbers and the corresponding cluster boundaries in a studying system can be simultaneously and automatically determined and the plausibility is erected on the Hohenberg-Kohn theorems. For the method validation and pragmatic applications, interdisciplinary problems from physical to biological systems were enumerated. The amalgamation of uncharged atomic clusters validated the unsupervised searching process of the cluster numbers and the corresponding cluster boundaries were exhibited likewise. High accurate clustering results of the Fisher's iris dataset showed the feasibility and the flexibility of the proposed scheme. Brain tumor detections from low-dimensional magnetic resonance imaging datasets and segmentations of high-dimensional neural network imageries in the Brainbow system were also used to inspect the method practicality. The experimental results exhibit the successful connection between the physical theory and the machine learning methods and will benefit the clinical diagnoses.

  13. Gaussian-3 theory using density functional geometries and zero-point energies

    International Nuclear Information System (INIS)

    Baboul, A.G.; Curtiss, L.A.; Redfern, P.C.; Raghavachari, K.

    1999-01-01

    A variation of Gaussian-3 (G3) theory is presented in which the geometries and zero-point energies are obtained from B3LYP density functional theory [B3LYP/6-31G(d)] instead of geometries from second-order perturbation theory [MP2(FU)/6-31G(d)] and zero-point energies from Hartree - Fock theory [HF/6-31G(d)]. This variation, referred to as G3//B3LYP, is assessed on 299 energies (enthalpies of formation, ionization potentials, electron affinities, proton affinities) from the G2/97 test set [J. Chem. Phys. 109, 42 (1998)]. The G3//B3LYP average absolute deviation from experiment for the 299 energies is 0.99 kcal/mol compared to 1.01 kcal/mol for G3 theory. Generally, the results from the two methods are similar, with some exceptions. G3//B3LYP theory gives significantly improved results for several cases for which MP2 theory is deficient for optimized geometries, such as CN and O 2 + . However, G3//B3LYP does poorly for ionization potentials that involve a Jahn - Teller distortion in the cation (CH 4 + , BF 3 + , BCl 3 + ) because of the B3LYP/6-31G(d) geometries. The G3(MP2) method is also modified to use B3LYP/6-31G(d) geometries and zero-point energies. This variation, referred to as G3(MP2)//B3LYP, has an average absolute deviation of 1.25 kcal/mol compared to 1.30 kcal/mol for G3(MP2) theory. Thus, use of density functional geometries and zero-point energies in G3 and G3(MP2) theories is a useful alternative to MP2 geometries and HF zero-point energies. copyright 1999 American Institute of Physics

  14. On the contact values of the density profiles in an electric double layer using density functional theory

    Directory of Open Access Journals (Sweden)

    L.B. Bhuiyan

    2012-06-01

    Full Text Available A recently proposed, local second contact value theorem [Henderson D., Boda D., J. Electroanal. Chem., 2005, Vol. 582, 16] for the charge profile of an electric double layer is used in conjunction with existing Monte Carlo data from the literature to assess the contact behavior of the electrode-ion distributions predicted by the density functional theory. The results for the contact values of the co- and counterion distributions and their product are obtained for the symmetric valency, restricted primitive model planar double layer for a range of electrolyte concentrations and temperatures. Overall the theoretical results satisfy the second contact value theorem reasonably well the agreement with the simulations being semi-quantitative or better. The product of the co- and counterion contact values as a function of the electrode surface charge density is qualitative with the simulations with increasing deviations at higher concentrations.

  15. Analytic calculations of hyper-Raman spectra from density functional theory hyperpolarizability gradients

    Energy Technology Data Exchange (ETDEWEB)

    Ringholm, Magnus; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø – The Arctic University of Norway, 9037 Tromsø (Norway); Bast, Radovan [Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, AlbaNova University Center, S-10691 Stockholm (Sweden); PDC Center for High Performance Computing, Royal Institute of Technology, S-10044 Stockholm (Sweden); Oggioni, Luca [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Tromsø – The Arctic University of Norway, 9037 Tromsø (Norway); Department of Physics G. Occhialini, University of Milano Bicocca, Piazza della scienza 3, 20126 Milan (Italy); Ekström, Ulf [Centre for Theoretical and Computational Chemistry, Department of Chemistry, University of Oslo, P.O. Box 1033 Blindern, 0315 Oslo (Norway)

    2014-10-07

    We present the first analytic calculations of the geometrical gradients of the first hyperpolarizability tensors at the density-functional theory (DFT) level. We use the analytically calculated hyperpolarizability gradients to explore the importance of electron correlation effects, as described by DFT, on hyper-Raman spectra. In particular, we calculate the hyper-Raman spectra of the all-trans and 11-cis isomers of retinal at the Hartree-Fock (HF) and density-functional levels of theory, also allowing us to explore the sensitivity of the hyper-Raman spectra on the geometrical characteristics of these structurally related molecules. We show that the HF results, using B3LYP-calculated vibrational frequencies and force fields, reproduce the experimental data for all-trans-retinal well, and that electron correlation effects are of minor importance for the hyper-Raman intensities.

  16. Recent progress in orbital-free density functional theory (recent advances in computational chemistry)

    CERN Document Server

    Wesolowski, Tomasz A

    2013-01-01

    This is a comprehensive overview of state-of-the-art computational methods based on orbital-free formulation of density functional theory completed by the most recent developments concerning the exact properties, approximations, and interpretations of the relevant quantities in density functional theory. The book is a compilation of contributions stemming from a series of workshops which had been taking place since 2002. It not only chronicles many of the latest developments but also summarises some of the more significant ones. The chapters are mainly reviews of sub-domains but also include original research. Readership: Graduate students, academics and researchers in computational chemistry. Atomic & molecular physicists, theoretical physicists, theoretical chemists, physical chemists and chemical physicists.

  17. Hydrogen plasmas beyond density-functional theory: dynamic correlations and the onset of localization

    International Nuclear Information System (INIS)

    Perrot, F.; Dharma-Wardana, M.W.C.

    1984-01-01

    The density-functional theory (DFT) equations - previously considered in their application to the study of a system of ions and electrons in thermodynamic equilibrium at arbitrary temperatures and pressure - are reviewed with attention given to extending their validity in obtaining the one-electron excitation spectrum. The DFT model developed here provides structure factors and Kohn-Sham eigenstates which are then used to calculate the self-energy of the one-electron Green function, thus transcending the local-density approximations and the well-known limitations of DFT, especially with regard to the excitation spectrum. The one-particle formalism used makes contact with the multiple-scattering theories of disordered materials, liquid metals, etc., and is a necessary first step to a future calculation of two-particle propagators and related properties. 28 references

  18. Covariant density functional theory beyond mean field and applications for nuclei far from stability

    International Nuclear Information System (INIS)

    Ring, P

    2010-01-01

    Density functional theory provides a very powerful tool for a unified microscopic description of nuclei all over the periodic table. It is not only successful in reproducing bulk properties of nuclear ground states such as binding energies, radii, or deformation parameters, but it also allows the investigation of collective phenomena, such as giant resonances and rotational excitations. However, it is based on the mean field concept and therefore it has its limits. We discuss here two methods based based on covariant density functional theory going beyond the mean field concept, (i) models with an energy dependent self energy allowing the coupling to complex configurations and a quantitative description of the width of giant resonances and (ii) methods of configuration mixing between Slater determinants with different deformation and orientation providing are very successful description of transitional nuclei and quantum phase transitions.

  19. Multicomponent Time-Dependent Density Functional Theory: Proton and Electron Excitation Energies.

    Science.gov (United States)

    Yang, Yang; Culpitt, Tanner; Hammes-Schiffer, Sharon

    2018-04-05

    The quantum mechanical treatment of both electrons and protons in the calculation of excited state properties is critical for describing nonadiabatic processes such as photoinduced proton-coupled electron transfer. Multicomponent density functional theory enables the consistent quantum mechanical treatment of more than one type of particle and has been implemented previously for studying ground state molecular properties within the nuclear-electronic orbital (NEO) framework, where all electrons and specified protons are treated quantum mechanically. To enable the study of excited state molecular properties, herein the linear response multicomponent time-dependent density functional theory (TDDFT) is derived and implemented within the NEO framework. Initial applications to FHF - and HCN illustrate that NEO-TDDFT provides accurate proton and electron excitation energies within a single calculation. As its computational cost is similar to that of conventional electronic TDDFT, the NEO-TDDFT approach is promising for diverse applications, particularly nonadiabatic proton transfer reactions, which may exhibit mixed electron-proton vibronic excitations.

  20. Time-dependent current-density functional theory for generalized open quantum systems.

    Science.gov (United States)

    Yuen-Zhou, Joel; Rodríguez-Rosario, César; Aspuru-Guzik, Alán

    2009-06-14

    In this article, we prove the one-to-one correspondence between vector potentials and particle and current densities in the context of master equations with arbitrary memory kernels, therefore extending time-dependent current-density functional theory (TD-CDFT) to the domain of generalized many-body open quantum systems (OQS). We also analyse the issue of A-representability for the Kohn-Sham (KS) scheme proposed by D'Agosta and Di Ventra for Markovian OQS [Phys. Rev. Lett. 2007, 98, 226403] and discuss its domain of validity. We suggest ways to expand their scheme, but also propose a novel KS scheme where the auxiliary system is both closed and non-interacting. This scheme is tested numerically with a model system, and several considerations for the future development of functionals are indicated. Our results formalize the possibility of practising TD-CDFT in OQS, hence expanding the applicability of the theory to non-Hamiltonian evolutions.

  1. Improved Accuracy of Density Functional Theory Calculations for CO2 Reduction and Metal-Air Batteries

    DEFF Research Database (Denmark)

    Christensen, Rune; Hansen, Heine Anton; Vegge, Tejs

    2015-01-01

    Density functional theory (DFT) calculations have greatly contributed to the atomic level understanding of electrochemical reactions. However, in some cases, the accuracy can be prohibitively low for a detailed understanding of, e.g. reaction mechanisms. Two cases are examined here, i.e. the elec......Density functional theory (DFT) calculations have greatly contributed to the atomic level understanding of electrochemical reactions. However, in some cases, the accuracy can be prohibitively low for a detailed understanding of, e.g. reaction mechanisms. Two cases are examined here, i.......47 eV and 0.17 eV using metals as reference. The presented approach for error identification is expected to be applicable to a very broad range of systems. References: [1] A. A. Peterson, F. Abild-Pedersen, F. Studt, J. Rossmeisl, and J. K. Nørskov, Energy Environ. Sci., 3,1311 (2010) [2] F. Studt, F...

  2. Density-functional theory for fluid-solid and solid-solid phase transitions.

    Science.gov (United States)

    Bharadwaj, Atul S; Singh, Yashwant

    2017-03-01

    We develop a theory to describe solid-solid phase transitions. The density functional formalism of classical statistical mechanics is used to find an exact expression for the difference in the grand thermodynamic potentials of the two coexisting phases. The expression involves both the symmetry conserving and the symmetry broken parts of the direct pair correlation function. The theory is used to calculate phase diagram of systems of soft spheres interacting via inverse power potentials u(r)=ε(σ/r)^{n}, where parameter n measures softness of the potential. We find that for 1/nfcc) structure while for 1/n≥0.154 the body-centred-cubic (bcc) structure is preferred. The bcc structure transforms into the fcc structure upon increasing the density. The calculated phase diagram is in good agreement with the one found from molecular simulations.

  3. Exact-exchange time-dependent density-functional theory for static and dynamic polarizabilities

    International Nuclear Information System (INIS)

    Hirata, So; Ivanov, Stanislav; Bartlett, Rodney J.; Grabowski, Ireneusz

    2005-01-01

    Time-dependent density-functional theory (TDDFT) employing the exact-exchange functional has been formulated on the basis of the optimized-effective-potential (OEP) method of Talman and Shadwick for second-order molecular properties and implemented into a Gaussian-basis-set, trial-vector algorithm. The only approximation involved, apart from the lack of correlation effects and the use of Gaussian-type basis functions, was the consistent use of the adiabatic approximation in the exchange kernel and in the linear response function. The static and dynamic polarizabilities and their anisotropy predicted by the TDDFT with exact exchange (TDOEP) agree accurately with the corresponding values from time-dependent Hartree-Fock theory, the exact-exchange counterpart in the wave function theory. The TDOEP is free from the nonphysical asymptotic decay of the exchange potential of most conventional density functionals or from any other manifestations of the incomplete cancellation of the self-interaction energy. The systematic overestimation of the absolute values and dispersion of polarizabilities that plagues most conventional TDDFT cannot be seen in the TDOEP

  4. Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation

    Science.gov (United States)

    Sison Escaño, Mary Clare; Lacdao Arevalo, Ryan; Gyenge, Elod; Kasai, Hideaki

    2014-09-01

    The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH4- on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements.

  5. Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters using Density Functional Theory

    Science.gov (United States)

    2017-05-05

    Naval Research Laboratory Washington, DC 20375-5320 NRL/MR/6390--17-9724 Equilibrium Structures and Absorption Spectra for SixOy Molecular Clusters...TELEPHONE NUMBER (include area code) b. ABSTRACT c. THIS PAGE 18. NUMBER OF PAGES 17. LIMITATION OF ABSTRACT Equilibrium Structures and Absorption...and electronic excited-state absorption spectra for eqilibrium structures of SixOy molecular clusters using density function theory (DFT) and time

  6. Optical properties of Al nanostructures from time dependent density functional theory

    KAUST Repository

    Mokkath, Junais Habeeb

    2016-04-05

    The optical properties of Al nanostructures are investigated by means of time dependent density functional theory, considering chains of varying length and ladders/stripes of varying aspect ratio. The absorption spectra show redshifting for increasing length and aspect ratio. For the chains the absorption is dominated by HOMO → LUMO transitions, whereas ladders and stripes reveal more complex spectra of plasmonic nature above a specific aspect ratio.

  7. Mechanisms for catalytic carbon nanofiber growth studied by ab initio density functional theory calculations

    DEFF Research Database (Denmark)

    Abild-Pedersen, Frank; Nørskov, Jens Kehlet; Rostrup-Nielsen, Jens

    2006-01-01

    Mechanisms and energetics of graphene growth catalyzed by nickel nanoclusters were studied using ab initio density functional theory calculations. It is demonstrated that nickel step-edge sites act as the preferential growth centers for graphene layers on the nickel surface. Carbon is transported......, and it is argued how these processes may lead to different nanofiber structures. The proposed growth model is found to be in good agreement with previous findings....

  8. Analytic derivatives for perturbatively corrected ''double hybrid'' density functionals: Theory, implementation, and applications

    International Nuclear Information System (INIS)

    Neese, Frank; Schwabe, Tobias; Grimme, Stefan

    2007-01-01

    A recently proposed new family of density functionals [S. Grimme, J. Chem. Phys. 124, 34108 (2006)] adds a fraction of nonlocal correlation as a new ingredient to density functional theory (DFT). This fractional correlation energy is calculated at the level of second-order many-body perturbation theory (PT2) and replaces some of the semilocal DFT correlation of standard hybrid DFT methods. The new ''double hybrid'' functionals (termed, e.g., B2-PLYP) contain only two empirical parameters that have been adjusted in thermochemical calculations on parts of the G2/3 benchmark set. The methods have provided the lowest errors ever obtained by any DFT method for the full G3 set of molecules. In this work, the applicability of the new functionals is extended to the exploration of potential energy surfaces with analytic gradients. The theory of the analytic gradient largely follows the standard theory of PT2 gradients with some additional subtleties due to the presence of the exchange-correlation terms in the self-consistent field operator. An implementation is reported for closed-shell as well as spin-unrestricted reference determinants. Furthermore, the implementation includes external point charge fields and also accommodates continuum solvation models at the level of the conductor like screening model. The density fitting resolution of the identity (RI) approximation can be applied to the evaluation of the PT2 part with large gains in computational efficiency. For systems with ∼500-600 basis functions the evaluation of the double hybrid gradient is approximately four times more expensive than the calculation of the standard hybrid DFT gradient. Extensive test calculations are provided for main group elements and transition metal containing species. The results reveal that the B2-PLYP functional provides excellent molecular geometries that are superior compared to those from standard DFT and MP2

  9. Bridging scales from molecular simulations to classical thermodynamics: density functional theory of capillary condensation in nanopores

    International Nuclear Information System (INIS)

    Neimark, Alexander V; Ravikovitch, Peter I; Vishnyakov, Aleksey

    2003-01-01

    With the example of the capillary condensation of Lennard-Jones fluid in nanopores ranging from 1 to 10 nm, we show that the non-local density functional theory (NLDFT) with properly chosen parameters of intermolecular interactions bridges the scale gap from molecular simulations to macroscopic thermodynamics. On the one hand, NLDFT correctly approximates the results of Monte Carlo simulations (shift of vapour-liquid equilibrium, spinodals, density profiles, adsorption isotherms) for pores wider than about 2 nm. On the other hand, NLDFT smoothly merges (above 7-10 nm) with the Derjaguin-Broekhoff-de Boer equations which represent augmented Laplace-Kelvin equations of capillary condensation and desorption

  10. G-centers in irradiated silicon revisited: A screened hybrid density functional theory approach

    KAUST Repository

    Wang, H.

    2014-05-13

    Electronic structure calculations employing screened hybrid density functional theory are used to gain fundamental insight into the interaction of carbon interstitial (Ci) and substitutional (Cs) atoms forming the CiCs defect known as G-center in silicon (Si). The G-center is one of the most important radiation related defects in Czochralski grown Si. We systematically investigate the density of states and formation energy for different types of CiCs defects with respect to the Fermi energy for all possible charge states. Prevalence of the neutral state for the C-type defect is established.

  11. Nonadiabatic Dynamics in Single-Electron Tunneling Devices with Time-Dependent Density-Functional Theory

    Science.gov (United States)

    Dittmann, Niklas; Splettstoesser, Janine; Helbig, Nicole

    2018-04-01

    We simulate the dynamics of a single-electron source, modeled as a quantum dot with on-site Coulomb interaction and tunnel coupling to an adjacent lead in time-dependent density-functional theory. Based on this system, we develop a time-nonlocal exchange-correlation potential by exploiting analogies with quantum-transport theory. The time nonlocality manifests itself in a dynamical potential step. We explicitly link the time evolution of the dynamical step to physical relaxation timescales of the electron dynamics. Finally, we discuss prospects for simulations of larger mesoscopic systems.

  12. VV and VO2 defects in silicon studied with hybrid density functional theory

    KAUST Repository

    Christopoulos, Stavros Richard G

    2014-12-07

    The formation of VO (A-center), VV and VO2 defects in irradiated Czochralski-grown silicon (Si) is of technological importance. Recent theoretical studies have examined the formation and charge states of the A-center in detail. Here we use density functional theory employing hybrid functionals to analyze the formation of VV and VO2 defects. The formation energy as a function of the Fermi energy is calculated for all possible charge states. For the VV and VO2 defects double negatively charged and neutral states dominate, respectively.

  13. Nuclear reactivity indices in the context of spin polarized density functional theory

    International Nuclear Information System (INIS)

    Cardenas, Carlos; Lamsabhi, Al Mokhtar; Fuentealba, Patricio

    2006-01-01

    In this work, the nuclear reactivity indices of density functional theory have been generalized to the spin polarized case and their relationship to electron spin polarized indices has been established. In particular, the spin polarized version of the nuclear Fukui function has been proposed and a finite difference approximation has been used to evaluate it. Applications to a series of triatomic molecules demonstrate the ability of the new functions to predict the geometrical changes due to a change in the spin multiplicity. The main equations in the different ensembles have also been presented

  14. Density functional theory investigation of two-dimensional dipolar fermions in a harmonic trap

    International Nuclear Information System (INIS)

    Ustunel, Hande; Abedinpour, Saeed H; Tanatar, B

    2014-01-01

    We investigate the behavior of polarized dipolar fermions in a two-dimensional harmonic trap in the framework of the density functional theory (DFT) formalism using the local density approximation. We treat only a few particles interacting moderately. Important results were deduced concerning key characteristics of the system such as total energy and particle density. Our results indicate that, at variance with Coulombic systems, the exchange- correlation component was found to provide a large contribution to the total energy for a large range of interaction strengths and particle numbers. In addition, the density profiles of the dipoles are shown to display important features around the origin that is not possible to capture by earlier, simpler treatments of such systems

  15. Radical scavenging activity of some natural tropolones by density functional theory

    Directory of Open Access Journals (Sweden)

    A. G. Al-Sehemi

    2017-07-01

    Full Text Available The ground state neutral geometries of some natural tropolones, i.e. stipitatonic acid (AF1, stipitalide (AF2, stipitaldehydic acid (AF3 and methyl stipitate (AF4 have been optimized by using Density Functional Theory (DFT at B3LYP/6-31G*, B3LYP/6-31G**, B3LYP/6-31+G* and B3LYP/6-31+G** levels of theory. The excited state geometries of AF1-AF4 were optimized by adopting the Time Dependent Density Functional Theory (TDDFT at the same levels of theory. The frequencies and cation species of AF1-AF4 were also computed at all the above mentioned levels of theory. We shed light on the electro-optical and molecular properties, e.g. energy gaps, highest occupied molecular orbitals, lowest unoccupied molecular orbitals, absorption wavelengths, electronegativity (χ, hardness (η, electrophilicity (ω, softness (S, electrophilicity index (ωi and the radical scavenging activity (RSA. Hydrogen atom transfer (HAT and one-electron transfer mechanisms have been discussed to shed light on the RSA. The smallest ionization potential and bond dissociation energy of AF4 are revealing that this compound would have more RSA than those of other counterparts.

  16. Magnetic exchange couplings from constrained density functional theory: an efficient approach utilizing analytic derivatives.

    Science.gov (United States)

    Phillips, Jordan J; Peralta, Juan E

    2011-11-14

    We introduce a method for evaluating magnetic exchange couplings based on the constrained density functional theory (C-DFT) approach of Rudra, Wu, and Van Voorhis [J. Chem. Phys. 124, 024103 (2006)]. Our method shares the same physical principles as C-DFT but makes use of the fact that the electronic energy changes quadratically and bilinearly with respect to the constraints in the range of interest. This allows us to use coupled perturbed Kohn-Sham spin density functional theory to determine approximately the corrections to the energy of the different spin configurations and construct a priori the relevant energy-landscapes obtained by constrained spin density functional theory. We assess this methodology in a set of binuclear transition-metal complexes and show that it reproduces very closely the results of C-DFT. This demonstrates a proof-of-concept for this method as a potential tool for studying a number of other molecular phenomena. Additionally, routes to improving upon the limitations of this method are discussed. © 2011 American Institute of Physics

  17. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    International Nuclear Information System (INIS)

    Sundararaman, Ravishankar; Goddard, William A. III; Arias, Tomas A.

    2017-01-01

    First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Lastly, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.

  18. Grand canonical electronic density-functional theory: Algorithms and applications to electrochemistry

    Science.gov (United States)

    Sundararaman, Ravishankar; Goddard, William A.; Arias, Tomas A.

    2017-03-01

    First-principles calculations combining density-functional theory and continuum solvation models enable realistic theoretical modeling and design of electrochemical systems. When a reaction proceeds in such systems, the number of electrons in the portion of the system treated quantum mechanically changes continuously, with a balancing charge appearing in the continuum electrolyte. A grand-canonical ensemble of electrons at a chemical potential set by the electrode potential is therefore the ideal description of such systems that directly mimics the experimental condition. We present two distinct algorithms: a self-consistent field method and a direct variational free energy minimization method using auxiliary Hamiltonians (GC-AuxH), to solve the Kohn-Sham equations of electronic density-functional theory directly in the grand canonical ensemble at fixed potential. Both methods substantially improve performance compared to a sequence of conventional fixed-number calculations targeting the desired potential, with the GC-AuxH method additionally exhibiting reliable and smooth exponential convergence of the grand free energy. Finally, we apply grand-canonical density-functional theory to the under-potential deposition of copper on platinum from chloride-containing electrolytes and show that chloride desorption, not partial copper monolayer formation, is responsible for the second voltammetric peak.

  19. A physically motivated sparse cubature scheme with applications to molecular density-functional theory

    International Nuclear Information System (INIS)

    Rodriguez, Juan I; Thompson, David C; Anderson, James S M; Thomson, Jordan W; Ayers, Paul W

    2008-01-01

    We present a novel approach for performing multi-dimensional integration of arbitrary functions. The method starts with Smolyak-type sparse grids as cubature formulae on the unit cube and uses a transformation of coordinates based on the conditional distribution method to adapt those formulae to real space. Our method is tested on integrals in one, two, three and six dimensions. The three dimensional integration formulae are used to evaluate atomic interaction energies via the Gordon-Kim model. The six dimensional integration formulae are tested in conjunction with the nonlocal exchange-correlation energy functional proposed by Lee and Parr. This methodology is versatile and powerful; we contemplate application to frozen-density embedding, next-generation molecular-mechanics force fields, 'kernel-type' exchange-correlation energy functionals and pair-density functional theory

  20. A Comparative Density Functional Theory and Density Functional Tight Binding Study of Phases of Nitrogen Including a High Energy Density Material N8

    Directory of Open Access Journals (Sweden)

    Nicholas Capel

    2015-11-01

    Full Text Available We present a comparative dispersion-corrected Density Functional Theory (DFT and Density Functional Tight Binding (DFTB-D study of several phases of nitrogen, including the well-known alpha, beta, and gamma phases as well as recently discovered highly energetic phases: covalently bound cubic gauche (cg nitrogen and molecular (vdW-bound N8 crystals. Among several tested parametrizations of N–N interactions for DFTB, we identify only one that is suitable for modeling of all these phases. This work therefore establishes the applicability of DFTB-D to studies of phases, including highly metastable phases, of nitrogen, which will be of great use for modelling of dynamics of reactions involving these phases, which may not be practical with DFT due to large required space and time scales. We also derive a dispersion-corrected DFT (DFT-D setup (atom-centered basis parameters and Grimme dispersion parameters tuned for accurate description simultaneously of several nitrogen allotropes including covalently and vdW-bound crystals and including high-energy phases.

  1. PREFACE: Classical density functional theory methods in soft and hard matter Classical density functional theory methods in soft and hard matter

    Science.gov (United States)

    Haataja, Mikko; Gránásy, László; Löwen, Hartmut

    2010-08-01

    Herein we provide a brief summary of the background, events and results/outcome of the CECAM workshop 'Classical density functional theory methods in soft and hard matter held in Lausanne between October 21 and October 23 2009, which brought together two largely separately working communities, both of whom employ classical density functional techniques: the soft-matter community and the theoretical materials science community with interests in phase transformations and evolving microstructures in engineering materials. After outlining the motivation for the workshop, we first provide a brief overview of the articles submitted by the invited speakers for this special issue of Journal of Physics: Condensed Matter, followed by a collection of outstanding problems identified and discussed during the workshop. 1. Introduction Classical density functional theory (DFT) is a theoretical framework, which has been extensively employed in the past to study inhomogeneous complex fluids (CF) [1-4] and freezing transitions for simple fluids, amongst other things. Furthermore, classical DFT has been extended to include dynamics of the density field, thereby opening a new avenue to study phase transformation kinetics in colloidal systems via dynamical DFT (DDFT) [5]. While DDFT is highly accurate, the computations are numerically rather demanding, and cannot easily access the mesoscopic temporal and spatial scales where diffusional instabilities lead to complex solidification morphologies. Adaptation of more efficient numerical methods would extend the domain of DDFT towards this regime of particular interest to materials scientists. In recent years, DFT has re-emerged in the form of the so-called 'phase-field crystal' (PFC) method for solid-state systems [6, 7], and it has been successfully employed to study a broad variety of interesting materials phenomena in both atomic and colloidal systems, including elastic and plastic deformations, grain growth, thin film growth, solid

  2. Comment on "Density functional theory is straying from the path toward the exact functional"

    DEFF Research Database (Denmark)

    Kepp, Kasper Planeta

    2017-01-01

    Medvedev et al (Reports, 6 January 2017, p. 49) argue that recent density functionals stray from the path toward exactness. This conclusion rests on very compact 1s2 and 1s22s2 systems favored by the Hartree-Fock picture. Comparison to actual energies for the same systems indicates that the "stra...

  3. Multicomponent Density Functional Theory: Impact of Nuclear Quantum Effects on Proton Affinities and Geometries.

    Science.gov (United States)

    Brorsen, Kurt R; Yang, Yang; Hammes-Schiffer, Sharon

    2017-08-03

    Nuclear quantum effects such as zero point energy play a critical role in computational chemistry and often are included as energetic corrections following geometry optimizations. The nuclear-electronic orbital (NEO) multicomponent density functional theory (DFT) method treats select nuclei, typically protons, quantum mechanically on the same level as the electrons. Electron-proton correlation is highly significant, and inadequate treatments lead to highly overlocalized nuclear densities. A recently developed electron-proton correlation functional, epc17, has been shown to provide accurate nuclear densities for molecular systems. Herein, the NEO-DFT/epc17 method is used to compute the proton affinities for a set of molecules and to examine the role of nuclear quantum effects on the equilibrium geometry of FHF - . The agreement of the computed results with experimental and benchmark values demonstrates the promise of this approach for including nuclear quantum effects in calculations of proton affinities, pK a 's, optimized geometries, and reaction paths.

  4. Optimal control theory for quantum-classical systems: Ehrenfest molecular dynamics based on time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Castro, A; Gross, E K U

    2014-01-01

    We derive the fundamental equations of an optimal control theory for systems containing both quantum electrons and classical ions. The system is modeled with Ehrenfest dynamics, a non-adiabatic variant of molecular dynamics. The general formulation, that needs the fully correlated many-electron wavefunction, can be simplified by making use of time-dependent density-functional theory. In this case, the optimal control equations require some modifications that we will provide. The abstract general formulation is complemented with the simple example of the H 2 + molecule in the presence of a laser field. (paper)

  5. Density-functional theory based on the electron distribution on the energy coordinate

    Science.gov (United States)

    Takahashi, Hideaki

    2018-03-01

    We developed an electronic density functional theory utilizing a novel electron distribution n(ɛ) as a basic variable to compute ground state energy of a system. n(ɛ) is obtained by projecting the electron density n({\\boldsymbol{r}}) defined on the space coordinate {\\boldsymbol{r}} onto the energy coordinate ɛ specified with the external potential {\\upsilon }ext}({\\boldsymbol{r}}) of interest. It was demonstrated that the Kohn-Sham equation can also be formulated with the exchange-correlation functional E xc[n(ɛ)] that employs the density n(ɛ) as an argument. It turned out an exchange functional proposed in our preliminary development suffices to describe properly the potential energies of several types of chemical bonds with comparable accuracies to the corresponding functional based on local density approximation. As a remarkable feature of the distribution n(ɛ) it inherently involves the spatially non-local information of the exchange hole at the bond dissociation limit in contrast to conventional approximate functionals. By taking advantage of this property we also developed a prototype of the static correlation functional E sc including no empirical parameters, which showed marked improvements in describing the dissociations of covalent bonds in {{{H}}}2,{{{C}}}2{{{H}}}4 and {CH}}4 molecules.

  6. Obtaining Hartree-Fock and density functional theory doubly excited states with Car-Parrinello density matrix search

    Science.gov (United States)

    Liang, Wenkel; Isborn, Christine M.; Li, Xiaosong

    2009-11-01

    The calculation of doubly excited states is one of the major problems plaguing the modern day excited state workhorse methodology of linear response time dependent Hartree-Fock (TDHF) and density function theory (TDDFT). We have previously shown that the use of a resonantly tuned field within real-time TDHF and TDDFT is able to simultaneously excite both the α and β electrons to achieve the two-electron excited states of minimal basis H2 and HeH+ [C. M. Isborn and X. Li, J. Chem. Phys. 129, 204107 (2008)]. We now extend this method to many electron systems with the use of our Car-Parrinello density matrix search (CP-DMS) with a first-principles fictitious mass method for wave function optimization [X. Li, C. L. Moss, W. Liang, and Y. Feng, J. Chem. Phys. 130, 234115 (2009)]. Real-time TDHF/TDDFT is used during the application of the laser field perturbation, driving the electron density toward the doubly excited state. The CP-DMS method then converges the density to the nearest stationary state. We present these stationary state doubly excited state energies and properties at the HF and DFT levels for H2, HeH+, lithium hydride, ethylene, and butadiene.

  7. Differentiability in density-functional theory: Further study of the locality theorem

    International Nuclear Information System (INIS)

    Lindgren, Ingvar; Salomonson, Sten

    2004-01-01

    The locality theorem in density-functional theory (DFT) states that the functional derivative of the Hohenberg-Kohn universal functional can be expressed as a local multiplicative potential function, and this is the basis of DFT and of the successful Kohn-Sham model. Nesbet has in several papers [Phys. Rev. A 58, R12 (1998); ibid.65, 010502 (2001); Adv. Quant. Chem, 43, 1 (2003)] claimed that this theorem is in conflict with fundamental quantum physics, and as a consequence that the Hohenberg-Kohn theory cannot be generally valid. We have commented upon these works [Comment, Phys. Rev. A 67, 056501 (2003)] and recently extended the arguments [Adv. Quantum Chem. 43, 95 (2003)]. We have shown that there is no such conflict and that the locality theorem is inherently exact. In the present work we have furthermore verified this numerically by constructing a local Kohn-Sham potential for the 1s2s 3 S state of helium that generates the many-body electron density and shown that the corresponding 2s Kohn-Sham orbital eigenvalue agrees with the ionization energy to nine digits. Similar result is obtained with the Hartree-Fock density. Therefore, in addition to verifying the locality theorem, this result also confirms the so-called ionization-potential theorem

  8. Total-energy Assisted Tight-binding Method Based on Local Density Approximation of Density Functional Theory

    Science.gov (United States)

    Fujiwara, Takeo; Nishino, Shinya; Yamamoto, Susumu; Suzuki, Takashi; Ikeda, Minoru; Ohtani, Yasuaki

    2018-06-01

    A novel tight-binding method is developed, based on the extended Hückel approximation and charge self-consistency, with referring the band structure and the total energy of the local density approximation of the density functional theory. The parameters are so adjusted by computer that the result reproduces the band structure and the total energy, and the algorithm for determining parameters is established. The set of determined parameters is applicable to a variety of crystalline compounds and change of lattice constants, and, in other words, it is transferable. Examples are demonstrated for Si crystals of several crystalline structures varying lattice constants. Since the set of parameters is transferable, the present tight-binding method may be applicable also to molecular dynamics simulations of large-scale systems and long-time dynamical processes.

  9. Alternative definitions of the frozen energy in energy decomposition analysis of density functional theory calculations.

    Science.gov (United States)

    Horn, Paul R; Head-Gordon, Martin

    2016-02-28

    In energy decomposition analysis (EDA) of intermolecular interactions calculated via density functional theory, the initial supersystem wavefunction defines the so-called "frozen energy" including contributions such as permanent electrostatics, steric repulsions, and dispersion. This work explores the consequences of the choices that must be made to define the frozen energy. The critical choice is whether the energy should be minimized subject to the constraint of fixed density. Numerical results for Ne2, (H2O)2, BH3-NH3, and ethane dissociation show that there can be a large energy lowering associated with constant density orbital relaxation. By far the most important contribution is constant density inter-fragment relaxation, corresponding to charge transfer (CT). This is unwanted in an EDA that attempts to separate CT effects, but it may be useful in other contexts such as force field development. An algorithm is presented for minimizing single determinant energies at constant density both with and without CT by employing a penalty function that approximately enforces the density constraint.

  10. Nematic-smectic A and nematic-solid transitions of parallel hard spherocylinders from density functional theory

    NARCIS (Netherlands)

    University Utrecht

    1992-01-01

    A simple density functional theory for the various liquid-crystalline phases of parallel hard spherocylinders is formulated on the basis of Pynn's ansatz for the direct correlation function of the spherocylinders. Fair agreement with the computer simulations is found.

  11. Stopping of deuterium in warm dense deuterium from Ehrenfest time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Magyar, R.J.; Shulenburger, L.; Baczewski, A.D. [Sandia National Laboratories - Multi-scale Physics 1444 MS 1322, Albuquerque, NM (United States)

    2016-06-15

    In these proceedings, we show that time-dependent density functional theory is capable of stopping calculations at the extreme conditions of temperature and pressure seen in warm dense matter. The accuracy of the stopping curves tends to be up to about 20% lower than empirical models that are in use. However, TDDFT calculations are free from fitting parameters and assumptions about the model form of the dielectric function. This work allows the simulation of ion stopping in many materials that are difficult to study experimentally. (copyright 2016 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

  12. Vacancy formation in MoO3: hybrid density functional theory and photoemission experiments

    KAUST Repository

    Salawu, Omotayo Akande

    2016-09-29

    Molybdenum oxide (MoO3) is an important material that is being considered for numerous technological applications, including catalysis and electrochromism. In the present study, we apply hybrid density functional theory to investigate O and Mo vacancies in the orthorhombic phase. We determine the vacancy formation energies of different defect sites as functions of the electron chemical potential, addressing different charge states. In addition, we investigate the consequences of defects for the material properties. Ultraviolet photoemission spectroscopy is employed to study the valence band of stoichiometric and O defective MoO3. We show that O vacancies result in occupied in-gap states.

  13. Vacancy formation in MoO3: hybrid density functional theory and photoemission experiments

    KAUST Repository

    Salawu, Omotayo Akande; Chroneos, Alexander; Vasilopoulou, Maria; Kennou, Stella; Schwingenschlö gl, Udo

    2016-01-01

    Molybdenum oxide (MoO3) is an important material that is being considered for numerous technological applications, including catalysis and electrochromism. In the present study, we apply hybrid density functional theory to investigate O and Mo vacancies in the orthorhombic phase. We determine the vacancy formation energies of different defect sites as functions of the electron chemical potential, addressing different charge states. In addition, we investigate the consequences of defects for the material properties. Ultraviolet photoemission spectroscopy is employed to study the valence band of stoichiometric and O defective MoO3. We show that O vacancies result in occupied in-gap states.

  14. Many-body perturbation theory using the density-functional concept: beyond the GW approximation

    OpenAIRE

    Bruneval, Fabien; Sottile, Francesco; Olevano, Valerio; Del Sole, Rodolfo; Reining, Lucia

    2005-01-01

    We propose an alternative formulation of Many-Body Perturbation Theory that uses the density-functional concept. Instead of the usual four-point integral equation for the polarizability, we obtain a two-point one, that leads to excellent optical absorption and energy loss spectra. The corresponding three-point vertex function and self-energy are then simply calculated via an integration, for any level of approximation. Moreover, we show the direct impact of this formulation on the time-depend...

  15. Lattice dynamics calculations based on density-functional perturbation theory in real space

    Science.gov (United States)

    Shang, Honghui; Carbogno, Christian; Rinke, Patrick; Scheffler, Matthias

    2017-06-01

    A real-space formalism for density-functional perturbation theory (DFPT) is derived and applied for the computation of harmonic vibrational properties in molecules and solids. The practical implementation using numeric atom-centered orbitals as basis functions is demonstrated exemplarily for the all-electron Fritz Haber Institute ab initio molecular simulations (FHI-aims) package. The convergence of the calculations with respect to numerical parameters is carefully investigated and a systematic comparison with finite-difference approaches is performed both for finite (molecules) and extended (periodic) systems. Finally, the scaling tests and scalability tests on massively parallel computer systems demonstrate the computational efficiency.

  16. Remarks on time-dependent [current]-density functional theory for open quantum systems.

    Science.gov (United States)

    Yuen-Zhou, Joel; Aspuru-Guzik, Alán

    2013-08-14

    Time-dependent [current]-density functional theory for open quantum systems (OQS) has emerged as a formalism that can incorporate dissipative effects in the dynamics of many-body quantum systems. Here, we review and clarify some formal aspects of these theories that have been recently questioned in the literature. In particular, we provide theoretical support for the following conclusions: (1) contrary to what we and others had stated before, within the master equation framework, there is in fact a one-to-one mapping between vector potentials and current densities for fixed initial state, particle-particle interaction, and memory kernel; (2) regardless of the first conclusion, all of our recently suggested Kohn-Sham (KS) schemes to reproduce the current and particle densities of the original OQS, and in particular, the use of a KS closed driven system, remains formally valid; (3) the Lindblad master equation maintains the positivity of the density matrix regardless of the time-dependence of the Hamiltonian or the dissipation operators; (4) within the stochastic Schrödinger equation picture, a one-to-one mapping from stochastic vector potential to stochastic current density for individual trajectories has not been proven so far, except in the case where the vector potential is the same for every member of the ensemble, in which case, it reduces to the Lindblad master equation picture; (5) master equations may violate certain desired properties of the density matrix, such as positivity, but they remain as one of the most useful constructs to study OQS when the environment is not easily incorporated explicitly in the calculation. The conclusions support our previous work as formally rigorous, offer new insights into it, and provide a common ground to discuss related theories.

  17. Decay of hollow states in time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Kapoor, Varun; Bauer, Dieter [Institut fuer Physik, Wismarsche Str. 43-45, Universitaet Rostock, Rostock-18051 (Germany)

    2012-07-01

    Hollow or multiply excited states are inaccessible in time dependent density functional theory (TDDFT) using adiabatic Kohn-Sham potentials. We determine the exact Kohn Sham (KS) potential for doubly excited states in an exactly solvable model Helium atom. The exact single-particle density corresponds to the energetically lowest quasi-stationary state in the exact KS potential. We describe how this exact potential controls the decay by a barrier whose origin is traced back to phase of the exact KS orbital. The potential controls the barrier height and width in order for the density to tunnel out and decay with the same rate as the doubly excited state in the ab initio time-dependent Schroedinger calculation. Instead, adiabatic KS potentials only show direct photoionization but no autoionization. A frequency-dependent linear response kernel would be necessary in order to capture the decay of autoionizing states.

  18. Density Functional Theory Study of the Interaction of Hydrogen with Li6C60.

    Science.gov (United States)

    Wang, Qian; Jena, Puru

    2012-05-03

    Hydrogen storage properties of Li-coated C60 fullerene have been studied using density functional theory within the local density as well as generalized gradient approximation. Hydrogen atoms are found to bind to Li6C60 in two distinct forms, with the first set attaching to C atoms, not linked to Li, in atomic form. Once all such C atoms are saturated with hydrogen, the second set of hydrogen atoms bind quasi-molecularly to the Li atoms, five of which remain in the exohedral and the sixth in the endohedral position. The corresponding hydrogen gravimetric density in Li6C60H40 is 5 wt %. Desorption of hydrogen takes place in succession, the ones bound quasi-molecularly desorbing at a temperature lower than the ones bound atomically. The results are compared with the recent experiment on hydrogen adsorption in Li6C60.

  19. Density function theory study of the adsorption and dissociation of carbon monoxide on tungsten nanoparticles.

    Science.gov (United States)

    Weng, Meng-Hsiung; Ju, Shin-Pon; Chen, Hsin-Tsung; Chen, Hui-Lung; Lu, Jian-Ming; Lin, Ken-Huang; Lin, Jenn-Sen; Hsieh, Jin-Yuan; Yang, Hsi-Wen

    2013-02-01

    The adsorption and dissociation properties of carbon monoxide (CO) molecule on tungsten W(n) (n = 10-15) nanoparticles have been investigated by density-functional theory (DFT) calculations. The lowest-energy structures for W(n) (n = 10-15) nanoparticles are found by the basin-hopping method and big-bang method with the modified tight-binding many-body potential. We calculated the corresponding adsorption energies, C-O bond lengths and dissociation barriers for adsorption of CO on nanoparticles. The electronic properties of CO on nanoparticles are studied by the analysis of density of state and charge density. The characteristic of CO on W(n) nanoparticles are also compared with that of W bulk.

  20. MADNESS applied to density functional theory in chemistry and nuclear physics

    International Nuclear Information System (INIS)

    Fann, G I; Harrison, R J; Beylkin, G; Jia, J; Hartman-Baker, R; Shelton, W A; Sugiki, S

    2007-01-01

    We describe some recent mathematical results in constructing computational methods that lead to the development of fast and accurate multiresolution numerical methods for solving quantum chemistry and nuclear physics problems based on Density Functional Theory (DFT). Using low separation rank representations of functions and operators in conjunction with representations in multiwavelet bases, we developed a multiscale solution method for integral and differential equations and integral transforms. The Poisson equation, the Schrodinger equation, and the projector on the divergence free functions provide important examples with a wide range of applications in computational chemistry, nuclear physics, computational electromagnetic and fluid dynamics. We have implemented this approach along with adaptive representations of operators and functions in the multiwavelet basis and low separation rank (LSR) approximation of operators and functions. These methods have been realized and implemented in a software package called Multiresolution Adaptive Numerical Evaluation for Scientific Simulation (MADNESS)

  1. Density functional theory for field emission from carbon nano-structures.

    Science.gov (United States)

    Li, Zhibing

    2015-12-01

    Electron field emission is understood as a quantum mechanical many-body problem in which an electronic quasi-particle of the emitter is converted into an electron in vacuum. Fundamental concepts of field emission, such as the field enhancement factor, work-function, edge barrier and emission current density, will be investigated, using carbon nanotubes and graphene as examples. A multi-scale algorithm basing on density functional theory is introduced. We will argue that such a first principle approach is necessary and appropriate for field emission of nano-structures, not only for a more accurate quantitative description, but, more importantly, for deeper insight into field emission. Copyright © 2015 The Author. Published by Elsevier B.V. All rights reserved.

  2. Quantum computing without wavefunctions: time-dependent density functional theory for universal quantum computation.

    Science.gov (United States)

    Tempel, David G; Aspuru-Guzik, Alán

    2012-01-01

    We prove that the theorems of TDDFT can be extended to a class of qubit Hamiltonians that are universal for quantum computation. The theorems of TDDFT applied to universal Hamiltonians imply that single-qubit expectation values can be used as the basic variables in quantum computation and information theory, rather than wavefunctions. From a practical standpoint this opens the possibility of approximating observables of interest in quantum computations directly in terms of single-qubit quantities (i.e. as density functionals). Additionally, we also demonstrate that TDDFT provides an exact prescription for simulating universal Hamiltonians with other universal Hamiltonians that have different, and possibly easier-to-realize two-qubit interactions. This establishes the foundations of TDDFT for quantum computation and opens the possibility of developing density functionals for use in quantum algorithms.

  3. Polarizable embedding with a multiconfiguration short-range density functional theory linear response method

    DEFF Research Database (Denmark)

    Hedegård, Erik D.; Olsen, Jógvan Magnus Haugaard; Knecht, Stefan

    2015-01-01

    . To demonstrate the capabilities of PE-MC-srDFT, we also investigated the retinylidene Schiff base chromophore embedded in the channelrhodopsin protein. While using a much more compact reference wave function in terms of active space, our PE-MC-srDFT approach yields excitation energies comparable in quality......We present here the coupling of a polarizable embedding (PE) model to the recently developed multiconfiguration short-range density functional theory method (MC-srDFT), which can treat multiconfigurational systems with a simultaneous account for dynamical and static correlation effects. PE......-MC-srDFT is designed to combine efficient treatment of complicated electronic structures with inclusion of effects from the surrounding environment. The environmental effects encompass classical electrostatic interactions as well as polarization of both the quantum region and the environment. Using response theory...

  4. Dispersion- and Exchange-Corrected Density Functional Theory for Sodium Ion Hydration.

    Science.gov (United States)

    Soniat, Marielle; Rogers, David M; Rempe, Susan B

    2015-07-14

    A challenge in density functional theory is developing functionals that simultaneously describe intermolecular electron correlation and electron delocalization. Recent exchange-correlation functionals address those two issues by adding corrections important at long ranges: an atom-centered pairwise dispersion term to account for correlation and a modified long-range component of the electron exchange term to correct for delocalization. Here we investigate how those corrections influence the accuracy of binding free energy predictions for sodium-water clusters. We find that the dual-corrected ωB97X-D functional gives cluster binding energies closest to high-level ab initio methods (CCSD(T)). Binding energy decomposition shows that the ωB97X-D functional predicts the smallest ion-water (pairwise) interaction energy and larger multibody contributions for a four-water cluster than most other functionals - a trend consistent with CCSD(T) results. Also, ωB97X-D produces the smallest amounts of charge transfer and the least polarizable waters of the density functionals studied, which mimics the lower polarizability of CCSD. When compared with experimental binding free energies, however, the exchange-corrected CAM-B3LYP functional performs best (error <1 kcal/mol), possibly because of its parametrization to experimental formation enthalpies. For clusters containing more than four waters, "split-shell" coordination must be considered to obtain accurate free energies in comparison with experiment.

  5. Excitonic effects in solids : time-dependent density functional theory versus the Bethe-Salpeter equation

    International Nuclear Information System (INIS)

    Sagmeister, S.

    2009-01-01

    The aim of this work is to compare two state-of-the-art methods for the investigation of excitonic effects in solids, namely Time-Dependent Density Functional Theory (TDDFT) and Many-Body Perturbation Theory (MBPT), for selected simple gap systems as well as semiconducting polymers. Within TDDFT, the linear response framework is used and the Dyson equation for the density-density response function is solved, whereas within MBPT, the Bethe-Salpeter equation (BSE) for the electron-hole correlation function is solved. The dielectric function is obtained as a last step. Both techniques take into account the excitonic effects caused by the interaction of electron-hole pairs. In the former these effects are included in the exchange-correlation (xc) kernel, whereas in the latter they are located in the interaction kernel of the BSE. Kohn-Sham single-particle wave functions obtained from Density Functional Theory within the linearized augmented planewave (LAPW) method are used to calculate all relevant quantities of the formalism. For the simple systems GaAs, Si and LiF are chosen. The role of several approximations to the xc kernel is studied and it is found that for GaAs and Si simple semi-empirical models provide a dielectric function in accordance with the BSE. For the case of LiF, being a system with a weak screening and a strongly bound exciton, only an xc kernel derived from MBPT yields reasonable results but still a slight discrepancy to the BSE is observed. Finally, the semiconducting polymers poly-acetylene and poly(phenylene-vinylene) (PPV) are studied. For both materials the concept of semi-empirical approximations to the xc kernel turns out to be ambiguous due to their low-dimensional character. In the case of poly-acetylene, the xc kernel derived from MBPT yields a dielectric function which is in close but not exact agreement with the one obtained from the BSE. (author) [de

  6. Influence of van der Waals forces on the adsorption structure of benzene on silicon studied using density functional theory

    DEFF Research Database (Denmark)

    Johnston, Karen; Kleis, Jesper; Lundqvist, Bengt

    2008-01-01

    Two different adsorption configurations of benzene on the Si(001)-(2×1) surface, the tight-bridge and butterfly structures, were studied using density functional theory. Several exchange and correlation functionals were used, including the recently developed van der Waals density functional (vd...

  7. A comparison of density functional theory and coupled cluster methods for the calculation of electric dipole polarizability gradients of methane

    DEFF Research Database (Denmark)

    Paidarová, Ivana; Sauer, Stephan P. A.

    2012-01-01

    We have compared the performance of density functional theory (DFT) using five different exchange-correlation functionals with four coupled cluster theory based wave function methods in the calculation of geometrical derivatives of the polarizability tensor of methane. The polarizability gradient...

  8. The Density Functional Theory of Flies: Predicting distributions of interacting active organisms

    Science.gov (United States)

    Kinkhabwala, Yunus; Valderrama, Juan; Cohen, Itai; Arias, Tomas

    On October 2nd, 2016, 52 people were crushed in a stampede when a crowd panicked at a religious gathering in Ethiopia. The ability to predict the state of a crowd and whether it is susceptible to such transitions could help prevent such catastrophes. While current techniques such as agent based models can predict transitions in emergent behaviors of crowds, the assumptions used to describe the agents are often ad hoc and the simulations are computationally expensive making their application to real-time crowd prediction challenging. Here, we pursue an orthogonal approach and ask whether a reduced set of variables, such as the local densities, are sufficient to describe the state of a crowd. Inspired by the theoretical framework of Density Functional Theory, we have developed a system that uses only measurements of local densities to extract two independent crowd behavior functions: (1) preferences for locations and (2) interactions between individuals. With these two functions, we have accurately predicted how a model system of walking Drosophila melanogaster distributes itself in an arbitrary 2D environment. In addition, this density-based approach measures properties of the crowd from only observations of the crowd itself without any knowledge of the detailed interactions and thus it can make predictions about the resulting distributions of these flies in arbitrary environments, in real-time. This research was supported in part by ARO W911NF-16-1-0433.

  9. Quantum electrodynamical time-dependent density functional theory for many-electron systems on a lattice

    Science.gov (United States)

    Farzanehpour, Mehdi; Tokatly, Ilya; Nano-Bio Spectroscopy Group; ETSF Scientific Development Centre Team

    2015-03-01

    We present a rigorous formulation of the time-dependent density functional theory for interacting lattice electrons strongly coupled to cavity photons. We start with an example of one particle on a Hubbard dimer coupled to a single photonic mode, which is equivalent to the single mode spin-boson model or the quantum Rabi model. For this system we prove that the electron-photon wave function is a unique functional of the electronic density and the expectation value of the photonic coordinate, provided the initial state and the density satisfy a set of well defined conditions. Then we generalize the formalism to many interacting electrons on a lattice coupled to multiple photonic modes and prove the general mapping theorem. We also show that for a system evolving from the ground state of a lattice Hamiltonian any density with a continuous second time derivative is locally v-representable. Spanish Ministry of Economy and Competitiveness (Grant No. FIS2013-46159-C3-1-P), Grupos Consolidados UPV/EHU del Gobierno Vasco (Grant No. IT578-13), COST Actions CM1204 (XLIC) and MP1306 (EUSpec).

  10. Why do ultrasoft repulsive particles cluster and crystallize? Analytical results from density-functional theory.

    Science.gov (United States)

    Likos, Christos N; Mladek, Bianca M; Gottwald, Dieter; Kahl, Gerhard

    2007-06-14

    We demonstrate the accuracy of the hypernetted chain closure and of the mean-field approximation for the calculation of the fluid-state properties of systems interacting by means of bounded and positive pair potentials with oscillating Fourier transforms. Subsequently, we prove the validity of a bilinear, random-phase density functional for arbitrary inhomogeneous phases of the same systems. On the basis of this functional, we calculate analytically the freezing parameters of the latter. We demonstrate explicitly that the stable crystals feature a lattice constant that is independent of density and whose value is dictated by the position of the negative minimum of the Fourier transform of the pair potential. This property is equivalent with the existence of clusters, whose population scales proportionally to the density. We establish that regardless of the form of the interaction potential and of the location on the freezing line, all cluster crystals have a universal Lindemann ratio Lf=0.189 at freezing. We further make an explicit link between the aforementioned density functional and the harmonic theory of crystals. This allows us to establish an equivalence between the emergence of clusters and the existence of negative Fourier components of the interaction potential. Finally, we make a connection between the class of models at hand and the system of infinite-dimensional hard spheres, when the limits of interaction steepness and space dimension are both taken to infinity in a particularly described fashion.

  11. Size-dependent error of the density functional theory ionization potential in vacuum and solution.

    Science.gov (United States)

    Sosa Vazquez, Xochitl A; Isborn, Christine M

    2015-12-28

    Density functional theory is often the method of choice for modeling the energetics of large molecules and including explicit solvation effects. It is preferable to use a method that treats systems of different sizes and with different amounts of explicit solvent on equal footing. However, recent work suggests that approximate density functional theory has a size-dependent error in the computation of the ionization potential. We here investigate the lack of size-intensivity of the ionization potential computed with approximate density functionals in vacuum and solution. We show that local and semi-local approximations to exchange do not yield a constant ionization potential for an increasing number of identical isolated molecules in vacuum. Instead, as the number of molecules increases, the total energy required to ionize the system decreases. Rather surprisingly, we find that this is still the case in solution, whether using a polarizable continuum model or with explicit solvent that breaks the degeneracy of each solute, and we find that explicit solvent in the calculation can exacerbate the size-dependent delocalization error. We demonstrate that increasing the amount of exact exchange changes the character of the polarization of the solvent molecules; for small amounts of exact exchange the solvent molecules contribute a fraction of their electron density to the ionized electron, but for larger amounts of exact exchange they properly polarize in response to the cationic solute. In vacuum and explicit solvent, the ionization potential can be made size-intensive by optimally tuning a long-range corrected hybrid functional.

  12. Simulation of electron energy loss spectra of nanomaterials with linear-scaling density functional theory

    International Nuclear Information System (INIS)

    Tait, E W; Payne, M C; Ratcliff, L E; Haynes, P D; Hine, N D M

    2016-01-01

    Experimental techniques for electron energy loss spectroscopy (EELS) combine high energy resolution with high spatial resolution. They are therefore powerful tools for investigating the local electronic structure of complex systems such as nanostructures, interfaces and even individual defects. Interpretation of experimental electron energy loss spectra is often challenging and can require theoretical modelling of candidate structures, which themselves may be large and complex, beyond the capabilities of traditional cubic-scaling density functional theory. In this work, we present functionality to compute electron energy loss spectra within the onetep linear-scaling density functional theory code. We first demonstrate that simulated spectra agree with those computed using conventional plane wave pseudopotential methods to a high degree of precision. The ability of onetep to tackle large problems is then exploited to investigate convergence of spectra with respect to supercell size. Finally, we apply the novel functionality to a study of the electron energy loss spectra of defects on the (1 0 1) surface of an anatase slab and determine concentrations of defects which might be experimentally detectable. (paper)

  13. Difficulties in applying pure Kohn-Sham density functional theory electronic structure methods to protein molecules

    Science.gov (United States)

    Rudberg, Elias

    2012-02-01

    Self-consistency-based Kohn-Sham density functional theory (KS-DFT) electronic structure calculations with Gaussian basis sets are reported for a set of 17 protein-like molecules with geometries obtained from the Protein Data Bank. It is found that in many cases such calculations do not converge due to vanishing HOMO-LUMO gaps. A sequence of polyproline I helix molecules is also studied and it is found that self-consistency calculations using pure functionals fail to converge for helices longer than six proline units. Since the computed gap is strongly correlated to the fraction of Hartree-Fock exchange, test calculations using both pure and hybrid density functionals are reported. The tested methods include the pure functionals BLYP, PBE and LDA, as well as Hartree-Fock and the hybrid functionals BHandHLYP, B3LYP and PBE0. The effect of including solvent molecules in the calculations is studied, and it is found that the inclusion of explicit solvent molecules around the protein fragment in many cases gives a larger gap, but that convergence problems due to vanishing gaps still occur in calculations with pure functionals. In order to achieve converged results, some modeling of the charge distribution of solvent water molecules outside the electronic structure calculation is needed. Representing solvent water molecules by a simple point charge distribution is found to give non-vanishing HOMO-LUMO gaps for the tested protein-like systems also for pure functionals.

  14. Difficulties in applying pure Kohn-Sham density functional theory electronic structure methods to protein molecules

    International Nuclear Information System (INIS)

    Rudberg, Elias

    2012-01-01

    Self-consistency-based Kohn-Sham density functional theory (KS-DFT) electronic structure calculations with Gaussian basis sets are reported for a set of 17 protein-like molecules with geometries obtained from the Protein Data Bank. It is found that in many cases such calculations do not converge due to vanishing HOMO-LUMO gaps. A sequence of polyproline I helix molecules is also studied and it is found that self-consistency calculations using pure functionals fail to converge for helices longer than six proline units. Since the computed gap is strongly correlated to the fraction of Hartree-Fock exchange, test calculations using both pure and hybrid density functionals are reported. The tested methods include the pure functionals BLYP, PBE and LDA, as well as Hartree-Fock and the hybrid functionals BHandHLYP, B3LYP and PBE0. The effect of including solvent molecules in the calculations is studied, and it is found that the inclusion of explicit solvent molecules around the protein fragment in many cases gives a larger gap, but that convergence problems due to vanishing gaps still occur in calculations with pure functionals. In order to achieve converged results, some modeling of the charge distribution of solvent water molecules outside the electronic structure calculation is needed. Representing solvent water molecules by a simple point charge distribution is found to give non-vanishing HOMO-LUMO gaps for the tested protein-like systems also for pure functionals. (fast track communication)

  15. Electrocatalysis of borohydride oxidation: a review of density functional theory approach combined with experimental validation

    International Nuclear Information System (INIS)

    Sison Escaño, Mary Clare; Arevalo, Ryan Lacdao; Kasai, Hideaki; Gyenge, Elod

    2014-01-01

    The electrocatalysis of borohydride oxidation is a complex, up-to-eight-electron transfer process, which is essential for development of efficient direct borohydride fuel cells. Here we review the progress achieved by density functional theory (DFT) calculations in explaining the adsorption of BH 4 − on various catalyst surfaces, with implications for electrocatalyst screening and selection. Wherever possible, we correlate the theoretical predictions with experimental findings, in order to validate the proposed models and to identify potential directions for further advancements. (topical review)

  16. Electronic properties of T graphene-like C-BN sheets: A density functional theory study

    Science.gov (United States)

    Majidi, R.

    2015-11-01

    We have used density functional theory to study the electronic properties of T graphene-like C, C-BN and BN sheets. The planar T graphene with metallic property has been considered. The results show that the presence of BN has a considerable effect on the electronic properties of T graphene. The T graphene-like C-BN and BN sheets show semiconducting properties. The energy band gap is increased by enhancing the number of BN units. The possibility of opening and controlling band gap opens the door for T graphene in switchable electronic devices.

  17. Factors Influencing Mean Inner Potentials As Studied Using Electron Holography and Density Functional Theory

    DEFF Research Database (Denmark)

    Pennington, Robert S.

    reflect properties of the specimen. The phase can yield quantitative measurements of nanoscale electric and magnetic potentials. One such electrostatic potential is called the mean inner potential. The mean inner potential is the average electrostatic potential measured between the bulk of a material...... to analyze diffraction effects on the amplitude and the phase. There is relatively good comparison between image simulation and experimental data, but the experimental absorption parameter is found to differ between strongly and weakly diffracting conditions. Density functional theory simulations of the mean...

  18. Sequential double excitations from linear-response time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Mosquera, Martín A.; Ratner, Mark A.; Schatz, George C., E-mail: g-schatz@northwestern.edu [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chen, Lin X. [Department of Chemistry, Northwestern University, 2145 Sheridan Rd., Evanston, Illinois 60208 (United States); Chemical Sciences and Engineering Division, Argonne National Laboratory, 9700 South Cass Ave., Lemont, Illinois 60439 (United States)

    2016-05-28

    Traditional UV/vis and X-ray spectroscopies focus mainly on the study of excitations starting exclusively from electronic ground states. However there are many experiments where transitions from excited states, both absorption and emission, are probed. In this work we develop a formalism based on linear-response time-dependent density functional theory to investigate spectroscopic properties of excited states. We apply our model to study the excited-state absorption of a diplatinum(II) complex under X-rays, and transient vis/UV absorption of pyrene and azobenzene.

  19. Time-dependent density functional theory description of total photoabsorption cross sections

    Science.gov (United States)

    Tenorio, Bruno Nunes Cabral; Nascimento, Marco Antonio Chaer; Rocha, Alexandre Braga

    2018-02-01

    The time-dependent version of the density functional theory (TDDFT) has been used to calculate the total photoabsorption cross section of a number of molecules, namely, benzene, pyridine, furan, pyrrole, thiophene, phenol, naphthalene, and anthracene. The discrete electronic pseudo-spectra, obtained in a L2 basis set calculation were used in an analytic continuation procedure to obtain the photoabsorption cross sections. The ammonia molecule was chosen as a model system to compare the results obtained with TDDFT to those obtained with the linear response coupled cluster approach in order to make a link with our previous work and establish benchmarks.

  20. Density functional theory prediction for diffusion of lithium on boron-doped graphene surface

    International Nuclear Information System (INIS)

    Gao Shuanghong; Ren Zhaoyu; Wan Lijuan; Zheng Jiming; Guo Ping; Zhou Yixuan

    2011-01-01

    The density functional theory (DFT) investigation shows that graphene has changed from semimetal to semiconductor with the increasing number of doped boron atoms. Lithium and boron atoms acted as charge contributors and recipients, which attracted to each other. Further investigations show that, the potential barrier for lithium diffusion on boron-doped graphene is higher than that of intrinsic graphene. The potential barrier is up to 0.22 eV when six boron atoms doped (B 6 C 26 ), which is the lowest potential barrier in all the doped graphene. The potential barrier is dramatically affected by the surface structure of graphene.

  1. Hardness and softness reactivity kernels within the spin-polarized density-functional theory

    International Nuclear Information System (INIS)

    Chamorro, Eduardo; De Proft, Frank; Geerlings, Paul

    2005-01-01

    Generalized hardness and softness reactivity kernels are defined within a spin-polarized density-functional theory (SP-DFT) conceptual framework. These quantities constitute the basis for the global, local (i.e., r-position dependent), and nonlocal (i.e., r and r ' -position dependents) indices devoted to the treatment of both charge-transfer and spin-polarization processes in such a reactivity framework. The exact relationships between these descriptors within a SP-DFT framework are derived and the implications for chemical reactivity in such context are outlined

  2. On-the-Fly Machine Learning of Atomic Potential in Density Functional Theory Structure Optimization

    Science.gov (United States)

    Jacobsen, T. L.; Jørgensen, M. S.; Hammer, B.

    2018-01-01

    Machine learning (ML) is used to derive local stability information for density functional theory calculations of systems in relation to the recently discovered SnO2 (110 )-(4 ×1 ) reconstruction. The ML model is trained on (structure, total energy) relations collected during global minimum energy search runs with an evolutionary algorithm (EA). While being built, the ML model is used to guide the EA, thereby speeding up the overall rate by which the EA succeeds. Inspection of the local atomic potentials emerging from the model further shows chemically intuitive patterns.

  3. ONETEP: linear-scaling density-functional theory with plane-waves

    International Nuclear Information System (INIS)

    Haynes, P D; Mostof, A A; Skylaris, C-K; Payne, M C

    2006-01-01

    This paper provides a general overview of the methodology implemented in onetep (Order-N Electronic Total Energy Package), a parallel density-functional theory code for largescale first-principles quantum-mechanical calculations. The distinctive features of onetep are linear-scaling in both computational effort and resources, obtained by making well-controlled approximations which enable simulations to be performed with plane-wave accuracy. Titanium dioxide clusters of increasing size designed to mimic surfaces are studied to demonstrate the accuracy and scaling of onetep

  4. Magnetic edge states in MoS2 characterized using density-functional theory

    DEFF Research Database (Denmark)

    Vojvodic, Aleksandra; Hinnemann, B.; Nørskov, Jens Kehlet

    2009-01-01

    It is known that the edges of a two-dimensional slab of insulating MoS2 exhibit one-dimensional metallic edge states, the so-called "brim states." Here, we find from density-functional theory calculations that several edge structures, which are relevant for the hydrodesulfurization process......, are magnetic. The magnetism is an edge phenomenon associated with certain metallic edge states. Interestingly, we find that among the two low-index edges, only the S edge displays magnetism under hydrodesulfurization conditions. In addition, the implications of this on the catalytic activity are investigated...

  5. Simple descriptors for proton-conducting perovskites from density functional theory

    DEFF Research Database (Denmark)

    Bork, Nicolai Christian; Bonanos, Nikolaos; Rossmeisl, Jan

    2010-01-01

    series of (pseudo)cubic perovskites, ABO3, have been investigated using density functional theory calculations. The structures have been optimized and thermodynamic properties and activation energies for the relevant steps of the hydrogen/proton diffusion mechanism have been calculated using...... the nudged elastic band path technique. We find a strong correlation between the O-H binding energy for hydrogen/proton uptake in perovskites and the energy barriers involved in the observed Grotthuss-type diffusion process. We demonstrate the possibility of estimating diffusion rates based on O-H binding...

  6. First principles density functional theory study of Pb doped α-MnO2 catalytic materials

    Science.gov (United States)

    Song, Zilin; Yan, Zhiguo; Yang, Xiaojun; Bai, Hang; Duan, Yuhua; Yang, Bin; Leng, Li

    2018-03-01

    The impact of Pb in the tunnels of manganese oxide octahedral molecular sieves on chemical state of Mn species and lattice oxygen were investigated utilizing density functional theory calculations. The results show that the Pb dopant in the tunnels of OMS-2 could reduce the average valence states of Mn. The lower energy required for bulk oxygen defects formation in Pb-OMS-2 validates the activation of lattice oxygen by inclusion of tunnel dopant. The inclusion of Pb promotes the catalytic oxidation activity of OMS-2 by reducing the energy required for the surface lattice oxygen migration during the Mars - van Krevelen oxidation process.

  7. Site specific interaction between ZnO nanoparticles and tyrosine: A density functional theory study

    Science.gov (United States)

    Singh, Satvinder; Singh, Janpreet; Singh, Baljinder; Singh, Gurinder; Kaura, Aman; Tripathi, S. K.

    2018-05-01

    First Principles Calculations have been performed on ZnO/Tyrosine atomic complex to study site specific interaction of Tyrosine and ZnO nanoparticles. Calculated results shows that -COOH group present in Tyrosine is energetically more favorable than -NH2 group. Interactions show ionic bonding between ZnO and Tyrosine. All the calculations have been performed under the Density Functional Theory (DFT) framework. Structural and electronic properties of (ZnO)3/Tyrosine complex have been studied. Gaussian basis set approach has been adopted for the calculations. A ring type most stable (ZnO)3 atomic cluster has been modeled, analyzed and used for the calculations.

  8. Electronic Structures of Strained InAs x P1-x by Density Functional Theory.

    Science.gov (United States)

    Lee, Seung Mi; Kim, Min-Young; Kim, Young Heon

    2018-09-01

    We investigated the effects of strain on the electronic structures of InAsxP1-x using quantum mechanical density functional theory calculations. The electronic band gap and electron effective mass decreased with the increase of the uniaxial tensile strain along the [0001] direction of wurtzite InAs0.75P0.25. Therefore, faster electron movements are expected. These theoretical results are in good agreement with the experimental measurements of InAs0.75P0.25 nanowire.

  9. Investigation of the metal binding site in methionine aminopeptidase by density functional theory

    DEFF Research Database (Denmark)

    Jørgensen, Anne Techau; Norrby, Per-Ola; Liljefors, Tommy

    2002-01-01

    All methionine aminopeptidases exhibit the same conserved metal binding site. The structure of this site with either Co2+ ions or Zn2+ ions was investigated using density functional theory. The calculations showed that the structure of the site was not influenced by the identity of the metal ions....... This was the case for both of the systems studied; one based on the X-ray structure of the human methionine aminopeptidase type 2 (hMetAP-2) and the other based on the X-ray structure of the E. coli methionine aminopeptidase type 1 (eMetAP-1). Another important structural issue is the identity of the bridging...

  10. A density functional theory-based investigation of adhesion of poly(butylene terephthalate) on aluminum

    International Nuclear Information System (INIS)

    David, Melanie; Roman, Tanglaw; Nakanishi, Hiroshi; Kasai, Hideaki; Ando, Naoki; Naritomi, Masanori

    2006-01-01

    We investigate the adhesion of PBT on aluminum using density functional theory-based calculations. The geometric structure of the PBT monomer is first relaxed then an aluminum atom is connected to the monomer in different orientations. We calculate their total energies and determine the orientation that gives the strongest binding between the monomer and the aluminum atom. Binding is strongest when the Al connects linearly with the carbonyl oxygen in the ester group. We present binding mechanisms and total energy relationships for the different orientations

  11. Current Issues in Finite-T Density-Functional Theory and Warm-Correlated Matter †

    Directory of Open Access Journals (Sweden)

    M. W. C. Dharma-wardana

    2016-03-01

    Full Text Available Finite-temperature density functional theory (DFT has become of topical interest, partly due to the increasing ability to create novel states of warm-correlated matter (WCM.Warm-dense matter (WDM, ultra-fast matter (UFM, and high-energy density matter (HEDM may all be regarded as subclasses of WCM. Strong electron-electron, ion-ion and electron-ion correlation effects and partial degeneracies are found in these systems where the electron temperature Te is comparable to the electron Fermi energy EF. Thus, many electrons are in continuum states which are partially occupied. The ion subsystem may be solid, liquid or plasma, with many states of ionization with ionic charge Zj. Quasi-equilibria with the ion temperature Ti ≠ Te are common. The ion subsystem in WCM can no longer be treated as a passive “external potential”, as is customary in T = 0 DFT dominated by solid-state theory or quantum chemistry. Many basic questions arise in trying to implement DFT for WCM. Hohenberg-Kohn-Mermin theory can be adapted for treating these systems if suitable finite-T exchange-correlation (XC functionals can be constructed. They are functionals of both the one-body electron density ne and the one-body ion densities ρj. Here, j counts many species of nuclei or charge states. A method of approximately but accurately mapping the quantum electrons to a classical Coulomb gas enables one to treat electron-ion systems entirely classically at any temperature and arbitrary spin polarization, using exchange-correlation effects calculated in situ, directly from the pair-distribution functions. This eliminates the need for any XC-functionals. This classical map has been used to calculate the equation of state of WDM systems, and construct a finite-T XC functional that is found to be in close agreement with recent quantum path-integral simulation data. In this review, current developments and concerns in finite-T DFT, especially in the context of non-relativistic warm

  12. Edge reconstruction in armchair phosphorene nanoribbons revealed by discontinuous Galerkin density functional theory.

    Science.gov (United States)

    Hu, Wei; Lin, Lin; Yang, Chao

    2015-12-21

    With the help of our recently developed massively parallel DGDFT (Discontinuous Galerkin Density Functional Theory) methodology, we perform large-scale Kohn-Sham density functional theory calculations on phosphorene nanoribbons with armchair edges (ACPNRs) containing a few thousands to ten thousand atoms. The use of DGDFT allows us to systematically achieve a conventional plane wave basis set type of accuracy, but with a much smaller number (about 15) of adaptive local basis (ALB) functions per atom for this system. The relatively small number of degrees of freedom required to represent the Kohn-Sham Hamiltonian, together with the use of the pole expansion the selected inversion (PEXSI) technique that circumvents the need to diagonalize the Hamiltonian, results in a highly efficient and scalable computational scheme for analyzing the electronic structures of ACPNRs as well as their dynamics. The total wall clock time for calculating the electronic structures of large-scale ACPNRs containing 1080-10,800 atoms is only 10-25 s per self-consistent field (SCF) iteration, with accuracy fully comparable to that obtained from conventional planewave DFT calculations. For the ACPNR system, we observe that the DGDFT methodology can scale to 5000-50,000 processors. We use DGDFT based ab initio molecular dynamics (AIMD) calculations to study the thermodynamic stability of ACPNRs. Our calculations reveal that a 2 × 1 edge reconstruction appears in ACPNRs at room temperature.

  13. Electronic structure modeling of InAs/GaSb superlattices with hybrid density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Garwood, Tristan [Univ. of New Mexico, Albuquerque, NM (United States). Center for High Technology Materials; Modine, Normand A. [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Krishna, S. [Univ. of New Mexico, Albuquerque, NM (United States). Center for High Technology Materials

    2016-12-18

    The application of first-principles calculations holds promise for greatly improving our understanding of semiconductor superlattices. By developing a procedure to accurately predict band gaps using hybrid density functional theory, it lays the groundwork for future studies investigating more nuanced properties of these structures. Our approach allows a priori prediction of the properties of SLS structures using only the band gaps of the constituent materials. Furthermore, it should enable direct investigation of the effects of interface structure, e.g., intermixing or ordering at the interface, on SLS properties. In this paper, we present band gap data for various InAs/GaSb type-II superlattice structures calculated using the generalized Kohn-Sham formulation of density functional theory. A PBE0-type hybrid functional was used, and the portion of the exact exchange was tuned to fit the band gaps of the binary compounds InAs and GaSb with the best agreement to bulk experimental values obtained with 18% of the exact exchange. The heterostructures considered in this study are 6 monolayer (ML) InAs/6 ML GaSb, 8 ML InAs/8 ML GaSb and 10 ML InAs/10 ML GaSb with deviations from the experimental band gaps ranging from 3% to 11%.

  14. Dual descriptors within the framework of spin-polarized density functional theory.

    Science.gov (United States)

    Chamorro, E; Pérez, P; Duque, M; De Proft, F; Geerlings, P

    2008-08-14

    Spin-polarized density functional theory (SP-DFT) allows both the analysis of charge-transfer (e.g., electrophilic and nucleophilic reactivity) and of spin-polarization processes (e.g., photophysical changes arising from electron transitions). In analogy with the dual descriptor introduced by Morell et al. [J. Phys. Chem. A 109, 205 (2005)], we introduce new dual descriptors intended to simultaneously give information of the molecular regions where the spin-polarization process linking states of different multiplicity will drive electron density and spin density changes. The electronic charge and spin rearrangement in the spin forbidden radiative transitions S(0)-->T(n,pi(*)) and S(0)-->T(pi,pi(*)) in formaldehyde and ethylene, respectively, have been used as benchmark examples illustrating the usefulness of the new spin-polarization dual descriptors. These quantities indicate those regions where spin-orbit coupling effects are at work in such processes. Additionally, the qualitative relationship between the topology of the spin-polarization dual descriptors and the vertical singlet triplet energy gap in simple substituted carbene series has been also discussed. It is shown that the electron density and spin density rearrangements arise in agreement with spectroscopic experimental evidence and other theoretical results on the selected target systems.

  15. Fluids density functional theory and initializing molecular dynamics simulations of block copolymers

    Science.gov (United States)

    Brown, Jonathan R.; Seo, Youngmi; Maula, Tiara Ann D.; Hall, Lisa M.

    2016-03-01

    Classical, fluids density functional theory (fDFT), which can predict the equilibrium density profiles of polymeric systems, and coarse-grained molecular dynamics (MD) simulations, which are often used to show both structure and dynamics of soft materials, can be implemented using very similar bead-based polymer models. We aim to use fDFT and MD in tandem to examine the same system from these two points of view and take advantage of the different features of each methodology. Additionally, the density profiles resulting from fDFT calculations can be used to initialize the MD simulations in a close to equilibrated structure, speeding up the simulations. Here, we show how this method can be applied to study microphase separated states of both typical diblock and tapered diblock copolymers in which there is a region with a gradient in composition placed between the pure blocks. Both methods, applied at constant pressure, predict a decrease in total density as segregation strength or the length of the tapered region is increased. The predictions for the density profiles from fDFT and MD are similar across materials with a wide range of interfacial widths.

  16. Characterization of Phase Transition in Heisenberg Fluids from Density Functional Theory

    International Nuclear Information System (INIS)

    Li Liangsheng; Li Li; Chen Xiaosong

    2009-01-01

    The phase transition of Heisenberg fluid has been investigated with the density functional theory in mean-field approximation (MF). The matrix of the second derivatives of the grand canonical potential Ω with respect to the particle density fluctuations and the magnetization fluctuations has been investigated and diagonalized. The smallest eigenvalue being 0 signalizes the phase instability and the related eigenvector characterizes this phase transition. We find a Curie line where the order parameter is pure magnetization and a spinodal where the order parameter is a mixture of particle density and magnetization. Along the spinodal, the character of phase instability changes continuously from predominant condensation to predominant ferromagnetic phase transition with the decrease of total density. The spinodal meets the Curie line at the critical endpoint with the reduced density ρ* = ρσ 3 = 0.224 and the reduced temperature T* = kT/ element of = 1.87 (σ is the diameter of Heisenberg hard sphere and element of is the coupling constant).

  17. On the universality of the long-/short-range separation in multiconfigurational density-functional theory

    Science.gov (United States)

    Fromager, Emmanuel; Toulouse, Julien; Jensen, Hans Jørgen Aa.

    2007-02-01

    In many cases, the dynamic correlation can be calculated quite accurately and at a fairly low computational cost in Kohn-Sham density-functional theory (KS-DFT), using current standard approximate functionals. However, in general, KS-DFT does not treat static correlation effects (near degeneracy) adequately which, on the other hand, can be described in wave-function theory (WFT), for example, with a multiconfigurational self-consistent field (MCSCF) model. It is therefore of high interest to develop a hybrid model which combines the best of both WFT and DFT approaches. The merge of WFT and DFT can be achieved by splitting the two-electron interaction into long-range and short-range parts. The long-range part is then treated by WFT and the short-range part by DFT. In this work the authors consider the so-called "erf" long-range interaction erf(μr12)/r12, which is based on the standard error function, and where μ is a free parameter which controls the range of the long-/short-range decomposition. In order to formulate a general method, they propose a recipe for the definition of an optimal μopt parameter, which is independent of the approximate short-range functional and the approximate wave function, and they discuss its universality. Calculations on a test set consisting of He, Be, Ne, Mg, H2, N2, and H2O yield μopt≈0.4a.u.. A similar analysis on other types of test systems such as actinide compounds is currently in progress. Using the value of 0.4a.u. for μ, encouraging results are obtained with the hybrid MCSCF-DFT method for the dissociation energies of H2, N2, and H2O, with both short-range local-density approximation and PBE-type functionals.

  18. Time-Dependent Density Functional Theory for Open Systems and Its Applications.

    Science.gov (United States)

    Chen, Shuguang; Kwok, YanHo; Chen, GuanHua

    2018-02-20

    Photovoltaic devices, electrochemical cells, catalysis processes, light emitting diodes, scanning tunneling microscopes, molecular electronics, and related devices have one thing in common: open quantum systems where energy and matter are not conserved. Traditionally quantum chemistry is confined to isolated and closed systems, while quantum dissipation theory studies open quantum systems. The key quantity in quantum dissipation theory is the reduced system density matrix. As the reduced system density matrix is an O(M! × M!) matrix, where M is the number of the particles of the system of interest, quantum dissipation theory can only be employed to simulate systems of a few particles or degrees of freedom. It is thus important to combine quantum chemistry and quantum dissipation theory so that realistic open quantum systems can be simulated from first-principles. We have developed a first-principles method to simulate the dynamics of open electronic systems, the time-dependent density functional theory for open systems (TDDFT-OS). Instead of the reduced system density matrix, the key quantity is the reduced single-electron density matrix, which is an N × N matrix where N is the number of the atomic bases of the system of interest. As the dimension of the key quantity is drastically reduced, the TDDFT-OS can thus be used to simulate the dynamics of realistic open electronic systems and efficient numerical algorithms have been developed. As an application, we apply the method to study how quantum interference develops in a molecular transistor in time domain. We include electron-phonon interaction in our simulation and show that quantum interference in the given system is robust against nuclear vibration not only in the steady state but also in the transient dynamics. As another application, by combining TDDFT-OS with Ehrenfest dynamics, we study current-induced dissociation of water molecules under scanning tunneling microscopy and follow its time dependent

  19. Critique of the foundations of time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Schirmer, J.; Dreuw, A.

    2007-01-01

    The general expectation that, in principle, the time-dependent density-functional theory (TDDFT) is an exact formulation of the time evolution of an interacting N-electron system is critically reexamined. It is demonstrated that the previous TDDFT foundation, resting on four theorems by Runge and Gross (RG) [Phys. Rev. Lett. 52, 997 (1984)], is invalid because undefined phase factors corrupt the RG action integral functionals. Our finding confirms much of a previous analysis by van Leeuwen [Int. J. Mod. Phys. B 15, 1969 (2001)]. To analyze the RG theorems and other aspects of TDDFT, an utmost simplification of the Kohn-Sham (KS) concept has been introduced, in which the ground-state density is obtained from a single KS equation for one spatial (spinless) orbital. The time-dependent (TD) form of this radical Kohn-Sham (rKS) scheme, which has the same validity status as the ordinary KS version, has proved to be a valuable tool for analysis. The rKS concept is used to clarify also the alternative nonvariational formulation of TD KS theory. We argue that it is just a formal theory, allowing one to reproduce but not predict the time development of the exact density of the interacting N-electron system. Besides the issue of the formal exactness of TDDFT, it is shown that both the static and time-dependent KS linear response equations neglect the particle-particle (p-p) and hole-hole (h-h) matrix elements of the perturbing operator. For a local (multiplicative) operator this does not lead to a loss of information due to a remarkable general property of local operators. Accordingly, no logical inconsistency arises with respect to DFT, because DFT requires any external potential to be local. For a general nonlocal operator the error resulting from the neglected matrix elements is of second order in the electronic repulsion

  20. Obtaining macroscopic quantities for the contact line problem from Density Functional Theory using asymptotic methods

    Science.gov (United States)

    Sibley, David; Nold, Andreas; Kalliadasis, Serafim

    2015-11-01

    Density Functional Theory (DFT), a statistical mechanics of fluids approach, captures microscopic details of the fluid density structure in the vicinity of contact lines, as seen in computations in our recent study. Contact lines describe the location where interfaces between two fluids meet solid substrates, and have stimulated a wealth of research due to both their ubiquity in nature and technological applications and also due to their rich multiscale behaviour. Whilst progress can be made computationally to capture the microscopic to mesoscopic structure from DFT, complete analytical results to fully bridge to the macroscale are lacking. In this work, we describe our efforts to bring asymptotic methods to DFT to obtain results for contact angles and other macroscopic quantities in various parameter regimes. We acknowledge financial support from European Research Council via Advanced Grant No. 247031.

  1. A Density Functional Theory Study of Doped Tin Monoxide as a Transparent p-type Semiconductor

    KAUST Repository

    Bianchi Granato, Danilo

    2012-05-01

    In the pursuit of enhancing the electronic properties of transparent p-type semiconductors, this work uses density functional theory to study the effects of doping tin monoxide with nitrogen, antimony, yttrium and lanthanum. An overview of the theoretical concepts and a detailed description of the methods employed are given, including a discussion about the correction scheme for charged defects proposed by Freysoldt and others [Freysoldt 2009]. Analysis of the formation energies of the defects points out that nitrogen substitutes an oxygen atom and does not provide charge carriers. On the other hand, antimony, yttrium, and lanthanum substitute a tin atom and donate n-type carriers. Study of the band structure and density of states indicates that yttrium and lanthanum improves the hole mobility. Present results are in good agreement with available experimental works and help to improve the understanding on how to engineer transparent p-type materials with higher hole mobilities.

  2. Simulations of nanocrystals under pressure: Combining electronic enthalpy and linear-scaling density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Corsini, Niccolò R. C., E-mail: niccolo.corsini@imperial.ac.uk; Greco, Andrea; Haynes, Peter D. [Department of Physics and Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Hine, Nicholas D. M. [Department of Physics and Department of Materials, Imperial College London, Exhibition Road, London SW7 2AZ (United Kingdom); Cavendish Laboratory, J. J. Thompson Avenue, Cambridge CB3 0HE (United Kingdom); Molteni, Carla [Department of Physics, King' s College London, Strand, London WC2R 2LS (United Kingdom)

    2013-08-28

    We present an implementation in a linear-scaling density-functional theory code of an electronic enthalpy method, which has been found to be natural and efficient for the ab initio calculation of finite systems under hydrostatic pressure. Based on a definition of the system volume as that enclosed within an electronic density isosurface [M. Cococcioni, F. Mauri, G. Ceder, and N. Marzari, Phys. Rev. Lett.94, 145501 (2005)], it supports both geometry optimizations and molecular dynamics simulations. We introduce an approach for calibrating the parameters defining the volume in the context of geometry optimizations and discuss their significance. Results in good agreement with simulations using explicit solvents are obtained, validating our approach. Size-dependent pressure-induced structural transformations and variations in the energy gap of hydrogenated silicon nanocrystals are investigated, including one comparable in size to recent experiments. A detailed analysis of the polyamorphic transformations reveals three types of amorphous structures and their persistence on depressurization is assessed.

  3. Liquid direct correlation function, singlet densities and the theory of freezing

    International Nuclear Information System (INIS)

    March, N.H.; Tosi, M.P.

    1981-04-01

    We have examined the solutions for the singlet density rho(r) in the hierarchical equation connecting rho(r) with the liquid direct correlation function c(r). In addition to the homogeneous solution rho(r)=rhosub(liquid), we exhibit a periodic solution which can co-exist with the liquid solution. If the defining equation for this is linearized, we recover the bifurcation condition of Lovett and Buff. We stress the difference between the two treatments as that between first and second-order transitions. It turns out that the treatment presented here leads to the same periodic density as that derived, using the hypernetted chain approximation, by Ramakrishnan and Yussouff in their theory of freezing. Invoking that approximation is shown thereby to be inessential. (author)

  4. Doping strategies to control A-centres in silicon: Insights from hybrid density functional theory

    KAUST Repository

    Wang, Hao; Chroneos, Alexander I.; Londos, Charalampos A.; Sgourou, Efstratia N.; Schwingenschlö gl, Udo

    2014-01-01

    Hybrid density functional theory is used to gain insights into the interaction of intrinsic vacancies (V) and oxygen-vacancy pairs (VO, known as A-centres) with the dopants (D) germanium (Ge), tin (Sn), and lead (Pb) in silicon (Si). We determine the structures as well as binding and formation energies of the DVO and DV complexes. The results are discussed in terms of the density of states and in view of the potential of isovalent doping to control A-centres in Si. We argue that doping with Sn is the most efficient isovalent doping strategy to suppress A-centres by the formation of SnVO complexes, as these are charge neutral and strongly bound. © 2014 the Owner Societies.

  5. Analytic cubic and quartic force fields using density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Ringholm, Magnus; Gao, Bin; Thorvaldsen, Andreas J.; Ruud, Kenneth [Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Tromsø—The Arctic University of Norway, 9037 Tromsø (Norway); Jonsson, Dan [Centre for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Tromsø—The Arctic University of Norway, 9037 Tromsø (Norway); High Performance Computing Group, University of Tromsø—The Arctic University of Norway, 9037 Tromsø (Norway); Bast, Radovan [Theoretical Chemistry and Biology, School of Biotechnology, Royal Institute of Technology, AlbaNova University Center, S-10691 Stockholm, Sweden and PDC Center for High Performance Computing, Royal Institute of Technology, S-10044 Stockholm (Sweden); Ekström, Ulf; Helgaker, Trygve [Center for Theoretical and Computational Chemistry (CTCC), Department of Chemistry, University of Oslo, P.O. Box 1033, Blindern, 0315 Oslo (Norway)

    2014-01-21

    We present the first analytic implementation of cubic and quartic force constants at the level of Kohn–Sham density-functional theory. The implementation is based on an open-ended formalism for the evaluation of energy derivatives in an atomic-orbital basis. The implementation relies on the availability of open-ended codes for evaluation of one- and two-electron integrals differentiated with respect to nuclear displacements as well as automatic differentiation of the exchange–correlation kernels. We use generalized second-order vibrational perturbation theory to calculate the fundamental frequencies of methane, ethane, benzene, and aniline, comparing B3LYP, BLYP, and Hartree–Fock results. The Hartree–Fock anharmonic corrections agree well with the B3LYP corrections when calculated at the B3LYP geometry and from B3LYP normal coordinates, suggesting that the inclusion of electron correlation is not essential for the reliable calculation of cubic and quartic force constants.

  6. Basic Density-Functional Theory—an Overview

    Science.gov (United States)

    von Barth, U.

    In these notes I have given a personally flavored exposA~© of static density-functional theory (DFT). I have started from standard many-body physics at a very elementary level and then gradually introduced the basic concepts of DFT. Successively more advanced topics are added and at the end I even discuss a few not yet published theories. The discussion represents many of the personal views of the author and there is no attempt at being comprehensive. I fully realize that I am often ‘unfair’ in treating the achievements of other researchers. Many topics of standard DFT are deliberately left out like, e.g., time-dependence, excitations, and magnetic or relativistic effects. These notes represent a compilation of a series of lectures given at at the EXC!TING Summer School DFT beyond the ground state at RiksgrA~¤nsen, Sweden in June of 2003.

  7. Density functional theory study on the ionic liquid pyridinium hydrogen sulfate

    Science.gov (United States)

    Tankov, Ivaylo; Yankova, Rumyana; Genieva, Svetlana; Mitkova, Magdalena; Stratiev, Dicho

    2017-07-01

    The geometry, electronic structure and chemical reactivity of a pyridinium-based ionic liquid, pyridinium hydrogen sulfate ([H-Pyr]+[HSO4]-), have been discussed on the basis of quantum chemical density functional theory calculations using B3LYP/6-311+G(d,p) and B3LYP/6-311++G(2d,2p) approaches. The calculations indicated that [H-Pyr]+[HSO4]- exists in the form of an ion pair. A large electropositive potential was found on the pyridinium ring, while the regions of a negative electrostatic potential is linked with the lone pair of electronegative oxygen atoms in hydrogen sulfate anion ([HSO4]-). Electron transfer both within the anion, and between the anion and cation of an ion pair were described using natural bond orbital theory. The energy values of -7.1375 and -2.8801 eV were related to HOMO and LUMO orbitals, respectively.

  8. Multiple exciton generation in chiral carbon nanotubes: Density functional theory based computation

    Science.gov (United States)

    Kryjevski, Andrei; Mihaylov, Deyan; Kilina, Svetlana; Kilin, Dmitri

    2017-10-01

    We use a Boltzmann transport equation (BE) to study time evolution of a photo-excited state in a nanoparticle including phonon-mediated exciton relaxation and the multiple exciton generation (MEG) processes, such as exciton-to-biexciton multiplication and biexciton-to-exciton recombination. BE collision integrals are computed using Kadanoff-Baym-Keldysh many-body perturbation theory based on density functional theory simulations, including exciton effects. We compute internal quantum efficiency (QE), which is the number of excitons generated from an absorbed photon in the course of the relaxation. We apply this approach to chiral single-wall carbon nanotubes (SWCNTs), such as (6,2) and (6,5). We predict efficient MEG in the (6,2) and (6,5) SWCNTs within the solar spectrum range starting at the 2Eg energy threshold and with QE reaching ˜1.6 at about 3Eg, where Eg is the electronic gap.

  9. Exploring the surface reactivity of 3d metal endofullerenes: a density-functional theory study.

    Science.gov (United States)

    Estrada-Salas, Rubén E; Valladares, Ariel A

    2009-09-24

    Changes in the preferential sites of electrophilic, nucleophilic, and radical attacks on the pristine C60 surface with endohedral doping using 3d transition metal atoms were studied via two useful reactivity indices, namely the Fukui functions and the molecular electrostatic potential. Both of these were calculated at the density functional BPW91 level of theory with the DNP basis set. Our results clearly show changes in the preferential reactivity sites on the fullerene surface when it is doped with Mn, Fe, Co, or Ni atoms, whereas there are no significant changes in the preferential reactivity sites on the C60 surface upon endohedral doping with Cu and Zn atoms. Electron affinities (EA), ionization potentials (IP), and HOMO-LUMO gaps (Eg) were also calculated to complete the study of the endofullerene's surface reactivity. These findings provide insight into endofullerene functionalization, an important issue in their application.

  10. Local electric dipole moments for periodic systems via density functional theory embedding.

    Science.gov (United States)

    Luber, Sandra

    2014-12-21

    We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystem-density functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchange-correlation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries.

  11. Local electric dipole moments for periodic systems via density functional theory embedding

    Energy Technology Data Exchange (ETDEWEB)

    Luber, Sandra, E-mail: sandra.luber@chem.uzh.ch [Institut für Chemie, Universität Zürich, Winterthurerstrasse 190, 8057 Zürich (Switzerland)

    2014-12-21

    We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystem-density functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchange–correlation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries.

  12. Quantal density-functional theory in the presence of a magnetic field

    International Nuclear Information System (INIS)

    Yang Tao; Pan Xiaoyin; Sahni, Viraht

    2011-01-01

    We generalize the quantal density-functional theory (QDFT) of electrons in the presence of an external electrostatic field E(r)=-∇v(r) to include an external magnetostatic field B(r)=∇xA(r), where (v(r),A(r)) are the respective scalar and vector potentials. The generalized QDFT, valid for nondegenerate ground and excited states, is the mapping from the interacting system of electrons to a model of noninteracting fermions with the same density ρ(r) and physical current density j(r), and from which the total energy can be obtained. The properties (ρ(r),j(r)) constitute the basic quantum-mechanical variables because, as proved previously, for a nondegenerate ground state they uniquely determine the potentials (v(r),A(r)). The mapping to the noninteracting system is arbitrary in that the model fermions may be either in their ground or excited state. The theory is explicated by application to a ground state of the exactly solvable (two-dimensional) Hooke's atom in a magnetic field, with the mapping being to a model system also in its ground state. The majority of properties of the model are obtained in closed analytical or semianalytical form. A comparison with the corresponding mapping from a ground state of the (three-dimensional) Hooke's atom in the absence of a magnetic field is also made.

  13. Time-dependent density functional theory of open quantum systems in the linear-response regime.

    Science.gov (United States)

    Tempel, David G; Watson, Mark A; Olivares-Amaya, Roberto; Aspuru-Guzik, Alán

    2011-02-21

    Time-dependent density functional theory (TDDFT) has recently been extended to describe many-body open quantum systems evolving under nonunitary dynamics according to a quantum master equation. In the master equation approach, electronic excitation spectra are broadened and shifted due to relaxation and dephasing of the electronic degrees of freedom by the surrounding environment. In this paper, we develop a formulation of TDDFT linear-response theory (LR-TDDFT) for many-body electronic systems evolving under a master equation, yielding broadened excitation spectra. This is done by mapping an interacting open quantum system onto a noninteracting open Kohn-Sham system yielding the correct nonequilibrium density evolution. A pseudoeigenvalue equation analogous to the Casida equations of the usual LR-TDDFT is derived for the Redfield master equation, yielding complex energies and Lamb shifts. As a simple demonstration, we calculate the spectrum of a C(2 +) atom including natural linewidths, by treating the electromagnetic field vacuum as a photon bath. The performance of an adiabatic exchange-correlation kernel is analyzed and a first-order frequency-dependent correction to the bare Kohn-Sham linewidth based on the Görling-Levy perturbation theory is calculated.

  14. Quantum spin correction scheme based on spin-correlation functional for Kohn-Sham spin density functional theory

    International Nuclear Information System (INIS)

    Yamanaka, Shusuke; Takeda, Ryo; Nakata, Kazuto; Takada, Toshikazu; Shoji, Mitsuo; Kitagawa, Yasutaka; Yamaguchi, Kizashi

    2007-01-01

    We present a simple quantum correction scheme for ab initio Kohn-Sham spin density functional theory (KS-SDFT). This scheme is based on a mapping from ab initio results to a Heisenberg model Hamiltonian. The effective exchange integral is estimated by using energies and spin correlation functionals calculated by ab initio KS-SDFT. The quantum-corrected spin-correlation functional is open to be designed to cover specific quantum spin fluctuations. In this article, we present a simple correction for dinuclear compounds having multiple bonds. The computational results are discussed in relation to multireference (MR) DFT, by which we treat the quantum many-body effects explicitly

  15. Perspective: Fifty years of density-functional theory in chemical physics

    Energy Technology Data Exchange (ETDEWEB)

    Becke, Axel D., E-mail: axel.becke@dal.ca [Department of Chemistry, Dalhousie University, 6274 Coburg Rd., P.O. Box 15000, Halifax, Nova Scotia B3H 4R2 (Canada)

    2014-05-14

    Since its formal inception in 1964–1965, Kohn-Sham density-functional theory (KS-DFT) has become the most popular electronic structure method in computational physics and chemistry. Its popularity stems from its beautifully simple conceptual framework and computational elegance. The rise of KS-DFT in chemical physics began in earnest in the mid 1980s, when crucial developments in its exchange-correlation term gave the theory predictive power competitive with well-developed wave-function methods. Today KS-DFT finds itself under increasing pressure to deliver higher and higher accuracy and to adapt to ever more challenging problems. If we are not mindful, however, these pressures may submerge the theory in the wave-function sea. KS-DFT might be lost. I am hopeful the Kohn-Sham philosophical, theoretical, and computational framework can be preserved. This Perspective outlines the history, basic concepts, and present status of KS-DFT in chemical physics, and offers suggestions for its future development.

  16. Perspective: Fifty years of density-functional theory in chemical physics

    International Nuclear Information System (INIS)

    Becke, Axel D.

    2014-01-01

    Since its formal inception in 1964–1965, Kohn-Sham density-functional theory (KS-DFT) has become the most popular electronic structure method in computational physics and chemistry. Its popularity stems from its beautifully simple conceptual framework and computational elegance. The rise of KS-DFT in chemical physics began in earnest in the mid 1980s, when crucial developments in its exchange-correlation term gave the theory predictive power competitive with well-developed wave-function methods. Today KS-DFT finds itself under increasing pressure to deliver higher and higher accuracy and to adapt to ever more challenging problems. If we are not mindful, however, these pressures may submerge the theory in the wave-function sea. KS-DFT might be lost. I am hopeful the Kohn-Sham philosophical, theoretical, and computational framework can be preserved. This Perspective outlines the history, basic concepts, and present status of KS-DFT in chemical physics, and offers suggestions for its future development

  17. Range-separated density-functional theory for molecular excitation energies

    International Nuclear Information System (INIS)

    Rebolini, E.

    2014-01-01

    Linear-response time-dependent density-functional theory (TDDFT) is nowadays a method of choice to compute molecular excitation energies. However, within the usual adiabatic semi-local approximations, it is not able to describe properly Rydberg, charge-transfer or multiple excitations. Range separation of the electronic interaction allows one to mix rigorously density-functional methods at short range and wave function or Green's function methods at long range. When applied to the exchange functional, it already corrects most of these deficiencies but multiple excitations remain absent as they need a frequency-dependent kernel. In this thesis, the effects of range separation are first assessed on the excitation energies of a partially-interacting system in an analytic and numerical study in order to provide guidelines for future developments of range-separated methods for excitation energy calculations. It is then applied on the exchange and correlation TDDFT kernels in a single-determinant approximation in which the long-range part of the correlation kernel vanishes. A long-range frequency-dependent second-order correlation kernel is then derived from the Bethe-Salpeter equation and added perturbatively to the range-separated TDDFT kernel in order to take into account the effects of double excitations. (author)

  18. A density functional theory study of the influence of exchange-correlation functionals on the properties of FeAs.

    Science.gov (United States)

    Griffin, Sinéad M; Spaldin, Nicola A

    2017-06-01

    We use density functional theory within the local density approximation (LDA), LDA  +  U, generalised gradient approximation (GGA), GGA  +  U, and hybrid-functional methods to calculate the properties of iron monoarsenide. FeAs, which forms in the MnP structure, is of current interest for potential spintronic applications as well as being the parent compound for the pnictide superconductors. We compare the calculated structural, magnetic and electronic properties obtained using the different functionals to each other and to experiment, and investigate the origin of a recently reported magnetic spiral. Our results indicate the appropriateness or otherwise of the various functionals for describing FeAs and the related Fe-pnictide superconductors.

  19. Polymer density functional theory approach based on scaling second-order direct correlation function.

    Science.gov (United States)

    Zhou, Shiqi

    2006-06-01

    A second-order direct correlation function (DCF) from solving the polymer-RISM integral equation is scaled up or down by an equation of state for bulk polymer, the resultant scaling second-order DCF is in better agreement with corresponding simulation results than the un-scaling second-order DCF. When the scaling second-order DCF is imported into a recently proposed LTDFA-based polymer DFT approach, an originally associated adjustable but mathematically meaningless parameter now becomes mathematically meaningful, i.e., the numerical value lies now between 0 and 1. When the adjustable parameter-free version of the LTDFA is used instead of the LTDFA, i.e., the adjustable parameter is fixed at 0.5, the resultant parameter-free version of the scaling LTDFA-based polymer DFT is also in good agreement with the corresponding simulation data for density profiles. The parameter-free version of the scaling LTDFA-based polymer DFT is employed to investigate the density profiles of a freely jointed tangent hard sphere chain near a variable sized central hard sphere, again the predictions reproduce accurately the simulational results. Importance of the present adjustable parameter-free version lies in its combination with a recently proposed universal theoretical way, in the resultant formalism, the contact theorem is still met by the adjustable parameter associated with the theoretical way.

  20. Density functional theory for adsorption of gas mixtures in metal-organic frameworks.

    Science.gov (United States)

    Liu, Yu; Liu, Honglai; Hu, Ying; Jiang, Jianwen

    2010-03-04

    In this work, a recently developed density functional theory in three-dimensional space was extended to the adsorption of gas mixtures. Weighted density approximations to the excess free energy with different weighting functions were adopted for both repulsive and attractive contributions. An equation of state for hard-sphere mixtures and a modified Benedict-Webb-Rubin equation for Lennard-Jones mixtures were used to estimate the excess free energy of a uniform fluid. The theory was applied to the adsorption of CO(2)/CH(4) and CO(2)/N(2) mixtures in two metal-organic frameworks: ZIF-8 and Zn(2)(BDC)(2)(ted). To validate the theoretical predictions, grand canonical Monte Carlo simulations were also conducted. The predicted adsorption and selectivity from DFT were found to agree well with the simulation results. CO(2) has stronger adsorption than CH(4) and N(2), particularly in Zn(2)(BDC)(2)(ted). The selectivity of CO(2) over CH(4) or N(2) increases with increasing pressure as attributed to the cooperative interactions of adsorbed CO(2) molecules. The composition of the gas mixture exhibits a significant effect on adsorption but not on selectivity.

  1. The first naphthosemiquinone complex of K+ with vitamin K3 analog: Experiment and density functional theory

    Science.gov (United States)

    Kathawate, Laxmi; Gejji, Shridhar P.; Yeole, Sachin D.; Verma, Prakash L.; Puranik, Vedavati G.; Salunke-Gawali, Sunita

    2015-05-01

    Synthesis and characterization of potassium complex of 2-hydroxy-3-methyl-1,4-naphthoquinone (phthiocol), the vitamin K3 analog, has been carried out using FT-IR, UV-Vis, 1H and 13C NMR, EPR, cyclic voltammetry and single crystal X-ray diffraction experiments combined with the density functional theory. It has been observed that naphthosemiquinone binds to two K+ ions extending the polymeric chain through bridging oxygens O(2) and O(3). The crystal network possesses hydrogen bonding interactions from coordinated water molecules showing water channels along the c-axis. 13C NMR spectra revealed that the complexation of phthiocol with potassium ion engenders deshielding of C(2) signals, which appear at δ = ∼14.6 ppm whereas those of C(3) exhibit up-field signals near δ ∼ 6.9 ppm. These inferences are supported by the M06-2x based density functional theory. Electrochemical experiments further suggest that reduction of naphthosemiquinone results in only a cathodic peak from catechol. A triplet state arising from interactions between neighboring phthiocol anion lead to a half field signal at g = 4.1 in the polycrystalline X-band EPR spectra at 133 K.

  2. Density functional theory and evolution algorithm calculations of elastic properties of AlON

    Energy Technology Data Exchange (ETDEWEB)

    Batyrev, I. G.; Taylor, D. E.; Gazonas, G. A.; McCauley, J. W. [U.S. Army Research Laboratory, Aberdeen Proving Ground, Maryland 21005 (United States)

    2014-01-14

    Different models for aluminum oxynitride (AlON) were calculated using density functional theory and optimized using an evolutionary algorithm. Evolutionary algorithm and density functional theory (DFT) calculations starting from several models of AlON with different Al or O vacancy locations and different positions for the N atoms relative to the vacancy were carried out. The results show that the constant anion model [McCauley et al., J. Eur. Ceram. Soc. 29(2), 223 (2009)] with a random distribution of N atoms not adjacent to the Al vacancy has the lowest energy configuration. The lowest energy structure is in a reasonable agreement with experimental X-ray diffraction spectra. The optimized structure of a 55 atom unit cell was used to construct 220 and 440 atom models for simulation cells using DFT with a Gaussian basis set. Cubic elastic constant predictions were found to approach the experimentally determined AlON single crystal elastic constants as the model size increased from 55 to 440 atoms. The pressure dependence of the elastic constants found from simulated stress-strain relations were in overall agreement with experimental measurements of polycrystalline and single crystal AlON. Calculated IR intensity and Raman spectra are compared with available experimental data.

  3. Surface effects on mean inner potentials studied using density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Pennington, Robert S., E-mail: robert.pennington@uni-ulm.de [Institute for Experimental Physics, Ulm University, Albert-Einstein-Allee 11, 89081 Ulm (Germany); Boothroyd, Chris B.; Dunin-Borkowski, Rafal E. [Ernst Ruska-Centre and Peter Grüneberg Institute, Forschungzentrum Jülich, 52425 Jülich (Germany)

    2015-12-15

    Quantitative materials characterization using electron holography frequently requires knowledge of the mean inner potential, but reported experimental mean inner potential measurements can vary widely. Using density functional theory, we have simulated the mean inner potential for materials with a range of different surface conditions and geometries. We use both “thin-film” and “nanowire” specimen geometries. We consider clean bulk-terminated surfaces with different facets and surface reconstructions using atom positions from both structural optimization and experimental data and we also consider surfaces both with and without adsorbates. We find that the mean inner potential is surface-dependent, with the strongest dependency on surface adsorbates. We discuss the outlook and perspective for future mean inner potential measurements. - Highlights: • Density functional theory (DFT) is used to simulate mean inner potentials (MIP). • Applications for MIP electron holography measurements are considered. • MIPs are found to be surface-dependent, for thin-film and nanowire geometries. • The DFT simulation precision is extensively tested for multiple materials. • Surface adsorbates can create a strong positive or negative effect.

  4. Uncertainty quantification for nuclear density functional theory and information content of new measurements.

    Science.gov (United States)

    McDonnell, J D; Schunck, N; Higdon, D; Sarich, J; Wild, S M; Nazarewicz, W

    2015-03-27

    Statistical tools of uncertainty quantification can be used to assess the information content of measured observables with respect to present-day theoretical models, to estimate model errors and thereby improve predictive capability, to extrapolate beyond the regions reached by experiment, and to provide meaningful input to applications and planned measurements. To showcase new opportunities offered by such tools, we make a rigorous analysis of theoretical statistical uncertainties in nuclear density functional theory using Bayesian inference methods. By considering the recent mass measurements from the Canadian Penning Trap at Argonne National Laboratory, we demonstrate how the Bayesian analysis and a direct least-squares optimization, combined with high-performance computing, can be used to assess the information content of the new data with respect to a model based on the Skyrme energy density functional approach. Employing the posterior probability distribution computed with a Gaussian process emulator, we apply the Bayesian framework to propagate theoretical statistical uncertainties in predictions of nuclear masses, two-neutron dripline, and fission barriers. Overall, we find that the new mass measurements do not impose a constraint that is strong enough to lead to significant changes in the model parameters. The example discussed in this study sets the stage for quantifying and maximizing the impact of new measurements with respect to current modeling and guiding future experimental efforts, thus enhancing the experiment-theory cycle in the scientific method.

  5. Uncertainty quantification for nuclear density functional theory and information content of new measurements

    Energy Technology Data Exchange (ETDEWEB)

    McDonnell, J. D. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Schunck, N. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States); Higdon, D. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Sarich, J. [Argonne National Lab. (ANL), Argonne, IL (United States); Wild, S. M. [Argonne National Lab. (ANL), Argonne, IL (United States); Nazarewicz, W. [Michigan State Univ., East Lansing, MI (United States); Oak Ridge National Lab., Oak Ridge, TN (United States); Univ. of Warsaw, Warsaw (Poland)

    2015-03-24

    Statistical tools of uncertainty quantification can be used to assess the information content of measured observables with respect to present-day theoretical models, to estimate model errors and thereby improve predictive capability, to extrapolate beyond the regions reached by experiment, and to provide meaningful input to applications and planned measurements. To showcase new opportunities offered by such tools, we make a rigorous analysis of theoretical statistical uncertainties in nuclear density functional theory using Bayesian inference methods. By considering the recent mass measurements from the Canadian Penning Trap at Argonne National Laboratory, we demonstrate how the Bayesian analysis and a direct least-squares optimization, combined with high-performance computing, can be used to assess the information content of the new data with respect to a model based on the Skyrme energy density functional approach. Employing the posterior probability distribution computed with a Gaussian process emulator, we apply the Bayesian framework to propagate theoretical statistical uncertainties in predictions of nuclear masses, two-neutron dripline, and fission barriers. Overall, we find that the new mass measurements do not impose a constraint that is strong enough to lead to significant changes in the model parameters. As a result, the example discussed in this study sets the stage for quantifying and maximizing the impact of new measurements with respect to current modeling and guiding future experimental efforts, thus enhancing the experiment-theory cycle in the scientific method.

  6. Density functional theory study on the electronic structure of UAl3 and USn3

    International Nuclear Information System (INIS)

    Tan Mingqiu; Tao Xiangming; Xu Xiaojun; Cai Jianqiu

    2003-01-01

    Authors report an ab initio study on the electronic properties of 5f states in U X 3 (X=Al, Sn) by full-potential linear muffin-tin orbitals L(S)DA calculations. The relativistic effects which are quite remarkable for heavy atoms such as U, have been treated by using scalar relativistic and spin-orbital coupling corrections. The calculations presented in this article have addressed following issues: firstly, the numerical results illustrates the different U 5f itineracy in UAl 3 and USn 3 qualitatively, and then the heavy fermion behavior of USn 3 ; secondly, using Stuttgart-fatband analysis, authors have confirmed the above conclusion quantitatively. In addition to the above results, the calculation involved in this research has resolved the discrepancy between previous density functional theory studies on these compounds, especially the band structure dispersion in M-X direction of simple cubic USn 3 . In conclusion, this study has approached a more precise description for these uranium compounds on the basis of modern density functional theory calculation and described USn 3 as a heavy fermion system due to its localized U 5f electronic states theoretically

  7. Validation of experimental molecular crystal structures with dispersion-corrected density functional theory calculations

    International Nuclear Information System (INIS)

    Streek, Jacco van de; Neumann, Marcus A.

    2010-01-01

    The accuracy of a dispersion-corrected density functional theory method is validated against 241 experimental organic crystal structures from Acta Cryst. Section E. This paper describes the validation of a dispersion-corrected density functional theory (d-DFT) method for the purpose of assessing the correctness of experimental organic crystal structures and enhancing the information content of purely experimental data. 241 experimental organic crystal structures from the August 2008 issue of Acta Cryst. Section E were energy-minimized in full, including unit-cell parameters. The differences between the experimental and the minimized crystal structures were subjected to statistical analysis. The r.m.s. Cartesian displacement excluding H atoms upon energy minimization with flexible unit-cell parameters is selected as a pertinent indicator of the correctness of a crystal structure. All 241 experimental crystal structures are reproduced very well: the average r.m.s. Cartesian displacement for the 241 crystal structures, including 16 disordered structures, is only 0.095 Å (0.084 Å for the 225 ordered structures). R.m.s. Cartesian displacements above 0.25 Å either indicate incorrect experimental crystal structures or reveal interesting structural features such as exceptionally large temperature effects, incorrectly modelled disorder or symmetry breaking H atoms. After validation, the method is applied to nine examples that are known to be ambiguous or subtly incorrect

  8. Analysis of self-consistency effects in range-separated density-functional theory with Møller-Plesset perturbation theory

    DEFF Research Database (Denmark)

    Fromager, Emmanuel; Jensen, Hans Jørgen Aagaard

    2011-01-01

    Range-separated density-functional theory combines wave function theory for the long-range part of the two-electron interaction with density-functional theory for the short-range part. When describing the long-range interaction with non-variational methods, such as perturbation or coupled......-cluster theories, self-consistency effects are introduced in the density functional part, which for an exact solution requires iterations. They are generally assumed to be small but no detailed study has been performed so far. Here, the authors analyze self-consistency when using Møller-Plesset-type (MP......) perturbation theory for the long range interaction. The lowest-order self-consistency corrections to the wave function and the energy, that enter the perturbation expansions at the second and fourth order, respectively, are both expressed in terms of the one-electron reduced density matrix. The computational...

  9. Configurational forces in electronic structure calculations using Kohn-Sham density functional theory

    Science.gov (United States)

    Motamarri, Phani; Gavini, Vikram

    2018-04-01

    We derive the expressions for configurational forces in Kohn-Sham density functional theory, which correspond to the generalized variational force computed as the derivative of the Kohn-Sham energy functional with respect to the position of a material point x . These configurational forces that result from the inner variations of the Kohn-Sham energy functional provide a unified framework to compute atomic forces as well as stress tensor for geometry optimization. Importantly, owing to the variational nature of the formulation, these configurational forces inherently account for the Pulay corrections. The formulation presented in this work treats both pseudopotential and all-electron calculations in a single framework, and employs a local variational real-space formulation of Kohn-Sham density functional theory (DFT) expressed in terms of the nonorthogonal wave functions that is amenable to reduced-order scaling techniques. We demonstrate the accuracy and performance of the proposed configurational force approach on benchmark all-electron and pseudopotential calculations conducted using higher-order finite-element discretization. To this end, we examine the rates of convergence of the finite-element discretization in the computed forces and stresses for various materials systems, and, further, verify the accuracy from finite differencing the energy. Wherever applicable, we also compare the forces and stresses with those obtained from Kohn-Sham DFT calculations employing plane-wave basis (pseudopotential calculations) and Gaussian basis (all-electron calculations). Finally, we verify the accuracy of the forces on large materials systems involving a metallic aluminum nanocluster containing 666 atoms and an alkane chain containing 902 atoms, where the Kohn-Sham electronic ground state is computed using a reduced-order scaling subspace projection technique [P. Motamarri and V. Gavini, Phys. Rev. B 90, 115127 (2014), 10.1103/PhysRevB.90.115127].

  10. No need for external orthogonality in subsystem density-functional theory.

    Science.gov (United States)

    Unsleber, Jan P; Neugebauer, Johannes; Jacob, Christoph R

    2016-08-03

    Recent reports on the necessity of using externally orthogonal orbitals in subsystem density-functional theory (SDFT) [Annu. Rep. Comput. Chem., 8, 2012, 53; J. Phys. Chem. A, 118, 2014, 9182] are re-investigated. We show that in the basis-set limit, supermolecular Kohn-Sham-DFT (KS-DFT) densities can exactly be represented as a sum of subsystem densities, even if the subsystem orbitals are not externally orthogonal. This is illustrated using both an analytical example and in basis-set free numerical calculations for an atomic test case. We further show that even with finite basis sets, SDFT calculations using accurate reconstructed potentials can closely approach the supermolecular KS-DFT density, and that the deviations between SDFT and KS-DFT decrease as the basis-set limit is approached. Our results demonstrate that formally, there is no need to enforce external orthogonality in SDFT, even though this might be a useful strategy when developing projection-based DFT embedding schemes.

  11. Spin-adapted open-shell time-dependent density functional theory. II. Theory and pilot application.

    Science.gov (United States)

    Li, Zhendong; Liu, Wenjian; Zhang, Yong; Suo, Bingbing

    2011-04-07

    The excited states of open-shell systems calculated by unrestricted Kohn-Sham-based time-dependent density functional theory (U-TD-DFT) are often heavily spin-contaminated and hence meaningless. This is solved ultimately by the recently proposed spin-adapted time-dependent density functional theory (TD-DFT) (S-TD-DFT) [J. Chem. Phys. 133, 064106 (2010)]. Unlike the standard restricted open-shell Kohn-Sham-based TD-DFT (R-TD-DFT) which can only access the singlet-coupled single excitations, the S-TD-DFT can capture both the singlet- and triplet-coupled single excitations with the same computational effort as the U-TD-DFT. The performances of the three approaches (U-TD-DFT, R-TD-DFT, and S-TD-DFT) are compared for both the spin-conserving and spin-flip excitations of prototypical open-shell systems, the nitrogen (N(2)(+)) and naphthalene (C(10)H(8)(+)) cations. The results show that the S-TD-DFT gives rise to balanced descriptions of excited states of open-shell systems.

  12. Fragment approach to constrained density functional theory calculations using Daubechies wavelets

    International Nuclear Information System (INIS)

    Ratcliff, Laura E.; Genovese, Luigi; Mohr, Stephan; Deutsch, Thierry

    2015-01-01

    In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments

  13. Fragment approach to constrained density functional theory calculations using Daubechies wavelets

    Energy Technology Data Exchange (ETDEWEB)

    Ratcliff, Laura E., E-mail: lratcliff@anl.gov [Argonne Leadership Computing Facility, Argonne National Laboratory, Lemont, Illinois 60439 (United States); Université de Grenoble Alpes, CEA, INAC-SP2M, L-Sim, F-38000 Grenoble (France); Genovese, Luigi; Mohr, Stephan; Deutsch, Thierry [Université de Grenoble Alpes, CEA, INAC-SP2M, L-Sim, F-38000 Grenoble (France)

    2015-06-21

    In a recent paper, we presented a linear scaling Kohn-Sham density functional theory (DFT) code based on Daubechies wavelets, where a minimal set of localized support functions are optimized in situ and therefore adapted to the chemical properties of the molecular system. Thanks to the systematically controllable accuracy of the underlying basis set, this approach is able to provide an optimal contracted basis for a given system: accuracies for ground state energies and atomic forces are of the same quality as an uncontracted, cubic scaling approach. This basis set offers, by construction, a natural subset where the density matrix of the system can be projected. In this paper, we demonstrate the flexibility of this minimal basis formalism in providing a basis set that can be reused as-is, i.e., without reoptimization, for charge-constrained DFT calculations within a fragment approach. Support functions, represented in the underlying wavelet grid, of the template fragments are roto-translated with high numerical precision to the required positions and used as projectors for the charge weight function. We demonstrate the interest of this approach to express highly precise and efficient calculations for preparing diabatic states and for the computational setup of systems in complex environments.

  14. Condensation pressures in small pores: An analytical model based on density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    R. H. Nilson; S. K. Griffiths

    1999-02-01

    Adsorption and condensation are critical to many applications of porous materials including filtration, separation, and the storage of gases. Integral methods are used to derive an analytical expression describing fluid condensation pressures in slit pores bounded by parallel plane walls. To obtain this result, the governing equations of Density Functional Theory (DFT) are integrated across the pore width assuming that fluid densities within adsorbed layers are spatially uniform. The thickness, density, and energy of these layers are expressed as composite functions constructed from asymptotic limits applicable to small and large pores. By equating the total energy of the adsorbed layers to that of a liquid-full pore, the authors arrive at a closed-form expression for the condensation pressure in terms of the pore size, surface tension, and Lennard-Jones parameters of the adsorbent and adsorbate molecules. The resulting equation reduces to the Kelvin equation in the large-pore limit. It further reproduces the condensation pressures computed by means of the full DFT equations for all pore sizes in which phase transitions are abrupt. Finally, in the limit of extremely small pores, for which phase transitions may be smooth and continuous, this simple analytical expression provides a good approximation to the apparent condensation pressure indicated by the steepest portion of the adsorption isotherm computed via DFT.

  15. Condensation pressures in small pores: An analytical model based on density functional theory

    International Nuclear Information System (INIS)

    Nilson, R.H.; Griffiths, S.K.

    1999-01-01

    Integral methods are used to derive an analytical expression describing fluid condensation pressures in slit pores bounded by parallel plane walls. To obtain this result, the governing equations of density functional theory (DFT) are integrated across the pore width assuming that fluid densities within adsorbed layers are spatially uniform. The thickness, density, and free energy of these layers are expressed as composite functions constructed from asymptotic limits applicable to small and large pores. By equating the total free energy of the adsorbed layers to that of a liquid-full pore, we arrive at a closed-form expression for the condensation pressure in terms of the pore size, surface tension, and Lennard-Jones parameters of the adsorbent and adsorbate molecules. The resulting equation reduces to the Kelvin equation in the large-pore limit. It further reproduces the condensation pressures computed by means of the full DFT equations for all pore sizes in which phase transitions are abrupt. Finally, in the limit of extremely small pores, for which phase transitions may be smooth and continuous, this simple analytical expression provides a good approximation to the apparent condensation pressure indicated by the steepest portion of the adsorption isotherm computed via DFT. copyright 1999 American Institute of Physics

  16. Optimal catalyst curves: Connecting density functional theory calculations with industrial reactor design and catalyst selection

    DEFF Research Database (Denmark)

    Jacobsen, C.J.H.; Dahl, Søren; Boisen, A.

    2002-01-01

    For ammonia synthesis catalysts a volcano-type relationship has been found experimentally. We demonstrate that by combining density functional theory calculations with a microkinetic model the position of the maximum of the volcano curve is sensitive to the reaction conditions. The catalytic...... ammonia synthesis activity, to a first approximation, is a function only of the binding energy of nitrogen to the catalyst. Therefore, it is possible to evaluate which nitrogen binding energy is optimal under given reaction conditions. This leads to the concept of optimal catalyst curves, which illustrate...... the nitrogen binding energies of the optimal catalysts at different temperatures, pressures, and synthesis gas compositions. Using this concept together with the ability to prepare catalysts with desired binding energies it is possible to optimize the ammonia process. In this way a link between first...

  17. Quasi-particle energy spectra in local reduced density matrix functional theory.

    Science.gov (United States)

    Lathiotakis, Nektarios N; Helbig, Nicole; Rubio, Angel; Gidopoulos, Nikitas I

    2014-10-28

    Recently, we introduced [N. N. Lathiotakis, N. Helbig, A. Rubio, and N. I. Gidopoulos, Phys. Rev. A 90, 032511 (2014)] local reduced density matrix functional theory (local RDMFT), a theoretical scheme capable of incorporating static correlation effects in Kohn-Sham equations. Here, we apply local RDMFT to molecular systems of relatively large size, as a demonstration of its computational efficiency and its accuracy in predicting single-electron properties from the eigenvalue spectrum of the single-particle Hamiltonian with a local effective potential. We present encouraging results on the photoelectron spectrum of molecular systems and the relative stability of C20 isotopes. In addition, we propose a modelling of the fractional occupancies as functions of the orbital energies that further improves the efficiency of the method useful in applications to large systems and solids.

  18. Density functional theory investigation of elastic properties and martensitic transformation of Ti-Ta alloys

    Energy Technology Data Exchange (ETDEWEB)

    Chakraborty, Tanmoy; Rogal, Jutta; Drautz, Ralf [Interdisciplinary Centre for Advanced Materials Simulation, Ruhr- Universitaet Bochum (Germany)

    2016-07-01

    Ti-Ta alloys are considered as promising materials for high temperature shape memory alloys as well as biomedical applications. The properties of these alloys have been shown to be strongly composition dependent. The temperature for the martensitic transformation between the high temperature cubic austenite and the low temperature orthorhombic martensite decreases linearly with increasing Ta content. Likewise, the elastic properties show clear trends with changing composition. We use density functional theory to investigate the involved phases in Ti-Ta where the disordered phases are treated by special quasi-random structures. To compare the stability of the involved phases as a function of temperature we calculate free energies using the quasi-harmonic Debye model. The obtained trends in the stability are consistent with experimentally measured transformation temperatures. Furthermore, we determine elastic properties which are in good agreement with experimentally observed trends.

  19. Density functional theory study of inter-layer coupling in bulk tin selenide

    Science.gov (United States)

    Song, Hong-Yue; Lü, Jing-Tao

    2018-03-01

    We study the inter-layer coupling in bulk tin selenide (SnSe) through density functional theory based calculations. Different approximations for the exchange-correlation functionals and the van der Waals interaction are employed. By performing comparison with graphite, MoS2 and black phosphorus, we analyze the inter-layer coupling from different points of view, including the binding energy, the low frequency inter-layer optical phonons, and the inter-layer charge transfer. We find that, there is a strong charge transfer between layers of SnSe, resulting in the strongest inter-layer coupling. Moreover, the charge transfer renders the inter-layer coupling in SnSe not of van der Waals type. Mechanical exfoliation has been used to fabricate mono- or few-layer graphene, MoS2 and black phosphorus. But, our results show that it may be difficult to apply similar technique to SnSe.

  20. A time-dependent density functional theory investigation of plasmon resonances of linear Au atomic chains

    International Nuclear Information System (INIS)

    Liu Dan-Dan; Zhang Hong

    2011-01-01

    We report theoretical studies on the plasmon resonances in linear Au atomic chains by using ab initio time-dependent density functional theory. The dipole responses are investigated each as a function of chain length. They converge into a single resonance in the longitudinal mode but split into two transverse modes. As the chain length increases, the longitudinal plasmon mode is redshifted in energy while the transverse modes shift in the opposite direction (blueshifts). In addition, the energy gap between the two transverse modes reduces with chain length increasing. We find that there are unique characteristics, different from those of other metallic chains. These characteristics are crucial to atomic-scale engineering of single-molecule sensing, optical spectroscopy, and so on. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  1. Covalent addition of chitosan to graphene sheets: Density functional theory explorations of quadrupole coupling constants

    Science.gov (United States)

    Mokhtari, Ali; Harismah, Kun; Mirzaei, Mahmoud

    2015-12-01

    Density functional theory (DFT) calculations have been performed to detect the stabilities and properties of chitosan-functionalized graphene and graphene-oxide structures (G-Chit and GO-Chit). The model systems with two different sizes of sheets have been optimized and the molecular and atomic properties have been evaluated for them. The results indicated that investigated G-Chit and GO-Chit structures could be considered as stable structures but with different properties. The properties for GO and GO-Chit structures are almost similar; however, they are different from the original G and G-Chit structures. The results also indicated that the properties could be also size-dependent, in which different molecular and atomic properties have been observed for the investigate G sheets.

  2. Corrections to the density-functional theory electronic spectrum: Copper phthalocyanine

    DEFF Research Database (Denmark)

    Vazquez, Hector; Jelinek, P.; Brandbyge, Mads

    2009-01-01

    A method for improving the electronic spectrum of standard Density-Functional Theory (DFT) calculations (i.e., LDA or GGA approximations) is presented, and its application is discussed for the case of the copper phthalocyanine (CuPc) molecule. The method is based on a treatment of exchange...... and correlation in a many-body Hamiltonian, and it leads to easy-to-evaluate corrections to the DFT eigenvalues. Self-interaction is largely corrected, so that the modified energy levels do not suffer from spurious crossings, as often encountered for CuPc in DFT, and they remedy the standard underestimation...... or semiempirical functionals for molecular levels, it can be easily applied to any local-orbital DFT approach, improving on several important limitations of standard DFT methods....

  3. IR and Raman spectra of nitroanthracene isomers: substitional effects based on density functional theory study.

    Science.gov (United States)

    Alparone, Andrea; Librando, Vito

    2012-04-01

    Structure, IR and Raman spectra of 1-, 2- and 9-nitroanthracene isomers (1-NA, 2-NA and 9-NA) were calculated and analyzed through density functional theory computations using the B3LYP functional with the 6-311+G** basis set. Steric and π-conjugative effects determine the characteristic ONCC dihedral angles, which vary from 0° (2-NA) to 28-29° (1-NA) and 59° (9-NA), influencing the relative order of stability along the series 9-NA3000 cm(-1) and utility to discriminate the NA isomers. Structural and spectroscopic results suggest that the unknown mutagenic activity of 1-NA is expected to be between that of 9-NA and 2-NA. Copyright © 2011 Elsevier B.V. All rights reserved.

  4. Temperature-dependent study of isotropic-nematic transition for a Gay-Berne fluid using density-functional theory

    International Nuclear Information System (INIS)

    Singh, Ram Chandra

    2007-01-01

    We have used the density-functional theory to study the effect of varying temperature on the isotropic-nematic transition of a fluid of molecules interacting via the Gay-Berne intermolecular potential. The nematic phase is found to be stable with respect to isotropic phase in the temperature range 0.80≤T*≤1.25. Pair correlation functions needed as input information in density-functional theory is calculated using the Percus-Yevick integral equation theory. We find that the density-functional theory is good for studying the isotropic-nematic transition in molecular fluids if the values of the pair-correlation functions in the isotropic phase are known accurately. We have also compared our results with computer simulation results wherever they are available

  5. Performance of exchange-correlation functionals in density functional theory calculations for liquid metal: A benchmark test for sodium

    Science.gov (United States)

    Han, Jeong-Hwan; Oda, Takuji

    2018-04-01

    The performance of exchange-correlation functionals in density-functional theory (DFT) calculations for liquid metal has not been sufficiently examined. In the present study, benchmark tests of Perdew-Burke-Ernzerhof (PBE), Armiento-Mattsson 2005 (AM05), PBE re-parameterized for solids, and local density approximation (LDA) functionals are conducted for liquid sodium. The pair correlation function, equilibrium atomic volume, bulk modulus, and relative enthalpy are evaluated at 600 K and 1000 K. Compared with the available experimental data, the errors range from -11.2% to 0.0% for the atomic volume, from -5.2% to 22.0% for the bulk modulus, and from -3.5% to 2.5% for the relative enthalpy depending on the DFT functional. The generalized gradient approximation functionals are superior to the LDA functional, and the PBE and AM05 functionals exhibit the best performance. In addition, we assess whether the error tendency in liquid simulations is comparable to that in solid simulations, which would suggest that the atomic volume and relative enthalpy performances are comparable between solid and liquid states but that the bulk modulus performance is not. These benchmark test results indicate that the results of liquid simulations are significantly dependent on the exchange-correlation functional and that the DFT functional performance in solid simulations can be used to roughly estimate the performance in liquid simulations.

  6. Electron transport in polycyclic aromatic hydrocarbons/boron nitride hybrid structures: density functional theory combined with the nonequilibrium Green's function.

    Science.gov (United States)

    Panahi, S F K S; Namiranian, Afshin; Soleimani, Maryam; Jamaati, Maryam

    2018-02-07

    We investigate the electronic transport properties of two types of junction based on single polyaromatic hydrocarbons (PAHs) and PAHs embedded in boron nitride (h-BN) nanoribbons, using nonequilibrium Green's functions (NEGF) and density functional theory (DFT). In the PAH junctions, a Fano resonance line shape at the Fermi energy in the transport feature can be clearly seen. In hybrid junctions, structural asymmetries enable interactions between the electronic states, leading to observation of interface-based transport. Our findings reveal that the interface of PAH/h-BN strongly affects the transport properties of the structures.

  7. Exchange-Correlation Effects for Noncovalent Interactions in Density Functional Theory.

    Science.gov (United States)

    Otero-de-la-Roza, A; DiLabio, Gino A; Johnson, Erin R

    2016-07-12

    In this article, we develop an understanding of how errors from exchange-correlation functionals affect the modeling of noncovalent interactions in dispersion-corrected density-functional theory. Computed CCSD(T) reference binding energies for a collection of small-molecule clusters are decomposed via a molecular many-body expansion and are used to benchmark density-functional approximations, including the effect of semilocal approximation, exact-exchange admixture, and range separation. Three sources of error are identified. Repulsion error arises from the choice of semilocal functional approximation. This error affects intermolecular repulsions and is present in all n-body exchange-repulsion energies with a sign that alternates with the order n of the interaction. Delocalization error is independent of the choice of semilocal functional but does depend on the exact exchange fraction. Delocalization error misrepresents the induction energies, leading to overbinding in all induction n-body terms, and underestimates the electrostatic contribution to the 2-body energies. Deformation error affects only monomer relaxation (deformation) energies and behaves similarly to bond-dissociation energy errors. Delocalization and deformation errors affect systems with significant intermolecular orbital interactions (e.g., hydrogen- and halogen-bonded systems), whereas repulsion error is ubiquitous. Many-body errors from the underlying exchange-correlation functional greatly exceed in general the magnitude of the many-body dispersion energy term. A functional built to accurately model noncovalent interactions must contain a dispersion correction, semilocal exchange, and correlation components that minimize the repulsion error independently and must also incorporate exact exchange in such a way that delocalization error is absent.

  8. Density functional theory study of bulk and single-layer magnetic semiconductor CrPS4

    Science.gov (United States)

    Zhuang, Houlong L.; Zhou, Jia

    2016-11-01

    Searching for two-dimensional (2D) materials with multifunctionality is one of the main goals of current research in 2D materials. Magnetism and semiconducting are certainly two desirable functional properties for a single 2D material. In line with this goal, here we report a density functional theory (DFT) study of bulk and single-layer magnetic semiconductor CrPS4. We find that the ground-state magnetic structure of bulk CrPS4 exhibits the A-type antiferromagnetic ordering, which transforms to ferromagnetic (FM) ordering in single-layer CrPS4. The calculated formation energy and phonon spectrum confirm the stability of single-layer CrPS4. The band gaps of FM single-layer CrPS4 calculated with a hybrid density functional are within the visible-light range. We also study the effects of FM ordering on the optical absorption spectra and band alignments for water splitting, indicating that single-layer CrPS4 could be a potential photocatalyst. Our work opens up ample opportunities of energy-related applications of single-layer CrPS4.

  9. DGDFT: A massively parallel method for large scale density functional theory calculations.

    Science.gov (United States)

    Hu, Wei; Lin, Lin; Yang, Chao

    2015-09-28

    We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10(-4) Hartree/atom in terms of the error of energy and 6.2 × 10(-4) Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail.

  10. Dibenzothiophene adsorption at boron doped carbon nanoribbons studied within density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    López-Albarrán, P. [Facultad de Ingeniería en Tecnología de la Madera, Universidad Michoacana de San Nicolás de Hidalgo, Santiago Tapia 403, CP 58000, Morelia, Michoacán (Mexico); Navarro-Santos, P., E-mail: pnavarrosa@conacyt.mx [Instituto de Investigaciones Químico-Biológicas, Universidad Michoacana de San Nicolás de Hidalgo, Santiago Tapia 403, CP 58000, Morelia, Michoacán (Mexico); Garcia-Ramirez, M. A. [Research Centre for Innovation in Aeronautical Engineering, Universidad Autónoma de Nuevo León, Ciudad Universitaria, San Nicolás de los Garza, CP 66451 Nuevo León (Mexico); Ricardo-Chávez, J. L. [Instituto Potosino de Investigación Científica y Tecnológica, Camino a la Presa San José 2055, Lomas 4" asección, CP 78216, San Luis Potosí, S. L. P. (Mexico)

    2015-06-21

    The adsorption of dibenzothiophene (DBT) on bare and boron-doped armchair carbon nanoribbons (ACNRs) is being investigated in the framework of the density functional theory by implementing periodic boundary conditions that include corrections from dispersion interactions. The reactivity of the ACNRs is characterized by using the Fukui functions as well as the electrostatic potential as local descriptors. Non-covalent adsorption mechanism is found when using the local Perdew-Becke-Ernzerhof functional, regardless of the DBT orientation and adsorption location. The dispersion interactions addition is a milestone to describe the adsorption process. The charge defects introduced in small number (i.e., by doping with B atoms), within the ACNRs increases the selectivity towards sulfur mainly due to the charge depletion at B sites. The DBT magnitude in the adsorption energy shows non-covalent interactions. As a consequence, the configurations where the DBT is adsorbed on a BC{sub 3} island increase the adsorption energy compared to random B arrangements. The stability of these configurations can be explained satisfactorily in terms of dipole interactions. Nevertheless, from the charge-density difference analysis and the weak Bader charge-distribution interactions cannot be ruled out completely. This is why the electronic properties of the ribbons are analyzed in order to elucidate the key role played by the B and DBT states in the adsorbed configurations.

  11. DGDFT: A massively parallel method for large scale density functional theory calculations

    Energy Technology Data Exchange (ETDEWEB)

    Hu, Wei, E-mail: whu@lbl.gov; Yang, Chao, E-mail: cyang@lbl.gov [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Lin, Lin, E-mail: linlin@math.berkeley.edu [Computational Research Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States); Department of Mathematics, University of California, Berkeley, California 94720 (United States)

    2015-09-28

    We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10{sup −4} Hartree/atom in terms of the error of energy and 6.2 × 10{sup −4} Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail.

  12. DGDFT: A massively parallel method for large scale density functional theory calculations

    International Nuclear Information System (INIS)

    Hu, Wei; Yang, Chao; Lin, Lin

    2015-01-01

    We describe a massively parallel implementation of the recently developed discontinuous Galerkin density functional theory (DGDFT) method, for efficient large-scale Kohn-Sham DFT based electronic structure calculations. The DGDFT method uses adaptive local basis (ALB) functions generated on-the-fly during the self-consistent field iteration to represent the solution to the Kohn-Sham equations. The use of the ALB set provides a systematic way to improve the accuracy of the approximation. By using the pole expansion and selected inversion technique to compute electron density, energy, and atomic forces, we can make the computational complexity of DGDFT scale at most quadratically with respect to the number of electrons for both insulating and metallic systems. We show that for the two-dimensional (2D) phosphorene systems studied here, using 37 basis functions per atom allows us to reach an accuracy level of 1.3 × 10 −4 Hartree/atom in terms of the error of energy and 6.2 × 10 −4 Hartree/bohr in terms of the error of atomic force, respectively. DGDFT can achieve 80% parallel efficiency on 128,000 high performance computing cores when it is used to study the electronic structure of 2D phosphorene systems with 3500-14 000 atoms. This high parallel efficiency results from a two-level parallelization scheme that we will describe in detail

  13. Optical rotation calculated with time-dependent density functional theory: the OR45 benchmark.

    Science.gov (United States)

    Srebro, Monika; Govind, Niranjan; de Jong, Wibe A; Autschbach, Jochen

    2011-10-13

    Time-dependent density functional theory (TDDFT) computations are performed for 42 organic molecules and three transition metal complexes, with experimental molar optical rotations ranging from 2 to 2 × 10(4) deg cm(2) dmol(-1). The performances of the global hybrid functionals B3LYP, PBE0, and BHLYP, and of the range-separated functionals CAM-B3LYP and LC-PBE0 (the latter being fully long-range corrected), are investigated. The performance of different basis sets is studied. When compared to liquid-phase experimental data, the range-separated functionals do, on average, not perform better than B3LYP and PBE0. Median relative deviations between calculations and experiment range from 25 to 29%. A basis set recently proposed for optical rotation calculations (LPol-ds) on average does not give improved results compared to aug-cc-pVDZ in TDDFT calculations with B3LYP. Individual cases are discussed in some detail, among them norbornenone for which the LC-PBE0 functional produced an optical rotation that is close to available data from coupled-cluster calculations, but significantly smaller in magnitude than the liquid-phase experimental value. Range-separated functionals and BHLYP perform well for helicenes and helicene derivatives. Metal complexes pose a challenge to first-principles calculations of optical rotation.

  14. The structural and electronic properties of amine-functionalized boron nitride nanotubes via ammonia plasmas: a density functional theory study

    International Nuclear Information System (INIS)

    Cao Fenglei; Ji Yuemeng; Zhao Cunyuan; Ren Wei

    2009-01-01

    The reaction behavior of the chemical modification of boron nitride nanotubes (BNNTs) with ammonia plasmas has been investigated by density functional theory (DFT) calculations. Unlike previously studied functionalization with NH 3 and amino functional groups, we found that NH 2 * radicals involved in the ammonia plasmas can be covalently incorporated to BNNTs through a strong single B-N bond. Subsequently, the H * radicals also involved in the ammonia plasmas would prefer to combine with the N atoms neighboring the NH 2 -functionalized B atoms. Our study revealed that this reaction behavior can be elucidated using the frontier orbital theory. The calculated band structures and density of states (DOS) indicate that this modification is an effective method to modulate the electronic properties of BNNTs. We have discussed various defects on the surface of BNNTs generated by collisions of N 2 + ions. For most defects considered, the reactivity of the functionalization of BNNTs with NH 2 * are enhanced. Our conclusions are independent of the chirality, and the diameter dependence of the reaction energies is presented.

  15. Use of density functional theory orbitals in the GVVPT2 variant of second-order multistate multireference perturbation theory.

    Science.gov (United States)

    Hoffmann, Mark R; Helgaker, Trygve

    2015-03-05

    A new variation of the second-order generalized van Vleck perturbation theory (GVVPT2) for molecular electronic structure is suggested. In contrast to the established procedure, in which CASSCF or MCSCF orbitals are first obtained and subsequently used to define a many-electron model (or reference) space, the use of an orbital space obtained from the local density approximation (LDA) variant of density functional theory is considered. Through a final, noniterative diagonalization of an average Fock matrix within orbital subspaces, quasicanonical orbitals that are otherwise indistinguishable from quasicanonical orbitals obtained from a CASSCF or MCSCF calculation are obtained. Consequently, all advantages of the GVVPT2 method are retained, including use of macroconfigurations to define incomplete active spaces and rigorous avoidance of intruder states. The suggested variant is vetted on three well-known model problems: the symmetric stretching of the O-H bonds in water, the dissociation of N2, and the stretching of ground and excited states C2 to more than twice the equilibrium bond length of the ground state. It is observed that the LDA-based GVVPT2 calculations yield good results, of comparable quality to conventional CASSCF-based calculations. This is true even for the C2 model problem, in which the orbital space for each state was defined by the LDA orbitals. These results suggest that GVVPT2 can be applied to much larger problems than previously accessible.

  16. Communication: Orbital instabilities and triplet states from time-dependent density functional theory and long-range corrected functionals

    Science.gov (United States)

    Sears, John S.; Koerzdoerfer, Thomas; Zhang, Cai-Rong; Brédas, Jean-Luc

    2011-10-01

    Long-range corrected hybrids represent an increasingly popular class of functionals for density functional theory (DFT) that have proven to be very successful for a wide range of chemical applications. In this Communication, we examine the performance of these functionals for time-dependent (TD)DFT descriptions of triplet excited states. Our results reveal that the triplet energies are particularly sensitive to the range-separation parameter; this sensitivity can be traced back to triplet instabilities in the ground state coming from the large effective amounts of Hartree-Fock exchange included in these functionals. As such, the use of standard long-range corrected functionals for the description of triplet states at the TDDFT level is not recommended.

  17. Wavelet-based linear-response time-dependent density-functional theory

    Science.gov (United States)

    Natarajan, Bhaarathi; Genovese, Luigi; Casida, Mark E.; Deutsch, Thierry; Burchak, Olga N.; Philouze, Christian; Balakirev, Maxim Y.

    2012-06-01

    Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BIGDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program DEMON2K for the calculation of electronic absorption spectra of N2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BIGDFT than for DEMON2K. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BIGDFT, while all virtual orbitals are included in TD-DFT calculations in DEMON2K. As a reality check, we report the X-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1, 2-a]pyridin-3-amine.

  18. Adsorption Properties of Typical Lung Cancer Breath Gases on Ni-SWCNTs through Density Functional Theory

    Directory of Open Access Journals (Sweden)

    Qianqian Wan

    2017-01-01

    Full Text Available A lot of useful information is contained in the human breath gases, which makes it an effective way to diagnose diseases by detecting the typical breath gases. This work investigated the adsorption of typical lung cancer breath gases: benzene, styrene, isoprene, and 1-hexene onto the surface of intrinsic and Ni-doped single wall carbon nanotubes through density functional theory. Calculation results show that the typical lung cancer breath gases adsorb on intrinsic single wall carbon nanotubes surface by weak physisorption. Besides, the density of states changes little before and after typical lung cancer breath gases adsorption. Compared with single wall carbon nanotubes adsorption, single Ni atom doping significantly improves its adsorption properties to typical lung cancer breath gases by decreasing adsorption distance and increasing adsorption energy and charge transfer. The density of states presents different degrees of variation during the typical lung cancer breath gases adsorption, resulting in the specific change of conductivity of gas sensing material. Based on the different adsorption properties of Ni-SWCNTs to typical lung cancer breath gases, it provides an effective way to build a portable noninvasive portable device used to evaluate and diagnose lung cancer at early stage in time.

  19. Dissecting molecular descriptors into atomic contributions in density functional reactivity theory

    Energy Technology Data Exchange (ETDEWEB)

    Rong, Chunying [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Lu, Tian [School of Chemical and Biological Engineering, University of Science and Technology Beijing, Beijing (China); Liu, Shubin, E-mail: shubin@email.unc.edu [Key Laboratory of Chemical Biology and Traditional Chinese Medicine Research (Ministry of Education of China) and Key Laboratory of Resource Fine-Processing and Advanced Materials of Hunan Province, College of Chemistry and Chemical Engineering, Hunan Normal University, Changsha, Hunan 410081 (China); Research Computing Center, University of North Carolina, Chapel Hill, North Carolina 27599-3420 (United States)

    2014-01-14

    Density functional reactivity theory (DFRT) employs the electron density of a molecule and its related quantities such as gradient and Laplacian to describe its structure and reactivity properties. Proper descriptions at both molecular (global) and atomic (local) levels are equally important and illuminating. In this work, we make use of Bader's zero-flux partition scheme and consider atomic contributions for a few global reactivity descriptors in DFRT, including the density-based quantification of steric effect and related indices. Earlier, we proved that these quantities are intrinsically correlated for atomic and molecular systems [S. B. Liu, J. Chem. Phys. 126, 191107 (2007); ibid. 126, 244103 (2007)]. In this work, a new basin-based integration algorithm has been implemented, whose reliability and effectiveness have been extensively examined. We also investigated a list of simple hydrocarbon systems and different scenarios of bonding processes, including stretching, bending, and rotating. Interesting changing patterns for the atomic and molecular values of these quantities have been revealed for different systems. This work not only confirms the strong correlation between these global reactivity descriptors for molecular systems, as theoretically proven earlier by us, it also provides new and unexpected changing patterns for their atomic values, which can be employed to understand the origin and nature of chemical phenomena.

  20. Dissecting molecular descriptors into atomic contributions in density functional reactivity theory

    International Nuclear Information System (INIS)

    Rong, Chunying; Lu, Tian; Liu, Shubin

    2014-01-01

    Density functional reactivity theory (DFRT) employs the electron density of a molecule and its related quantities such as gradient and Laplacian to describe its structure and reactivity properties. Proper descriptions at both molecular (global) and atomic (local) levels are equally important and illuminating. In this work, we make use of Bader's zero-flux partition scheme and consider atomic contributions for a few global reactivity descriptors in DFRT, including the density-based quantification of steric effect and related indices. Earlier, we proved that these quantities are intrinsically correlated for atomic and molecular systems [S. B. Liu, J. Chem. Phys. 126, 191107 (2007); ibid. 126, 244103 (2007)]. In this work, a new basin-based integration algorithm has been implemented, whose reliability and effectiveness have been extensively examined. We also investigated a list of simple hydrocarbon systems and different scenarios of bonding processes, including stretching, bending, and rotating. Interesting changing patterns for the atomic and molecular values of these quantities have been revealed for different systems. This work not only confirms the strong correlation between these global reactivity descriptors for molecular systems, as theoretically proven earlier by us, it also provides new and unexpected changing patterns for their atomic values, which can be employed to understand the origin and nature of chemical phenomena

  1. Numerical implementation of time-dependent density functional theory for extended systems in extreme environments

    Energy Technology Data Exchange (ETDEWEB)

    Baczewski, Andrew David; Shulenburger, Luke; Desjarlais, Michael Paul; Magyar, Rudolph J.

    2014-02-01

    In recent years, DFT-MD has been shown to be a useful computational tool for exploring the properties of WDM. These calculations achieve excellent agreement with shock compression experiments, which probe the thermodynamic parameters of the Hugoniot state. New X-ray Thomson Scattering diagnostics promise to deliver independent measurements of electronic density and temperature, as well as structural information in shocked systems. However, they require the development of new levels of theory for computing the associated observables within a DFT framework. The experimentally observable x-ray scattering cross section is related to the electronic density-density response function, which is obtainable using TDDFT - a formally exact extension of conventional DFT that describes electron dynamics and excited states. In order to develop a capability for modeling XRTS data and, more generally, to establish a predictive capability for rst principles simulations of matter in extreme conditions, real-time TDDFT with Ehrenfest dynamics has been implemented in an existing PAW code for DFT-MD calculations. The purpose of this report is to record implementation details and benchmarks as the project advances from software development to delivering novel scienti c results. Results range from tests that establish the accuracy, e ciency, and scalability of our implementation, to calculations that are veri ed against accepted results in the literature. Aside from the primary XRTS goal, we identify other more general areas where this new capability will be useful, including stopping power calculations and electron-ion equilibration.

  2. Can Unrestricted Density-Functional Theory Describe Open Shell Singlet Biradicals?

    Directory of Open Access Journals (Sweden)

    Dieter Cremer

    2002-04-01

    Full Text Available Abstract: Unrestricted density functional theory (UDFT can be used for the description of open-shell singlet (OSS biradicals provided a number of precautions are considered. Biradicals that require a two-determinantal wave function (e.g. OSS state of carbenes cannot be described by UDFT for principal reasons. However, if the overlap between the open-shell orbitals is small (the single electrons are located at different atomic centers errors become small and, then, the principal failure of UDFT in these cases is not apparent and may even be disguised by the fact that UDFT has the advantage of describing spin polarization better than any restricted open shell DFT method. In the case of OSS biradicals with two- or multiconfigurational character (but a onedeterminantal form of the leading configuration, reasonable results can be obtained by broken-symmetry (BS-UDFT, however in each case this has to be checked. In no case is it reasonable to lower the symmetry of a molecule to get a suitable UDFT description. Hybrid functionals such as B3LYP perform better than pure DFT functionals in BS-UDFT calculations because the former reduce the self-interaction error of DFT exchange functionals, which mimics unspecified static electron correlation effects, so that the inclusion of specific static electron correlation effects via the form of the wavefunction becomes more effective.

  3. Reaction energetics on long-range corrected density functional theory: Diels-Alder reactions.

    Science.gov (United States)

    Singh, Raman K; Tsuneda, Takao

    2013-02-15

    The possibility of quantitative reaction analysis on the orbital energies of long-range corrected density functional theory (LC-DFT) is presented. First, we calculated the Diels-Alder reaction enthalpies that have been poorly given by conventional functionals including B3LYP functional. As a result, it is found that the long-range correction drastically improves the reaction enthalpies. The barrier height energies were also computed for these reactions. Consequently, we found that dispersion correlation correction is also crucial to give accurate barrier height energies. It is, therefore, concluded that both long-range exchange interactions and dispersion correlations are essentially required in conventional functionals to investigate Diels-Alder reactions quantitatively. After confirming that LC-DFT accurately reproduces the orbital energies of the reactant and product molecules of the Diels-Alder reactions, the global hardness responses, the halves of highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, along the intrinsic reaction coordinates of two Diels-Alder reactions were computed. We noticed that LC-DFT results satisfy the maximum hardness rule for overall reaction paths while conventional functionals violate this rule on the reaction pathways. Furthermore, our results also show that the HOMO-LUMO gap variations are close to the reaction enthalpies for these Diels-Alder reactions. Based on these results, we foresee quantitative reaction analysis on the orbital energies. Copyright © 2012 Wiley Periodicals, Inc.

  4. General atomistic approach for modeling metal-semiconductor interfaces using density functional theory and nonequilibrium Green's function

    DEFF Research Database (Denmark)

    Stradi, Daniele; Martinez, Umberto; Blom, Anders

    2016-01-01

    Metal-semiconductor contacts are a pillar of modern semiconductor technology. Historically, their microscopic understanding has been hampered by the inability of traditional analytical and numerical methods to fully capture the complex physics governing their operating principles. Here we introduce...... an atomistic approach based on density functional theory and nonequilibrium Green's function, which includes all the relevant ingredients required to model realistic metal-semiconductor interfaces and allows for a direct comparison between theory and experiments via I-Vbias curve simulations. We apply...... interfaces as it neglects electron tunneling, and that finite-size atomistic models have problems in describing these interfaces in the presence of doping due to a poor representation of space-charge effects. Conversely, the present method deals effectively with both issues, thus representing a valid...

  5. Dynamics of two-phase interfaces and surface tensions: A density-functional theory perspective

    Science.gov (United States)

    Yatsyshin, Petr; Sibley, David N.; Duran-Olivencia, Miguel A.; Kalliadasis, Serafim

    2016-11-01

    Classical density functional theory (DFT) is a statistical mechanical framework for the description of fluids at the nanoscale, where the inhomogeneity of the fluid structure needs to be carefully accounted for. By expressing the grand free-energy of the fluid as a functional of the one-body density, DFT offers a theoretically consistent and computationally accessible way to obtain two-phase interfaces and respective interfacial tensions in a ternary solid-liquid-gas system. The dynamic version of DFT (DDFT) can be rigorously derived from the Smoluchowsky picture of the dynamics of colloidal particles in a solvent. It is generally agreed that DDFT can capture the diffusion-driven evolution of many soft-matter systems. In this context, we use DDFT to investigate the dynamic behaviour of two-phase interfaces in both equilibrium and dynamic wetting and discuss the possibility of defining a time-dependent surface tension, which still remains in debate. We acknowledge financial support from the European Research Council via Advanced Grant No. 247031 and from the Engineering and Physical Sciences Research Council of the UK via Grants No. EP/L027186 and EP/L020564.

  6. Accurate and systematically improvable density functional theory embedding for correlated wavefunctions

    International Nuclear Information System (INIS)

    Goodpaster, Jason D.; Barnes, Taylor A.; Miller, Thomas F.; Manby, Frederick R.

    2014-01-01

    We analyze the sources of error in quantum embedding calculations in which an active subsystem is treated using wavefunction methods, and the remainder using density functional theory. We show that the embedding potential felt by the electrons in the active subsystem makes only a small contribution to the error of the method, whereas the error in the nonadditive exchange-correlation energy dominates. We test an MP2 correction for this term and demonstrate that the corrected embedding scheme accurately reproduces wavefunction calculations for a series of chemical reactions. Our projector-based embedding method uses localized occupied orbitals to partition the system; as with other local correlation methods, abrupt changes in the character of the localized orbitals along a reaction coordinate can lead to discontinuities in the embedded energy, but we show that these discontinuities are small and can be systematically reduced by increasing the size of the active region. Convergence of reaction energies with respect to the size of the active subsystem is shown to be rapid for all cases where the density functional treatment is able to capture the polarization of the environment, even in conjugated systems, and even when the partition cuts across a double bond

  7. Study of chemical bonding in the interhalogen complexes based on density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Poleshchuk, O. Kh., E-mail: poleshch@tspu.edu.ru [National Research Tomsk Polytechnic University (Russian Federation); Fateev, A. V.; Yarkova, A. G. [Tomsk State Pedagogical University (Russian Federation); Ermakhanov, M. N.; Saidakhmetov, P. A. [M. Auezov South Kazakhstan State University (Kazakhstan)

    2016-12-15

    The density functional theory analysis was used for a number XYL complexes (XY is a dihalogen molecule and L is a Lewis base), formed between molecules I{sub 2}, ICl, IBr and pyridine. The calculated geometrical parameters, IR spectra and nuclear quadrupole interaction constants of iodine are consistent with the data of microwave spectroscopy and nuclear quadrupole resonance. The good correlation between the experimental and calculated binding energies of the inner electrons of iodine, chlorine and nitrogen atoms were found with the calculation using both Gaussian and Slater functions. The comparison of experimental and calculated changes in the electron density on the atoms upon complex formation suggested the choice of scheme for calculating the effective charge on the atoms, which allow us to interpret the experimental spectra. It is shown that the use of both calculated schemes allows us to predict the enthalpy of complex formation in close agreement with the experimental values. The energy analysis shows that in the complexes the electrostatic binding energy dominates that of covalent binding.

  8. Density functional theory investigation of oxygen interaction with boron-doped graphite

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Juan; Wang, Chen [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Liang, Tongxiang, E-mail: txliang@tsinghua.edu.cn [State Key Lab of New Ceramic and Fine Processing, Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084 (China); Lai, Wensheng [Advanced Material Laboratory, School of Materials Science & Engineering, Tsinghua University, Beijing, 100084 (China)

    2016-12-30

    Highlights: • Density-functional approach is applied to study the interaction of oxygen with boron-doped graphite. • Adsorption and diffusion of oxygen atoms on boron doped graphite surfaces are studied. • Recombination of oxygen is investigated by ER and LH mechanisms. • Low boron concentration facilitates O{sub 2} formation while high boron loading inhibits the recombination. • The presence of B−B bonds due to boron accumulation makes it impossible for oxygen recombination. - Abstract: Boron inserted as impurity by substitution of carbon atoms in graphite is known to change (improve or deteriorate) oxidation resistance of nuclear graphite, but the reason for both catalytic and inhibiting oxidation is still uncertain. As a first step, this work is more specially devoted to the adsorption and diffusion of oxygen atoms on the surface and related to the problem of oxygen retention on the pure and boron-containing graphite surfaces. Adsorption energies and energy barriers associated to the diffusion for molecular oxygen recombination are calculated in the density functional theory framework. The existence of boron modifies the electronic structure of the surface, which results in an increase of the adsorption energy for O. However, low boron loading makes it easier for the recombination into molecular oxygen. For high boron concentration, it induces a better O retention capability in graphite because the presence of B-B bonds decreases recombination of the adsorbed oxygen atoms. A possible explanation for both catalytic and inhibiting effects of boron in graphite is proposed.

  9. The role of the wave function in the GRW matter density theory

    Energy Technology Data Exchange (ETDEWEB)

    Egg, Matthias [University of Lausanne (Switzerland)

    2014-07-01

    Every approach to quantum mechanics postulating some kind of primitive ontology (e.g., Bohmian particles, a mass density field or flash-like collapse events) faces the challenge of clarifying the ontological status of the wave function. More precisely, one needs to spell out in what sense the wave function ''governs'' the behaviour of the primitive ontology, such that the empirical predictions of standard quantum mechanics are recovered. For Bohmian mechanics, this challenge has been addressed in recent papers by Belot and Esfeld et al. In my talk, I do the same for the matter density version of the Ghirardi-Rimini-Weber theory (GRWm). Doing so will highlight relevant similarities and differences between Bohmian mechanics and GRWm. The differences are a crucial element in the evaluation of the relative strengths and weaknesses of the two approaches, while the similarities can shed light on general characteristics of the primitive ontology approach, as opposed to other interpretative approaches to quantum mechanics.

  10. Modeling of Materials for Energy Storage: A Challenge for Density Functional Theory

    Science.gov (United States)

    Kaltak, Merzuk; Fernandez-Serra, Marivi; Hybertsen, Mark S.

    Hollandite α-MnO2 is a promising material for rechargeable batteries and is studied extensively in the community because of its interesting tunnel structure and the corresponding large capacity for lithium as well as sodium ions. However, the presence of partially reduced Mn ions due to doping with Ag or during lithiation makes hollandite a challenging system for density functional theory and the conventionally employed PBE+U method. A naive attempt to model the ternary system LixAgyMnO2 with density functionals, similar to those employed for the case y = 0 , fails and predicts a strong monoclinic distortion of the experimentally observed tetragonal unit cell for Ag2Mn8O16. Structure and binding energies are compared with experimental data and show the importance of van der Waals interactions as well as the necessity for an accurate description of the cooperative Jan-Teller effects for silver hollandite AgyMnO2. Based on these observations a ternary phase diagram is calculated allowing to predict the physical and chemical properties of LixAgyMnO2, such as stable stoichiometries, open circuit voltages, the formation of Ag metal and the structural change during lithiation. Department of Energy (DOE) under award #DE-SC0012673.

  11. Designing mixed metal halide ammines for ammonia storage using density functional theory and genetic algorithms.

    Science.gov (United States)

    Jensen, Peter Bjerre; Lysgaard, Steen; Quaade, Ulrich J; Vegge, Tejs

    2014-09-28

    Metal halide ammines have great potential as a future, high-density energy carrier in vehicles. So far known materials, e.g. Mg(NH3)6Cl2 and Sr(NH3)8Cl2, are not suitable for automotive, fuel cell applications, because the release of ammonia is a multi-step reaction, requiring too much heat to be supplied, making the total efficiency lower. Here, we apply density functional theory (DFT) calculations to predict new mixed metal halide ammines with improved storage capacities and the ability to release the stored ammonia in one step, at temperatures suitable for system integration with polymer electrolyte membrane fuel cells (PEMFC). We use genetic algorithms (GAs) to search for materials containing up to three different metals (alkaline-earth, 3d and 4d) and two different halides (Cl, Br and I) - almost 27,000 combinations, and have identified novel mixtures, with significantly improved storage capacities. The size of the search space and the chosen fitness function make it possible to verify that the found candidates are the best possible candidates in the search space, proving that the GA implementation is ideal for this kind of computational materials design, requiring calculations on less than two percent of the candidates to identify the global optimum.

  12. Density functional theory for field emission from carbon nano-structures

    Energy Technology Data Exchange (ETDEWEB)

    Li, Zhibing, E-mail: stslzb@mail.sysu.edu.cn

    2015-12-15

    Electron field emission is understood as a quantum mechanical many-body problem in which an electronic quasi-particle of the emitter is converted into an electron in vacuum. Fundamental concepts of field emission, such as the field enhancement factor, work-function, edge barrier and emission current density, will be investigated, using carbon nanotubes and graphene as examples. A multi-scale algorithm basing on density functional theory is introduced. We will argue that such a first principle approach is necessary and appropriate for field emission of nano-structures, not only for a more accurate quantitative description, but, more importantly, for deeper insight into field emission. - Highlights: • Applications of DFT to electron field emission of nano-structures are reviewed. • Fundamental concepts of field emission are re-visited with emphasis on the many-body effects. • New insights to field emission of nano-structures are obtained by multi-scale DFT calculations. • It is shown that the exchange–correlation effect on the emission barrier is significant. • Spontaneous symmetry breaking in field emission of CNT has been predicted.

  13. Two- and three-dimensional nonlocal density functional theory for inhomogeneous fluids. 1. Algorithms and parallelization

    International Nuclear Information System (INIS)

    Frink, L.J.D.; Salinger, A.G.

    2000-01-01

    Fluids adsorbed near surfaces, near macromolecules, and in porous materials are inhomogeneous, exhibiting spatially varying density distributions. This inhomogeneity in the fluid plays an important role in controlling a wide variety of complex physical phenomena including wetting, self-assembly, corrosion, and molecular recognition. One of the key methods for studying the properties of inhomogeneous fluids in simple geometries has been density functional theory (DFT). However, there has been a conspicuous lack of calculations in complex two- and three-dimensional geometries. The computational difficulty arises from the need to perform nested integrals that are due to nonlocal terms in the free energy functional. These integral equations are expensive both in evaluation time and in memory requirements; however, the expense can be mitigated by intelligent algorithms and the use of parallel computers. This paper details the efforts to develop efficient numerical algorithms so that nonlocal DFT calculations in complex geometries that require two or three dimensions can be performed. The success of this implementation will enable the study of solvation effects at heterogeneous surfaces, in zeolites, in solvated (bio)polymers, and in colloidal suspensions

  14. Intuitive Density Functional Theory-Based Energy Decomposition Analysis for Protein-Ligand Interactions.

    Science.gov (United States)

    Phipps, M J S; Fox, T; Tautermann, C S; Skylaris, C-K

    2017-04-11

    First-principles quantum mechanical calculations with methods such as density functional theory (DFT) allow the accurate calculation of interaction energies between molecules. These interaction energies can be dissected into chemically relevant components such as electrostatics, polarization, and charge transfer using energy decomposition analysis (EDA) approaches. Typically EDA has been used to study interactions between small molecules; however, it has great potential to be applied to large biomolecular assemblies such as protein-protein and protein-ligand interactions. We present an application of EDA calculations to the study of ligands that bind to the thrombin protein, using the ONETEP program for linear-scaling DFT calculations. Our approach goes beyond simply providing the components of the interaction energy; we are also able to provide visual representations of the changes in density that happen as a result of polarization and charge transfer, thus pinpointing the functional groups between the ligand and protein that participate in each kind of interaction. We also demonstrate with this approach that we can focus on studying parts (fragments) of ligands. The method is relatively insensitive to the protocol that is used to prepare the structures, and the results obtained are therefore robust. This is an application to a real protein drug target of a whole new capability where accurate DFT calculations can produce both energetic and visual descriptors of interactions. These descriptors can be used to provide insights for tailoring interactions, as needed for example in drug design.

  15. A general range-separated double-hybrid density-functional theory.

    Science.gov (United States)

    Kalai, Cairedine; Toulouse, Julien

    2018-04-28

    A range-separated double-hybrid (RSDH) scheme which generalizes the usual range-separated hybrids and double hybrids is developed. This scheme consistently uses a two-parameter Coulomb-attenuating-method (CAM)-like decomposition of the electron-electron interaction for both exchange and correlation in order to combine Hartree-Fock exchange and second-order Møller-Plesset (MP2) correlation with a density functional. The RSDH scheme relies on an exact theory which is presented in some detail. Several semi-local approximations are developed for the short-range exchange-correlation density functional involved in this scheme. After finding optimal values for the two parameters of the CAM-like decomposition, the RSDH scheme is shown to have a relatively small basis dependence and to provide atomization energies, reaction barrier heights, and weak intermolecular interactions globally more accurate or comparable to range-separated MP2 or standard MP2. The RSDH scheme represents a new family of double hybrids with minimal empiricism which could be useful for general chemical applications.

  16. Density functional theory based study of chlorine doped WS2-metal interface

    International Nuclear Information System (INIS)

    Chanana, Anuja; Mahapatra, Santanu

    2016-01-01

    Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS 2 with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS 2 supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS 2 .

  17. Density functional theory based study of chlorine doped WS{sub 2}-metal interface

    Energy Technology Data Exchange (ETDEWEB)

    Chanana, Anuja; Mahapatra, Santanu, E-mail: santanu@dese.iisc.ernet.in [NanoScale Device Research Laboratory, Department of Electronic Systems Engineering, Indian Institute of Science, Bengaluru, Karnataka 560012 (India)

    2016-03-07

    Investigation of a transition metal dichalcogenide (TMD)-metal interface is essential for the effective functioning of monolayer TMD based field effect transistors. In this work, we employ the Density Functional Theory calculations to analyze the modulation of the electronic structure of monolayer WS{sub 2} with chlorine doping and the relative changes in the contact properties when interfaced with gold and palladium. We initially examine the atomic and electronic structures of pure and doped monolayer WS{sub 2} supercell and explore the formation of midgap states with band splitting near the conduction band edge. Further, we analyze the contact nature of the pure supercell with Au and Pd. We find that while Au is physiosorbed and forms n-type contact, Pd is chemisorped and forms p-type contact with a higher valence electron density. Next, we study the interface formed between the Cl-doped supercell and metals and observe a reduction in the Schottky barrier height (SBH) in comparison to the pure supercell. This reduction found is higher for Pd in comparison to Au, which is further validated by examining the charge transfer occurring at the interface. Our study confirms that Cl doping is an efficient mechanism to reduce the n-SBH for both Au and Pd, which form different types of contact with WS{sub 2}.

  18. Density Functional Theory Calculations of Activation Energies for Carrier Capture by Defects in Semiconductors

    Science.gov (United States)

    Modine, N. A.; Wright, A. F.; Lee, S. R.

    The rate of defect-induced carrier recombination is determined by both defect levels and carrier capture cross-sections. Density functional theory (DFT) has been widely and successfully used to predict defect levels, but only recently has work begun to focus on using DFT to determine carrier capture cross-sections. Lang and Henry developed the theory of carrier-capture by multiphonon emission in the 1970s and showed that carrier-capture cross-sections differ between defects primarily due to differences in their carrier capture activation energies. We present an approach to using DFT to calculate carrier capture activation energies that does not depend on an assumed configuration coordinate and that fully accounts for anharmonic effects, which can substantially modify carrier activation energies. We demonstrate our approach for intrinisic defects in GaAs and GaN and discuss how our results depend on the choice of exchange-correlation functional and the treatment of spin polarization. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94AL85000.

  19. Dynamical density functional theory for arbitrary-shape colloidal fluids including inertia and hydrodynamic interactions

    Science.gov (United States)

    Duran-Olivencia, Miguel A.; Goddard, Ben; Kalliadasis, Serafim

    2015-11-01

    Over the last few decades the classical density-functional theory (DFT) and its dynamic extensions (DDFTs) have become a remarkably powerful tool in the study of colloidal fluids. Recently there has been extensive research to generalise all previous DDFTs finally yielding a general DDFT equation (for spherical particles) which takes into account both inertia and hydrodynamic interactions (HI) which strongly influence non-equilibrium properties. The present work will be devoted to a further generalisation of such a framework to systems of anisotropic particles. To this end, the kinetic equation for the Brownian particle distribution function is derived starting from the Liouville equation and making use of Zwanzig's projection-operator techniques. By averaging over all but one particle, a DDFT equation is finally obtained with some similarities to that for spherical colloids. However, there is now an inevitable translational-rotational coupling which affects the diffusivity of asymmetric particles. Lastly, in the overdamped (high friction) limit the theory is notably simplified leading to a DDFT equation which agrees with previous derivations. We acknowledge financial support from European Research Council via Advanced Grant No. 247031.

  20. Ground-state properties of rare-earth metals: an evaluation of density-functional theory

    International Nuclear Information System (INIS)

    Söderlind, Per; Turchi, P E A; Landa, A; Lordi, V

    2014-01-01

    The rare-earth metals have important technological applications due to their magnetic properties, but are scarce and expensive. Development of high-performance magnetic materials with less rare-earth content is desired, but theoretical modeling is hampered by complexities of the rare earths electronic structure. The existence of correlated (atomic-like) 4f electrons in the vicinity of the valence band makes any first-principles theory challenging. Here, we apply and evaluate the efficacy of density-functional theory for the series of lanthanides (rare earths), investigating the influence of the electron exchange and correlation functional, spin-orbit interaction, and orbital polarization. As a reference, the results are compared with those of the so-called ‘standard model’ of the lanthanides in which electrons are constrained to occupy 4f core states with no hybridization with the valence electrons. Some comparisons are also made with models designed for strong electron correlations. Our results suggest that spin–orbit coupling and orbital polarization are important, particularly for the magnitude of the magnetic moments, and that calculated equilibrium volumes, bulk moduli, and magnetic moments show correct trends overall. However, the precision of the calculated properties is not at the level of that found for simpler metals in the Periodic Table of Elements, and the electronic structures do not accurately reproduce x-ray photoemission spectra. (paper)

  1. Lattice density functional theory investigation of pore shape effects. I. Adsorption in single nonperiodic pores.

    Science.gov (United States)

    Malanoski, A P; van Swol, Frank

    2002-10-01

    A fully explicit in three dimensions lattice density functional theory is used to investigate adsorption in single nonperiodic pores. The effect of varying pore shape from the slits and cylinders that are normally simulated was our primary interest. A secondary concern was the results for pores with very large diameters. The shapes investigated were square pores with or without surface roughness, cylinders, right triangle pores, and trapezoidal pores. It was found that pores with very similar shape factors gave similar results but that the introduction of acute angled corners or very large side ratio lengths in rectangular pores gave results that were significantly different. Further, a rectangular pore going towards the limit of infinite side ratio does not approach the results of a slit pore. In all of these cases, the importance of features that are present for only a small portion of the pore is demonstrated.

  2. Structural and Electronic Properties of α2-Graphyne Nanotubes: A Density Functional Theory Study

    Science.gov (United States)

    Majidi, Roya

    2018-02-01

    Another form of carbon-based two-dimensional material in the graphene family, named the α2-graphyne sheet, was predicted very recently. The α2-graphyne sheet was created by doubling each acetylenic linker in an α-graphyne sheet. It exhibited semimetallic Dirac point features similar to graphene and α-graphyne sheets. In the present work, single -walled carbon nanotubes based on an α2-graphyne sheet was introduced. The structural and electronic properties of these nanotubes were studied using density functional theory. It was found that armchair α2-graphyne nanotubes showed metallic behavior, while zigzag α2-graphyne nanotubes were found to have semiconducting or metallic properties depending on tube size. The energy band gap of zigzag α2-graphyne nanotubes decreased with increasing tube diameter. The results indicated that the α2-graphyne sheet and its nanotubes can be proper materials for future nanoelectronics.

  3. Mechanical properties of novel forms of graphyne under strain: A density functional theory study

    Science.gov (United States)

    Majidi, Roya

    2017-06-01

    The mechanical properties of two forms of graphyne sheets named α-graphyne and α2-graphyne under uniaxial and biaxial strains were studied. In-plane stiffness, bulk modulus, and shear modulus were calculated based on density functional theory. The in-plane stiffness, bulk modulus, and shear modulus of α2-graphyne were found to be larger than that of α-graphyne. The maximum values of supported uniaxial and biaxial strains before failure were determined. The α-graphyne was entered into the plastic region with the higher magnitude of tension in comparison to α2-graphyne. The mechanical properties of α-graphyne family revealed that these forms of graphyne are proper materials for use in nanomechanical applications.

  4. Modelling the evaporation of thin films of colloidal suspensions using dynamical density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Robbins, M J; Archer, A J; Thiele, U [Department of Mathematical Sciences, Loughborough University, Leicestershire LE11 3TU (United Kingdom)

    2011-10-19

    Recent experiments have shown that various structures may be formed during the evaporative dewetting of thin films of colloidal suspensions. Nanoparticle deposits of strongly branched 'flower-like', labyrinthine and network structures are observed. They are caused by the different transport processes and the rich phase behaviour of the system. We develop a model for the system, based on a dynamical density functional theory, which reproduces these structures. The model is employed to determine the influences of the solvent evaporation and of the diffusion of the colloidal particles and of the liquid over the surface. Finally, we investigate the conditions needed for 'liquid-particle' phase separation to occur and discuss its effect on the self-organized nanostructures. (paper)

  5. Density Functional Theory Study of Leaching Performance of Different Acids on Pyrochlore (100) Surface

    Science.gov (United States)

    Yang, Xiuli; Fang, Qing; Ouyang, Hui

    2018-06-01

    Pyrochlore leaching using hydrofluoric, sulfuric, and hydrochloric acids has been studied via experimental methods for years, but the interactions between niobium atoms on the pyrochlore surface and different acids have not been investigated. In this work, first-principles calculations based on density functional theory were used to elucidate the leaching performance of these three acids from the viewpoint of geometrical and electronic structures. The calculation results indicate that sulfate, chloride, and fluoride anions influence the geometric structure of pyrochlore (100) to different extents, decreasing in the order: sulfate, fluoride, chloride. Orbitals of O1 and O2 atoms of sulfate hybridized with those of surface niobium atom. Fluorine orbitals hybridized with those of surface niobium atoms. However, no obvious overlap exists between any orbitals of chlorine and surface niobium, revealing that chlorine does not interact chemically with surface niobium atoms.

  6. Hydrodynamic perspective on memory in time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Thiele, M.; Kuemmel, S.

    2009-01-01

    The adiabatic approximation of time-dependent density-functional theory is studied in the context of nonlinear excitations of two-electron singlet systems. We compare the exact time evolution of these systems to the adiabatically exact one obtained from time-dependent Kohn-Sham calculations relying on the exact ground-state exchange-correlation potential. Thus, we can show under which conditions the adiabatic approximation breaks down and memory effects become important. The hydrodynamic formulation of quantum mechanics allows us to interpret these results and relate them to dissipative effects in the Kohn-Sham system. We show how the breakdown of the adiabatic approximation can be inferred from the rate of change of the ground-state noninteracting kinetic energy.

  7. Atom probe tomography simulations and density functional theory calculations of bonding energies in Cu3Au

    KAUST Repository

    Boll, Torben

    2012-10-01

    In this article the Cu-Au binding energy in Cu3Au is determined by comparing experimental atom probe tomography (APT) results to simulations. The resulting bonding energy is supported by density functional theory calculations. The APT simulations are based on the Müller-Schottky equation, which is modified to include different atomic neighborhoods and their characteristic bonds. The local environment is considered up to the fifth next nearest neighbors. To compare the experimental with simulated APT data, the AtomVicinity algorithm, which provides statistical information about the positions of the neighboring atoms, is applied. The quality of this information is influenced by the field evaporation behavior of the different species, which is connected to the bonding energies. © Microscopy Society of America 2012.

  8. Density functional theory study on the formation of reactive benzoquinone imines by hydrogen abstraction

    DEFF Research Database (Denmark)

    Leth, Rasmus; Rydberg, Patrik; Jørgensen, Flemming Steen

    2015-01-01

    Many drug compounds are oxidized by cytochrome P450 (CYP) enzymes to form reactive metabolites. This study presents density functional theory calculations of the CYP-mediated metabolism of acetaminophen and a series of related compounds that can form reactive metabolites by hydrogen abstraction....... The substitution pattern affects the activation barrier for hydrogen abstraction by up to 30 kJ/mol. A correlation (R(2) = 0.72) between the transition-state energies and the corresponding substrate radical energies has been established. Using this correlation is significantly less time-demanding than using...... the porphyrin model to determine the activation energies. We have used this correlation on monosubstituted phenols to rationalize the effect of the various substituents in the drug compounds. In addition to facilitating a chemical interpretation, the approach is sufficiently fast and reliable to be used...

  9. Identifying Tm-C82 isomers with density functional theory calculations

    International Nuclear Information System (INIS)

    Zheng Limin; He Hongqing; Yang Minghui; Zeng Qun; Yang Mingli

    2010-01-01

    Density functional theory calculations have been performed to study the geometrical and electronic properties of endohedral metallofullerene Tm-C 82 isomers. Three energetically favorable isomers (with C s , C 2 and C 2v symmetry, respectively) are identified which are consistent with the nuclear magnetic resonance (NMR) observations. The simulated ultraviolet photoelectron spectra (UPS) based on the three structures agree well with the measurements. Particularly, the parent cage of the experimentally observed Tm-C 82 isomer with C s symmetry is newly assigned, which matches the experiments better than early assignments. In addition, strong interaction between an endohedral Tm atom and the C 82 cage is discussed and is thought to be responsible for the dramatic change in the relative stability of C 82 isomers when Tm is encapsulated.

  10. Theoretical modelling of photoactive molecular systems: insights using the Density Functional Theory

    Energy Technology Data Exchange (ETDEWEB)

    Ciofini, I.; Adamo, C. [Ecole Nationale Superieure de Chimie de Paris, Lab. d' Electrochimie et Chimie Analytique, CNRS UMR 7575, 75 - Paris (France); Laine, Ph.P. [Universite Rene-Descartes, Lab. de Chimie et Biochimie Pharmacologiques et Toxicologiques, CNRS UMR 8601, 75 - Paris (France); Bedioui, F. [Ecole Nationale Superieure de Chimie de Paris, Lab. de Pharmacologie Chimique et Genetique, CNRS FRE 2463 and INSERM U 640, 75 - Paris (France); Daul, C.A. [Fribourg Univ., Dept. de Chimie (Switzerland)

    2006-02-15

    An account of the performance of a modern and efficient approach to Density Functional Theory (DFT) for the prediction of the photophysical behavior of a series of Ru(II) and Os(II) complexes is given. The time-dependent-DFT method was used to interpret their electronic spectra. Two different types of compounds have been analyzed: (1) a complex undergoing a light induced isomerization of one of its coordination bonds; (2) an inorganic dyads expected to undergo intramolecular photoinduced electron transfer to form a charge separated (CS) sate. Besides the noticeable quantitative agreement between computed and experimental absorption spectra, our results allow to clarify, by first principles, both the nature of the excited states and the photochemical behavior of these complex systems, thus underlying the predictive character of the theoretical approach. (authors)

  11. Accuracy of finite-difference harmonic frequencies in density functional theory.

    Science.gov (United States)

    Liu, Kuan-Yu; Liu, Jie; Herbert, John M

    2017-07-15

    Analytic Hessians are often viewed as essential for the calculation of accurate harmonic frequencies, but the implementation of analytic second derivatives is nontrivial and solution of the requisite coupled-perturbed equations engenders a sizable memory footprint for large systems, given that these equations are not required for energy and gradient calculations in density functional theory. Here, we benchmark the alternative approach to harmonic frequencies based on finite differences of analytic first derivatives, a procedure that is amenable to large-scale parallelization. Not only for absolute frequencies but also for isotopic and conformer-dependent frequency shifts in flexible molecules, we find that the finite-difference approach exhibits mean errors numbers. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  12. Navigating Glycerol Conversion Roadmap and Heterogeneous Catalyst Selection Aided by Density Functional Theory: A Review

    Directory of Open Access Journals (Sweden)

    Bin Liu

    2018-01-01

    Full Text Available Glycerol has been utilized in an extremely diversified manner throughout human civilization—ranging from food, to various consumer products, to pharmaceuticals, and even explosives. Large surplus in glycerol supply thanks to biodiesel production and biomass processing has created a demand to further boost its utility. One growing area is to expand the use of glycerol as an alternative feedstock to supplement fuels and chemicals production. Various catalytic processes have been developed. This review summarizes catalytic materials for glycerol reforming, hydrodeoxygenation, and oxidation. In particular, rationale for catalyst selection and new catalyst design will be discussed aided by the knowledge of reaction mechanisms. The role of theoretical density functional theory (DFT in elucidating complex glycerol conversion chemistries is particularly emphasized.

  13. Methyl Butanoate Adsorption on MoS2 Surface: A Density Functional Theory Investigation

    Directory of Open Access Journals (Sweden)

    Prabowo Wahyu Aji Eko

    2018-01-01

    Full Text Available Methyl butanoate is one of the compound which is obtained from triglyceride molecule. It has hydrocarbon components and hence may produce hydrocarbon through hydrodeoxygenation (HDO or decarbonylation (DCO processes. The first step to uncover the underlying mechanism of HDO or DCO is to find the active site of methyl butanoate adsorption over the catalyst. This study attempts to investigate the active site of methyl butanoate adsorption on MoS2 surface. Stable bonding configuration for methyl butanoate adsorption on MoS2 is investigated by using density functional theory (DFT. This investigation consists of geometry optimisation and adsorption energy calculations. The stable configuration of methyl butanoate adsorption on MoS2 surface is found to be on top of Mo atom in Mo-edge surface.

  14. Threshold defect production in silicon determined by density functional theory molecular dynamics simulations

    International Nuclear Information System (INIS)

    Holmstroem, E.; Kuronen, A.; Nordlund, K.

    2008-01-01

    We studied threshold displacement energies for creating stable Frenkel pairs in silicon using density functional theory molecular dynamics simulations. The average threshold energy over all lattice directions was found to be 36±2 STAT ±2 SYST eV, and thresholds in the directions and were found to be 20±2 SYST eV and 12.5±1.5 SYST eV, respectively. Moreover, we found that in most studied lattice directions, a bond defect complex is formed with a lower threshold than a Frenkel pair. The average threshold energy for producing either a bond defect or a Frenkel pair was found to be 24±1 STAT ±2 SYST eV

  15. Predicting the stability of ternary intermetallics with density functional theory and machine learning

    Science.gov (United States)

    Schmidt, Jonathan; Chen, Liming; Botti, Silvana; Marques, Miguel A. L.

    2018-06-01

    We use a combination of machine learning techniques and high-throughput density-functional theory calculations to explore ternary compounds with the AB2C2 composition. We chose the two most common intermetallic prototypes for this composition, namely, the tI10-CeAl2Ga2 and the tP10-FeMo2B2 structures. Our results suggest that there may be ˜10 times more stable compounds in these phases than previously known. These are mostly metallic and non-magnetic. While the use of machine learning reduces the overall calculation cost by around 75%, some limitations of its predictive power still exist, in particular, for compounds involving the second-row of the periodic table or magnetic elements.

  16. Direct decarbonylation of furfural to furan: A density functional theory study on Pt-graphene

    Science.gov (United States)

    Fellah, Mehmet Ferdi

    2017-05-01

    The catalytic mechanism of direct decarbonylation of furfural to furan on Pt graphene surface has been investigated by means of density functional theory (DFT) calculations. The main catalytic mechanism proposed in this study has six steps such as furfural adsorption, dissociation of H from adsorbed furfural, dissociation of carbon monoxide (molecularly) from adsorbed complex, furan formation and desorption of products. It has been concluded that the rate determining step for direct decarbonylation of furfural to furan is furan formation step and global activation barrier for this catalytic system is 82 kJ/mol consisting of zero point energy and thermal energy corrections. Pt-graphene structure has an important role on the catalytic decarbonylation of furfural to furan without any other reactants. This accordingly points out that Pt doped graphene structure might be an encouraging catalyst for direct decarbonylation of furfural to furan molecule as a valuable chemical material.

  17. Adsorption isoterms and capillary condensation in a nanoslit with rough walls: a density functional theory.

    Science.gov (United States)

    Berim, Gersh O; Ruckenstein, Eli

    2012-08-07

    Adsorption isoterms and capillary condensation in an open slit with walls decorated with arrays of pillars are examined using the density functional theory. Compared with the main substrate, the pillars can have the same or different parameters in the Lennard-Jones interaction potential between them and the fluid in the slit. The roughness of the solid surface, defined as the ratio between the area of the actual surface and the area of the surface free of pillars, is controlled by the height of the pillars. It is shown that the capillary condensation pressure first increases with increasing roughness, passes through a maximum, and then decreases. The amount of adsorbed fluid at constant volume of the slit has, in general, a nonmonotonic dependence on roughness. These features of adsorption and capillary condensation are results of increased surface area and changes in the fluid-solid potential energy due to changes in roughness.

  18. Conjugation-promoted reaction of open-cage fullerene: a density functional theory study.

    Science.gov (United States)

    Guo, Yong; Yan, Jingjing; Khashab, Niveen M

    2012-02-01

    Density functional theory calculations are performed to study the addition mechanism of e-rich moieties such as triethyl phosphite to a carbonyl group on the rim of a fullerene orifice. Three possible reaction channels have been investigated. The obtained results show that the reaction of a carbonyl group on a fullerene orifice with triethyl phosphite most likely proceeds along the classical Abramov reaction; however, the classical product is not stable and is converted into the experimental product. An attack on a fullerene carbonyl carbon will trigger a rearrangement of the phosphate group to the carbonyl oxygen as the conversion transition state is stabilized by fullerene conjugation. This work provides a new insight on the reactivity of open-cage fullerenes, which may prove helpful in designing new switchable fullerene systems. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  19. A density functional theory study of the TMG adsorption on the GaN surface

    Energy Technology Data Exchange (ETDEWEB)

    Ptasinska, Maria; Soltys, Jakub; Piechota, Jacek [Interdisciplinary Centre for Materials Modelling, University of Warsaw, ul. Pawinskiego 5a, 02-106 Warszawa (Poland); Krukowski, Stanislaw [Interdisciplinary Centre for Materials Modelling, University of Warsaw, ul. Pawinskiego 5a, 02-106 Warszawa (Poland); Institute of High Pressure Physics, Polish Academy of Sciences, ul. Sokolowska 29/37, 01-142 Warsaw (Poland)

    2011-07-01

    TMG (trimetylogallium) and NH{sub 3} (ammonia) are widely used reactants in the metal organic chemical vapor deposition (MOCVD) technique used in the growth of the GaN thin films. We have recently examined theoretically, with the help of the density functional theory (DFT), TMG adsorption on the GaN(0001) surface in order to study formation of bonds between Ga and N. Dangling bonds on the GaN(0001) surface were saturated with the hydrogen atoms. The slab polarization, which is due to the dangling bonds present on the GaN(0001) surface, and energy of the system in the vicinity of TMG was computed for different distances between the surface atoms and TMG. We also studied TMG diffusion on the GaN surface. As a result, the energy path for diffusion from Top N to Hollow was obtained.

  20. Fast plane wave density functional theory molecular dynamics calculations on multi-GPU machines

    International Nuclear Information System (INIS)

    Jia, Weile; Fu, Jiyun; Cao, Zongyan; Wang, Long; Chi, Xuebin; Gao, Weiguo; Wang, Lin-Wang

    2013-01-01

    Plane wave pseudopotential (PWP) density functional theory (DFT) calculation is the most widely used method for material simulations, but its absolute speed stagnated due to the inability to use large scale CPU based computers. By a drastic redesign of the algorithm, and moving all the major computation parts into GPU, we have reached a speed of 12 s per molecular dynamics (MD) step for a 512 atom system using 256 GPU cards. This is about 20 times faster than the CPU version of the code regardless of the number of CPU cores used. Our tests and analysis on different GPU platforms and configurations shed lights on the optimal GPU deployments for PWP-DFT calculations. An 1800 step MD simulation is used to study the liquid phase properties of GaInP

  1. A Hybrid Density Functional Theory/Molecular Mechanics Approach for Linear Response Properties in Heterogeneous Environments.

    Science.gov (United States)

    Rinkevicius, Zilvinas; Li, Xin; Sandberg, Jaime A R; Mikkelsen, Kurt V; Ågren, Hans

    2014-03-11

    We introduce a density functional theory/molecular mechanical approach for computation of linear response properties of molecules in heterogeneous environments, such as metal surfaces or nanoparticles embedded in solvents. The heterogeneous embedding environment, consisting from metallic and nonmetallic parts, is described by combined force fields, where conventional force fields are used for the nonmetallic part and capacitance-polarization-based force fields are used for the metallic part. The presented approach enables studies of properties and spectra of systems embedded in or placed at arbitrary shaped metallic surfaces, clusters, or nanoparticles. The capability and performance of the proposed approach is illustrated by sample calculations of optical absorption spectra of thymidine absorbed on gold surfaces in an aqueous environment, where we study how different organizations of the gold surface and how the combined, nonadditive effect of the two environments is reflected in the optical absorption spectrum.

  2. Research Update: Density functional theory investigation of the interactions of silver nanoclusters with guanine

    Directory of Open Access Journals (Sweden)

    Brandon B. Dale

    2017-05-01

    Full Text Available Bare and guanine-complexed silver clusters Ag n z (n = 2-6; z = 0-2 are examined using density functional theory to elucidate the geometries and binding motifs that are present experimentally. Whereas the neutral systems remain planar in this size range, a 2D-3D transition occurs at Ag 5 + for the cationic system and at Ag 4 2 + for the dicationic system. Neutral silver clusters can bind with nitrogen 3 or with the pi system of the base. However, positively charged clusters interact with nitrogen 7 and the neighboring carbonyl group. Thus, the cationic silver-DNA clusters present experimentally may preferentially interact at these sites.

  3. Electronic and Optical Properties of Sodium Niobate: A Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Daniel Fritsch

    2018-01-01

    Full Text Available In recent years, much effort has been devoted to replace the most commonly used piezoelectric ceramic lead zirconate titanate Pb[ZrxTi1−x]O3 (PZT with a suitable lead-free alternative for memory or piezoelectric applications. One possible alternative to PZT is sodium niobate as it exhibits electrical and mechanical properties that make it an interesting material for technological applications. The high-temperature simple cubic perovskite structure undergoes a series of structural phase transitions with decreasing temperature. However, particularly the phases at room temperature and below are not yet fully characterised and understood. Here, we perform density functional theory calculations for the possible phases at room temperature and below and report on the structural, electronic, and optical properties of the different phases in comparison to experimental findings.

  4. Study on models of O2 binding to heme using density functional theory

    Directory of Open Access Journals (Sweden)

    Hovorun D. M.

    2009-08-01

    Full Text Available Aim. To study a mechanism of molecular oxygen binding to heme three models of geometry structure of the complex are considered: the axis of O2 molecule is situated perpendicularly to the porphin macrocycle, parallel, and angularly. Methods. The Fe(II porphin complexes with dioxygen are calculated by the quantum-chemical method of density functional theory with the UB3LYP/6-311G approximation. Results. The optimized geometry and electron structures as well as the absorption IR spectra of the complexes in the high-spin (septet state are described. Conclusions. It is shown that the main mechanism of spin-orbit coupling during the O2 binding to heme is connected with peculiarity of the O2 molecule electronic structure.

  5. The hydrogen bond in ice probed by soft x-ray spectroscopy and density functional theory

    International Nuclear Information System (INIS)

    Nilsson, A.; Ogasawara, H.; Cavalleri, M.; Nordlund, D.; Nyberg, M.; Wernet, Ph.; Pettersson, L.G.M.

    2005-01-01

    We combine photoelectron and x-ray absorption spectroscopy with density functional theory to derive a molecular orbital picture of the hydrogen bond in ice. We find that the hydrogen bond involves donation and back-donation of charge between the oxygen lone pair and the O-H antibonding orbitals on neighboring molecules. Together with internal s-p rehybridization this minimizes the repulsive charge overlap of the connecting oxygen and hydrogen atoms, which is essential for a strong attractive electrostatic interaction. Our joint experimental and theoretical results demonstrate that an electrostatic model based on only charge induction from the surrounding medium fails to properly describe the internal charge redistributions upon hydrogen bonding

  6. Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

    International Nuclear Information System (INIS)

    Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

    2009-01-01

    We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

  7. Ab initio density functional theory investigation of structural and electronic properties of silicon carbide nanotube bundles

    Science.gov (United States)

    Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

    2008-10-01

    By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius.

  8. Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

    Science.gov (United States)

    Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

    2009-06-01

    We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated ( 6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated ( 6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

  9. Ab initio density functional theory investigation of structural and electronic properties of silicon carbide nanotube bundles

    International Nuclear Information System (INIS)

    Moradian, Rostam; Behzad, Somayeh; Chegel, Raad

    2008-01-01

    By using ab initio density functional theory the structural and electronic properties of isolated and bundled (8,0) and (6,6) silicon carbide nanotubes (SiCNTs) are investigated. Our results show that for such small diameter nanotubes the inter-tube interaction causes a very small radial deformation, while band splitting and reduction of the semiconducting energy band gap are significant. We compared the equilibrium interaction energy and inter-tube separation distance of (8,0) SiCNT bundle with (10,0) carbon nanotube (CNT) bundle where they have the same radius. We found that there is a larger inter-tube separation and weaker inter-tube interaction in the (8,0) SiCNT bundle with respect to (10,0) CNT bundle, although they have the same radius

  10. Ab initio density functional theory investigation of Li-intercalated silicon carbide nanotube bundles

    Energy Technology Data Exchange (ETDEWEB)

    Moradian, Rostam [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of); Nano Science and Technology Research Center, Razi University, Kermanshah (Iran, Islamic Republic of); Computational Physical Science Research Laboratory, Department of Nano Science, Institute for Studies in Theoretical Physics and Mathematics (IPM), PO Box 19395-5531, Tehran (Iran, Islamic Republic of)], E-mail: moradian.rostam@gmail.com; Behzad, Somayeh; Chegel, Raad [Physics Department, Faculty of Science, Razi University, Kermanshah (Iran, Islamic Republic of)

    2009-06-15

    We present the results of ab initio density functional theory calculations on the energetic, and geometric and electronic structure of Li-intercalated (6,6) silicon carbide nanotube (SiCNT) bundles. Our results show that intercalation of lithium leads to the significant changes in the geometrical structure. The most prominent effect of Li intercalation on the electronic band structure is a shift of the Fermi energy which occurs as a result of charge transfer from lithium to the SiCNTs. All the Li-intercalated (6,6) SiCNT bundles are predicted to be metallic representing a substantial change in electronic properties relative to the undoped bundle, which is a wide band gap semiconductor. Both inside of the nanotube and the interstitial space are susceptible for intercalation. The present calculations suggest that the SiCNT bundle is a promising candidate for the anode material in battery applications.

  11. A theoretical study of lithium-doped gallium clusters by density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Sentuerk, Suekrue; Ekincioglu, Yavuz [Dumlupinar Univ., Kutahya (Turkey). Dept. of Physics

    2012-05-15

    The geometrical structures, stabilities, and electronic properties of Ga{sub n}Li (n = 1-13) clusters were investigated within the density functional theory (DFT). The impurity lithium atom enhances the stability of Ga{sub n}Li (n = 1-13) clusters, especially Ga{sub n}Li (n = 9-13) compared to Ga{sub n} (n = 9-14), that is at either apex position or side position. The dissociation energy, second-order energy differences, and the energy gaps between highest occupied and lowest unoccupied molecular orbital (HOMO-LUMO) indicate that the Ga{sub 7}Li, Ga{sub 9}Li, and Ga{sub 11}Li clusters are more stable within the studied cluster range. Moreover, the variation of the average bond length of Ga - Li is due to the surface effect, and the binding strength increases resulting from the increase of charge amount. (orig.)

  12. Time-Dependent Density Functional Theory Analysis of Triphenylamine-Functionalized Graphene Doped with Transition Metals for Photocatalytic Hydrogen Production.

    Science.gov (United States)

    Mota, Elder A V; Neto, Abel F G; Marques, Francisco C; Mota, Gunar V S; Martins, Marcelo G; Costa, Fabio L P; Borges, Rosivaldo S; Neto, Antonio M J C

    2018-07-01

    The electronic structures and optical properties of triphenylamine-functionalized graphene (G-TPA) doped with transition metals, using water as a solvent, were theoretically investigated to verify the efficiency of photocatalytic hydrogen production with the use of transition metals. This study was performed by Density Functional Theory and Time-dependent Density Functional Theory through Gaussian 09W software, adopting the B3LYP functional for all structures. The 6-31g(d) basis set was used for H, C and N atoms, and the LANL2DZ basis set for transition metals using the Effective Core Potentials method. Two approaches were adopted: (1) using single metallic dopants (Ni, Pd, Fe, Os and Pt) and (2) using combinations of Ni with the other dopants (NiPd, NiPt, NiFe and NiOs). The DOS spectra reveal an increase of accessible states in the valence shell, in addition to a gap decrease for all dopants. This doping also increases the absorption in the visible region of solar radiation where sunlight is most intense (400 nm to 700 nm), with additional absorption peaks. The results lead us to propose the G-TPA structures doped with Ni, Pd, Pt, NiPt or NiPd to be novel catalysts for the conversion of solar energy for photocatalytic hydrogen production, since they improve the absorption of solar energy in the range of interest for solar radiation; and act as reaction centers, reducing the required overpotential for hydrogen production from water.

  13. The appropriateness of density-functional theory for the calculation of molecular electronics properties.

    Science.gov (United States)

    Reimers, Jeffrey R; Cai, Zheng-Li; Bilić, Ante; Hush, Noel S

    2003-12-01

    As molecular electronics advances, efficient and reliable computation procedures are required for the simulation of the atomic structures of actual devices, as well as for the prediction of their electronic properties. Density-functional theory (DFT) has had widespread success throughout chemistry and solid-state physics, and it offers the possibility of fulfilling these roles. In its modern form it is an empirically parameterized approach that cannot be extended toward exact solutions in a prescribed way, ab initio. Thus, it is essential that the weaknesses of the method be identified and likely shortcomings anticipated in advance. We consider four known systematic failures of modern DFT: dispersion, charge transfer, extended pi conjugation, and bond cleavage. Their ramifications for molecular electronics applications are outlined and we suggest that great care is required when using modern DFT to partition charge flow across electrode-molecule junctions, screen applied electric fields, position molecular orbitals with respect to electrode Fermi energies, and in evaluating the distance dependence of through-molecule conductivity. The causes of these difficulties are traced to errors inherent in the types of density functionals in common use, associated with their inability to treat very long-range electron correlation effects. Heuristic enhancements of modern DFT designed to eliminate individual problems are outlined, as are three new schemes that each represent significant departures from modern DFT implementations designed to provide a priori improvements in at least one and possible all problem areas. Finally, fully semiempirical schemes based on both Hartree-Fock and Kohn-Sham theory are described that, in the short term, offer the means to avoid the inherent problems of modern DFT and, in the long term, offer competitive accuracy at dramatically reduced computational costs.

  14. Statistical theory of electron densities

    International Nuclear Information System (INIS)

    Pratt, L.R.; Hoffman, G.G.; Harris, R.A.

    1988-01-01

    An optimized Thomas--Fermi theory is proposed which retains the simplicity of the original theory and is a suitable reference theory for Monte Carlo density functional treatments of condensed materials. The key ingredient of the optimized theory is a neighborhood sampled potential which contains effects of the inhomogeneities in the one-electron potential. In contrast to the traditional Thomas--Fermi approach, the optimized theory predicts a finite electron density in the vicinity of a nucleus. Consideration of the example of an ideal electron gas subject to a central Coulomb field indicates that implementation of the approach is straightforward. The optimized theory is found to fail completely when a classically forbidden region is approached. However, these circumstances are not of primary interest for calculations of interatomic forces. It is shown how the energy functional of the density may be constructed by integration of a generalized Hellmann--Feynman relation. This generalized Hellmann--Feynman relation proves to be equivalent to the variational principle of density functional quantum mechanics, and, therefore, the present density theory can be viewed as a variational consequence of the constructed energy functional

  15. Application of time-dependent current-density-functional theory to nonlocal exchange-correlation effects in polymers

    NARCIS (Netherlands)

    van Faassen, M; de Boeij, PL; van Leeuwen, R; Berger, JA; Snijders, JG

    2003-01-01

    We provide a successful approach towards the solution of the longstanding problem of the large overestimation of the static polarizability of conjugated oligomers obtained using the local density approximation within density-functional theory. The local approximation is unable to describe the highly

  16. A density functional theory investigation of the electronic structure and spin moments of magnetite

    KAUST Repository

    Noh, Junghyun; Osman, Osman I; Aziz, Saadullah G; Winget, Paul; Bredas, Jean-Luc

    2014-01-01

    We present the results of density functional theory (DFT) calculations on magnetite, Fe3O4, which has been recently considered as electrode in the emerging field of organic spintronics. Given the nature of the potential applications, we evaluated the magnetite room-temperature cubic phase in terms of structural, electronic, and magnetic properties. We considered GGA (PBE), GGA + U (PBE + U), and range-separated hybrid (HSE06 and HSE(15%)) functionals. Calculations using HSE06 and HSE(15%) functionals underline the impact that inclusion of exact exchange has on the electronic structure. While the modulation of the band gap with exact exchange has been seen in numerous situations, the dramatic change in the valence band nature and states near the Fermi level has major implications for even a qualitative interpretation of the DFT results. We find that HSE06 leads to highly localized states below the Fermi level while HSE(15%) and PBE + U result in delocalized states around the Fermi level. The significant differences in local magnetic moments and atomic charges indicate that describing room-temperature bulk materials, surfaces and interfaces may require different functionals than their low-temperature counterparts.

  17. A density functional theory investigation of the electronic structure and spin moments of magnetite

    KAUST Repository

    Noh, Junghyun

    2014-08-01

    We present the results of density functional theory (DFT) calculations on magnetite, Fe3O4, which has been recently considered as electrode in the emerging field of organic spintronics. Given the nature of the potential applications, we evaluated the magnetite room-temperature cubic phase in terms of structural, electronic, and magnetic properties. We considered GGA (PBE), GGA + U (PBE + U), and range-separated hybrid (HSE06 and HSE(15%)) functionals. Calculations using HSE06 and HSE(15%) functionals underline the impact that inclusion of exact exchange has on the electronic structure. While the modulation of the band gap with exact exchange has been seen in numerous situations, the dramatic change in the valence band nature and states near the Fermi level has major implications for even a qualitative interpretation of the DFT results. We find that HSE06 leads to highly localized states below the Fermi level while HSE(15%) and PBE + U result in delocalized states around the Fermi level. The significant differences in local magnetic moments and atomic charges indicate that describing room-temperature bulk materials, surfaces and interfaces may require different functionals than their low-temperature counterparts.

  18. Orientation of rod molecules in selective slits: a density functional theory

    International Nuclear Information System (INIS)

    Xu Xiaofei; Cao Dapeng; Wang Wenchuan

    2008-01-01

    A density functional theory (DFT) is used to investigate molecular orientation of rod fluids in selective slits. The DFT approach combines a modified fundamental measure theory (MFMT) for excluded-volume effect, the first-order thermodynamics perturbation theory for chain connectivity and the mean-field approximation for van der Waals (vdW) attraction. To study the molecular orientation, the intramolecular bonding orientation function is introduced into the DFT. First, we investigate the orientation of the surfactant-like rod molecule of AB 6 (i.e. ABBBBBB) in a nanoslit of H 20σ, where the walls selectively adsorb segment 'A'. It is observed that, with the increase of the surface energy of the wall to head segment (i.e. 'A' segment) of the rod molecule, the rod molecules adsorbed on the wall present the perpendicular orientation gradually, and assemble into a smectic-A-like monolayer finally. In addition, we also explore the molecular orientation of the rods with both end segments preferring to the wall, i.e. AB 8 A and AB 7 A, in a nanoslit of H = 10σ. Interestingly, the AB 8 A rod monolayer is compatible with either a smectic-A-like or a smectic-C-like organization, but AB 7 A rod molecules exhibit the smectic-A-like organization. The orientation factor of the AB 7 A rod molecule reaches 1, suggesting that AB 7 A rod molecules self-assemble into an ordered structure with perfectly perpendicular orientation to the wall.

  19. Ground-State Gas-Phase Structures of Inorganic Molecules Predicted by Density Functional Theory Methods

    KAUST Repository

    Minenkov, Yury

    2017-11-29

    We tested a battery of density functional theory (DFT) methods ranging from generalized gradient approximation (GGA) via meta-GGA to hybrid meta-GGA schemes as well as Møller–Plesset perturbation theory of the second order and a single and double excitation coupled-cluster (CCSD) theory for their ability to reproduce accurate gas-phase structures of di- and triatomic molecules derived from microwave spectroscopy. We obtained the most accurate molecular structures using the hybrid and hybrid meta-GGA approximations with B3PW91, APF, TPSSh, mPW1PW91, PBE0, mPW1PBE, B972, and B98 functionals, resulting in lowest errors. We recommend using these methods to predict accurate three-dimensional structures of inorganic molecules when intramolecular dispersion interactions play an insignificant role. The structures that the CCSD method predicts are of similar quality although at considerably larger computational cost. The structures that GGA and meta-GGA schemes predict are less accurate with the largest absolute errors detected with BLYP and M11-L, suggesting that these methods should not be used if accurate three-dimensional molecular structures are required. Because of numerical problems related to the integration of the exchange–correlation part of the functional and large scattering of errors, most of the Minnesota models tested, particularly MN12-L, M11, M06-L, SOGGA11, and VSXC, are also not recommended for geometry optimization. When maintaining a low computational budget is essential, the nonseparable gradient functional N12 might work within an acceptable range of error. As expected, the DFT-D3 dispersion correction had a negligible effect on the internuclear distances when combined with the functionals tested on nonweakly bonded di- and triatomic inorganic molecules. By contrast, the dispersion correction for the APF-D functional has been found to shorten the bonds significantly, up to 0.064 Å (AgI), in Ag halides, BaO, BaS, BaF, BaCl, Cu halides, and Li and

  20. Pressure-Dependent Electronic and Transport Properties of Bulk Platinum Oxide by Density Functional Theory

    Science.gov (United States)

    Kansara, Shivam; Gupta, Sanjeev K.; Sonvane, Yogesh; Nekrasov, Kirill A.; Kichigina, Natalia V.

    2018-02-01

    The structural, electronic, and vibrational properties of bulk platinum oxide (PtO) at compressive pressures in the interval from 0 GPa to 35 GPa are investigated using the density functional theory. The calculated electronic band structure of PtO shows poor metallicity at very low density of states on the Fermi level. However, the hybrid pseudopotential calculation yielded 0.78 eV and 1.30 eV direct band and indirect gap, respectively. Importantly, our results predict that PtO has a direct band gap within the framework of HSE06, and it prefers equally zero magnetic order at different pressures. In the Raman spectra, peaks are slightly shifted towards higher frequency with the decrease in pressure. We have also calculated the thermoelectric properties, namely the electronic thermal conductivity and electrical conductivity, with respect to temperature and thermodynamic properties such as entropy, specific heat at constant volume, enthalpy and Gibbs free energy with respect to pressure. The result shows that PtO is a promising candidate for use as a catalyst, in sensors, as a photo-cathode in water electrolysis, for thermal decomposition of inorganic salt and fuel cells.

  1. Density Functional Theory Calculations of the Quantum Capacitance of Graphene Oxide as a Supercapacitor Electrode.

    Science.gov (United States)

    Song, Ce; Wang, Jinyan; Meng, Zhaoliang; Hu, Fangyuan; Jian, Xigao

    2018-03-31

    Graphene oxide has become an attractive electrode-material candidate for supercapacitors thanks to its higher specific capacitance compared to graphene. The quantum capacitance makes relative contributions to the specific capacitance, which is considered as the major limitation of graphene electrodes, while the quantum capacitance of graphene oxide is rarely concerned. This study explores the quantum capacitance of graphene oxide, which bears epoxy and hydroxyl groups on its basal plane, by employing density functional theory (DFT) calculations. The results demonstrate that the total density of states near the Fermi level is significantly enhanced by introducing oxygen-containing groups, which is beneficial for the improvement of the quantum capacitance. Moreover, the quantum capacitances of the graphene oxide with different concentrations of these two oxygen-containing groups are compared, revealing that more epoxy and hydroxyl groups result in a higher quantum capacitance. Notably, the hydroxyl concentration has a considerable effect on the capacitive behavior. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  2. Wetting of heterogeneous substrates. A classical density-functional-theory approach

    Science.gov (United States)

    Yatsyshin, Peter; Parry, Andrew O.; Rascón, Carlos; Duran-Olivencia, Miguel A.; Kalliadasis, Serafim

    2017-11-01

    Wetting is a nucleation of a third phase (liquid) on the interface between two different phases (solid and gas). In many experimentally accessible cases of wetting, the interplay between the substrate structure, and the fluid-fluid and fluid-substrate intermolecular interactions leads to the appearance of a whole ``zoo'' of exciting interface phase transitions, associated with the formation of nano-droplets/bubbles, and thin films. Practical applications of wetting at small scales are numerous and include the design of lab-on-a-chip devices and superhydrophobic surfaces. In this talk, we will use a fully microscopic approach to explore the phase space of a planar wall, decorated with patches of different hydrophobicity, and demonstrate the highly non-trivial behaviour of the liquid-gas interface near the substrate. We will present fluid density profiles, adsorption isotherms and wetting phase diagrams. Our analysis is based on a formulation of statistical mechanics, commonly known as classical density-functional theory. It provides a computationally-friendly and rigorous framework, suitable for probing small-scale physics of classical fluids and other soft-matter systems. EPSRC Grants No. EP/L027186,EP/K503733;ERC Advanced Grant No. 247031.

  3. Experiment and density functional theory analyses of GdTaO4 single crystal

    Science.gov (United States)

    Ding, Shoujun; Kinross, Ashlie; Wang, Xiaofei; Yang, Huajun; Zhang, Qingli; Liu, Wenpeng; Sun, Dunlu

    2018-05-01

    GdTaO4 is a type of excellent materials that can be used as scintillation, laser matrix as well as self-activated phosphor has generated significant interest. Whereas its band structure, electronic structure and optical properties are still need elucidation. To solve this intriguing problem, high-quality GdTaO4 single crystal (M-type) was grown successfully using Czochralski method. Its structure as well as optical properties was determined in experiment. Moreover, a systematic theoretical calculation based on the density function theory methods were performed on M-type and M‧-type GdTaO4 and their band structure, density of state as well as optical properties were obtained. Combine with the performed experiment results, the calculated results were proved with high reliability. Hence, the calculated results obtained in this work could provide a deep understanding of GdTaO4 material, which also useful for the further investigation on GdTaO4 material.

  4. Molecular acidity: An accurate description with information-theoretic approach in density functional reactivity theory.

    Science.gov (United States)

    Cao, Xiaofang; Rong, Chunying; Zhong, Aiguo; Lu, Tian; Liu, Shubin

    2018-01-15

    Molecular acidity is one of the important physiochemical properties of a molecular system, yet its accurate calculation and prediction are still an unresolved problem in the literature. In this work, we propose to make use of the quantities from the information-theoretic (IT) approach in density functional reactivity theory and provide an accurate description of molecular acidity from a completely new perspective. To illustrate our point, five different categories of acidic series, singly and doubly substituted benzoic acids, singly substituted benzenesulfinic acids, benzeneseleninic acids, phenols, and alkyl carboxylic acids, have been thoroughly examined. We show that using IT quantities such as Shannon entropy, Fisher information, Ghosh-Berkowitz-Parr entropy, information gain, Onicescu information energy, and relative Rényi entropy, one is able to simultaneously predict experimental pKa values of these different categories of compounds. Because of the universality of the quantities employed in this work, which are all density dependent, our approach should be general and be applicable to other systems as well. © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

  5. Density functional theory based molecular dynamics study of hydration and electronic properties of aqueous La(3+).

    Science.gov (United States)

    Terrier, Cyril; Vitorge, Pierre; Gaigeot, Marie-Pierre; Spezia, Riccardo; Vuilleumier, Rodolphe

    2010-07-28

    Structural and electronic properties of La(3+) immersed in bulk water have been assessed by means of density functional theory (DFT)-based Car-Parrinello molecular dynamics (CPMD) simulations. Correct structural properties, i.e., La(III)-water distances and La(III) coordination number, can be obtained within the framework of Car-Parrinello simulations providing that both the La pseudopotential and conditions of the dynamics (fictitious mass and time step) are carefully set up. DFT-MD explicitly treats electronic densities and is shown here to provide a theoretical justification to the necessity of including polarization when studying highly charged cations such as lanthanoids(III) with classical MD. La(3+) was found to strongly polarize the water molecules located in the first shell, giving rise to dipole moments about 0.5 D larger than those of bulk water molecules. Finally, analyzing Kohn-Sham orbitals, we found La(3+) empty 4f orbitals extremely compact and to a great extent uncoupled from the water conduction band, while the 5d empty orbitals exhibit mixing with unoccupied states of water.

  6. Using Sandia's Z Machine and Density Functional Theory Simulations to Understand Planetary Materials

    Science.gov (United States)

    Root, Seth

    2017-06-01

    The use of Z, NIF, and Omega have produced many breakthrough results in high pressure physics. One area that has greatly benefited from these facilities is the planetary sciences. The high pressure behavior of planetary materials has implications for numerous geophysical and planetary processes. The continuing discovery of exosolar super-Earths demonstrates the need for accurate equation of state data to better inform our models of their interior structures. Planetary collision processes, such as the moon-forming giant impact, require understanding planetary materials over a wide-range of pressures and temperatures. Using Z, we examined the shock compression response of some common planetary materials: MgO, Mg2SiO4, and Fe2O3 (hematite). We compare the experimental shock compression measurements with density functional theory (DFT) based quantum molecular dynamics (QMD) simulations. The combination of experiment and theory provides clearer understanding of planetary materials properties at extreme conditions. Sandia National Laboratories is a multi-mission laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  7. Assessing Covalency in Cerium and Uranium Hexachlorides: A Correlated Wavefunction and Density Functional Theory Study

    Directory of Open Access Journals (Sweden)

    Reece Beekmeyer

    2015-11-01

    Full Text Available The electronic structure of a series of uranium and cerium hexachlorides in a variety of oxidation states was evaluated at both the correlated wavefunction and density functional (DFT levels of theory. Following recent experimental observations of covalency in tetravalent cerium hexachlorides, bonding character was studied using topological and integrated analysis based on the quantum theory of atoms in molecules (QTAIM. This analysis revealed that M–Cl covalency was strongly dependent on oxidation state, with greater covalency found in higher oxidation state complexes. Comparison of M–Cl delocalisation indices revealed a discrepancy between correlated wavefunction and DFT-derived values. Decomposition of these delocalisation indices demonstrated that the origin of this discrepancy lay in ungerade contributions associated with the f-manifold which we suggest is due to self-interaction error inherent to DFT-based methods. By all measures used in this study, extremely similar levels of covalency between complexes of U and Ce in the same oxidation state was found.

  8. Nonadiabatic dynamics with intersystem crossings: A time-dependent density functional theory implementation

    Energy Technology Data Exchange (ETDEWEB)

    Franco de Carvalho, F. [Centre Européen de Calcul Atomique et Moléculaire, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland); Tavernelli, I. [IBM Research GmbH, Zurich Research Laboratory, 8803 Ruschlikon (Switzerland)

    2015-12-14

    In this work, we derive a method to perform trajectory-based nonadiabatic dynamics that is able to describe both nonadiabatic transitions and intersystem crossing events (transitions between states of different spin-multiplicity) at the same level of theory, namely, time-dependent density functional theory (TDDFT). To this end, we combined our previously developed TDDFT-based trajectory surface hopping scheme with an accurate and efficient algorithm for the calculation of the spin-orbit coupling (SOC) matrix elements. More specifically, we designed two algorithms for the calculation of intersystem crossing transitions, one based on an extended Tully’s surface hopping scheme including SOC and the second based on a Landau-Zener approximation applied to the spin sector of the electronic Hilbert space. This development allows for the design of an efficient on-the-fly nonadiabatic approach that can handle, on an equal footing, nonadiabatic and intersystem crossing transitions. The method is applied to the study of the photophysics of sulfur dioxide (SO{sub 2}) in gas and liquid phases.

  9. A density functional theory study on the interactions between dibenzothiophene and tetrafluoroborate-based ionic liquids.

    Science.gov (United States)

    Lin, Jin; Lü, Renqing; Wu, Chongchong; Xiao, Ye; Liang, Fei; Famakinwa, Temilola

    2017-04-01

    The interactions between dibenzothiophene (DBT) and N-butyl-N-methylimidazolium tetrafluoroborate ([BMIM][BF 4 ]), N-butyl-N-methylmorpholinium tetrafluoroborate ([Bmmorpholinium][BF 4 ]), N-butyl-N-methylpiperdinium tetrafluoroborate ([BMPiper][BF 4 ]), N-butyl-N-methylpyrrolidinium tetrafluoroborate ([BMPyrro][BF 4 ]), and N-butylpyridinium tetrafluoroborate ([BPY][BF 4 ]) were investigated using density functional theory approach. Geometric, electron, and topological properties were analyzed using natural bond orbital, atoms in molecules theory, and noncovalent interaction methods in order to understand intermolecular interactions between DBT and ionic liquids. The result shows that hydrogen bond and van der Waals interactions are widespread in all the ionic liquids-DBT systems. Ion-π interactions between DBT and cation or anion are also observed, while π + -π interactions are only found in the [BMIM][BF 4 ]-DBT and [BPY][BF 4 ]-DBT systems. The order of interaction energy is [BPY][BF4]-DBT > [BMIM][BF 4 ]-DBT > [BMPiper][BF 4 ]-DBT > [BMPyrro][BF 4 ]-DBT > [BMmorpholinum][BF 4 ]-DBT. The energies between DBT and the two ionic liquids containing aromatic cations are significantly higher.

  10. Describing long-range charge-separation processes with subsystem density-functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Solovyeva, Alisa; Neugebauer, Johannes, E-mail: j.neugebauer@uni-muenster.de [Theoretische Organische Chemie, Organisch-Chemisches Institut and Center for Multiscale Theory and Simulation, Westfälische Wilhelms-Universität Münster, Corrensstraße 40, 48149 Münster (Germany); Pavanello, Michele, E-mail: m.pavanello@rutgers.edu [Department of Chemistry, Rutgers University, 73 Warren St., Newark, New Jersey 07102 (United States)

    2014-04-28

    Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants in Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge — charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange–correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states.

  11. Describing long-range charge-separation processes with subsystem density-functional theory

    International Nuclear Information System (INIS)

    Solovyeva, Alisa; Neugebauer, Johannes; Pavanello, Michele

    2014-01-01

    Long-range charge-transfer processes in extended systems are difficult to describe with quantum chemical methods. In particular, cost-effective (non-hybrid) approximations within time-dependent density functional theory (DFT) are not applicable unless special precautions are taken. Here, we show that the efficient subsystem DFT can be employed as a constrained DFT variant to describe the energetics of long-range charge-separation processes. A formal analysis of the energy components in subsystem DFT for such excitation energies is presented, which demonstrates that both the distance dependence and the long-range limit are correctly described. In addition, electronic couplings for these processes as needed for rate constants in Marcus theory can be obtained from this method. It is shown that the electronic structure of charge-separated states constructed by a positively charged subsystem interacting with a negatively charged one is difficult to converge — charge leaking from the negative subsystem to the positive one can occur. This problem is related to the delocalization error in DFT and can be overcome with asymptotically correct exchange–correlation (XC) potentials or XC potentials including a sufficiently large amount of exact exchange. We also outline an approximate way to obtain charge-transfer couplings between locally excited and charge-separated states

  12. Guaiacol hydrodeoxygenation mechanism on Pt(111): insights from density functional theory and linear free energy relations.

    Science.gov (United States)

    Lee, Kyungtae; Gu, Geun Ho; Mullen, Charles A; Boateng, Akwasi A; Vlachos, Dionisios G

    2015-01-01

    Density functional theory is used to study the adsorption of guaiacol and its initial hydrodeoxygenation (HDO) reactions on Pt(111). Previous Brønsted-Evans-Polanyi (BEP) correlations for small open-chain molecules are inadequate in estimating the reaction barriers of phenolic compounds except for the side group (methoxy) carbon-dehydrogenation. New BEP relations are established using a select group of phenolic compounds. These relations are applied to construct a potential-energy surface of guaiacol-HDO to catechol. Analysis shows that catechol is mainly produced via dehydrogenation of the methoxy functional group followed by the CHx (x<3) removal of the functional group and hydrogenation of the ring carbon, in contrast to a hypothesis of a direct demethylation path. Dehydroxylation and demethoxylation are slow, implying that phenol is likely produced from catechol but not through its direct dehydroxylation followed by aromatic carbon-ring hydrogenation. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  13. Time-dependent density functional theory beyond Kohn-Sham Slater determinants.

    Science.gov (United States)

    Fuks, Johanna I; Nielsen, Søren E B; Ruggenthaler, Michael; Maitra, Neepa T

    2016-08-03

    When running time-dependent density functional theory (TDDFT) calculations for real-time simulations of non-equilibrium dynamics, the user has a choice of initial Kohn-Sham state, and typically a Slater determinant is used. We explore the impact of this choice on the exchange-correlation potential when the physical system begins in a 50 : 50 superposition of the ground and first-excited state of the system. We investigate the possibility of judiciously choosing a Kohn-Sham initial state that minimizes errors when adiabatic functionals are used. We find that if the Kohn-Sham state is chosen to have a configuration matching the one that dominates the interacting state, this can be achieved for a finite time duration for some but not all such choices. When the Kohn-Sham system does not begin in a Slater determinant, we further argue that the conventional splitting of the exchange-correlation potential into exchange and correlation parts has limited value, and instead propose a decomposition into a "single-particle" contribution that we denote v, and a remainder. The single-particle contribution can be readily computed as an explicit orbital-functional, reduces to exchange in the Slater determinant case, and offers an alternative to the adiabatic approximation as a starting point for TDDFT approximations.

  14. Complex-energy approach to sum rules within nuclear density functional theory

    Science.gov (United States)

    Hinohara, Nobuo; Kortelainen, Markus; Nazarewicz, Witold; Olsen, Erik

    2015-04-01

    Background: The linear response of the nucleus to an external field contains unique information about the effective interaction, the correlations governing the behavior of the many-body system, and the properties of its excited states. To characterize the response, it is useful to use its energy-weighted moments, or sum rules. By comparing computed sum rules with experimental values, the information content of the response can be utilized in the optimization process of the nuclear Hamiltonian or the nuclear energy density functional (EDF). But the additional information comes at a price: compared to the ground state, computation of excited states is more demanding. Purpose: To establish an efficient framework to compute energy-weighted sum rules of the response that is adaptable to the optimization of the nuclear EDF and large-scale surveys of collective strength, we have developed a new technique within the complex-energy finite-amplitude method (FAM) based on the quasiparticle random-phase approximation (QRPA). Methods: To compute sum rules, we carry out contour integration of the response function in the complex-energy plane. We benchmark our results against the conventional matrix formulation of the QRPA theory, the Thouless theorem for the energy-weighted sum rule, and the dielectric theorem for the inverse-energy-weighted sum rule. Results: We derive the sum-rule expressions from the contour integration of the complex-energy FAM. We demonstrate that calculated sum-rule values agree with those obtained from the matrix formulation of the QRPA. We also discuss the applicability of both the Thouless theorem about the energy-weighted sum rule and the dielectric theorem for the inverse-energy-weighted sum rule to nuclear density functional theory in cases when the EDF is not based on a Hamiltonian. Conclusions: The proposed sum-rule technique based on the complex-energy FAM is a tool of choice when optimizing effective interactions or energy functionals. The method

  15. Calculation of spin-densities within the context of density functional theory. The crucial role of the correlation functional

    NARCIS (Netherlands)

    Filatov, M; Cremer, D

    2005-01-01

    It is demonstrated that the LYP correlation functional is not suited to be used for the calculation of electron spin resonance hyperfine structure (HFS) constants, nuclear magnetic resonance spin-spin coupling constants, magnetic, shieldings and other properties that require a balanced account of

  16. Application of an excited state LDA exchange energy functional for the calculation of transition energy of atoms within time-independent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Shamim, Md; Harbola, Manoj K, E-mail: sami@iitk.ac.i, E-mail: mkh@iitk.ac.i [Department of Physics, Indian Institute of Technology, Kanpur 208 016 (India)

    2010-11-14

    Transition energies of a new class of excited states (two-gap systems) of various atoms are calculated in time-independent density functional formalism by using a recently proposed local density approximation exchange energy functional for excited states. It is shown that the excitation energies calculated with this functional compare well with those calculated with exact exchange theories.

  17. Application of an excited state LDA exchange energy functional for the calculation of transition energy of atoms within time-independent density functional theory

    International Nuclear Information System (INIS)

    Shamim, Md; Harbola, Manoj K

    2010-01-01

    Transition energies of a new class of excited states (two-gap systems) of various atoms are calculated in time-independent density functional formalism by using a recently proposed local density approximation exchange energy functional for excited states. It is shown that the excitation energies calculated with this functional compare well with those calculated with exact exchange theories.

  18. Density functional theory calculations on alkali and the alkaline Ca atoms adsorbed on graphene monolayers

    International Nuclear Information System (INIS)

    Dimakis, Nicholas; Valdez, Danielle; Flor, Fernando Antonio; Salgado, Andres; Adjibi, Kolade; Vargas, Sarah; Saenz, Justin

    2017-01-01

    Highlights: • Li, K, Na, and Ca graphene interaction is primarily ionic, whereas small covalent interactions also co-exist in these cases. • Van der Waals interactions are revealed by comparing adatom-graphene geometries between 1.4% and 3% adatom coverages and using Grimme corrections. • The Li, K, Na graphene interactions are accurately described by both PBE0 and PBE functionals. For Ca/graphene, the PBE0 functional should not be used. • For Li, K, and Na adsorbed on graphene, adatom-graphene interaction weakens as the adatom coverages increases. • The Ca-graphene interaction strength, which is stronger at high coverages, is opposite to increases in the Ca–4s orbital population. - Abstract: The adsorption of the alkali Li, K, and Na and the alkaline Ca on graphene is studied using periodic density functional theory (DFT) under various adatom coverages. The charge transfers between the adatom and the graphene sheet and the almost unchanged densities-of-states spectra in the energy region near and below the Fermi level support an ionic bond pattern between the adatom and the graphene atoms. However, the presence of small orbital overlap between the metal and the nearest graphene atom is indicative of small covalent bonding. Van der Waals interactions are examined through a semiempirical correction in the DFT functional and by comparing adatom-graphene calculations between 3% and 1.4% adatom coverages. Optimized adatom-graphene geometries identify the preferred adatom sites, whereas the adatom-graphene strength is correlated with the adsorption energy and the adatom distance from the graphene plane. Calculated electronic properties and structural parameters are obtained using hybrid functionals and a generalized gradient approximation functional paired with basis sets of various sizes. We found that due to long range electrostatic forces between the alkali/alkaline adatoms and the graphene monolayer, the adatom-graphene structural and electronic

  19. Density functional theory calculations on alkali and the alkaline Ca atoms adsorbed on graphene monolayers

    Energy Technology Data Exchange (ETDEWEB)

    Dimakis, Nicholas, E-mail: nicholas.dimakis@utrgv.edu [Department of Physics, University of Texas Rio Grande Valley, Edinburg, TX (United States); Valdez, Danielle; Flor, Fernando Antonio; Salgado, Andres; Adjibi, Kolade [Department of Physics, University of Texas Rio Grande Valley, Edinburg, TX (United States); Vargas, Sarah; Saenz, Justin [Robert Vela High School, Edinburg, TX (United States)

    2017-08-15

    Highlights: • Li, K, Na, and Ca graphene interaction is primarily ionic, whereas small covalent interactions also co-exist in these cases. • Van der Waals interactions are revealed by comparing adatom-graphene geometries between 1.4% and 3% adatom coverages and using Grimme corrections. • The Li, K, Na graphene interactions are accurately described by both PBE0 and PBE functionals. For Ca/graphene, the PBE0 functional should not be used. • For Li, K, and Na adsorbed on graphene, adatom-graphene interaction weakens as the adatom coverages increases. • The Ca-graphene interaction strength, which is stronger at high coverages, is opposite to increases in the Ca–4s orbital population. - Abstract: The adsorption of the alkali Li, K, and Na and the alkaline Ca on graphene is studied using periodic density functional theory (DFT) under various adatom coverages. The charge transfers between the adatom and the graphene sheet and the almost unchanged densities-of-states spectra in the energy region near and below the Fermi level support an ionic bond pattern between the adatom and the graphene atoms. However, the presence of small orbital overlap between the metal and the nearest graphene atom is indicative of small covalent bonding. Van der Waals interactions are examined through a semiempirical correction in the DFT functional and by comparing adatom-graphene calculations between 3% and 1.4% adatom coverages. Optimized adatom-graphene geometries identify the preferred adatom sites, whereas the adatom-graphene strength is correlated with the adsorption energy and the adatom distance from the graphene plane. Calculated electronic properties and structural parameters are obtained using hybrid functionals and a generalized gradient approximation functional paired with basis sets of various sizes. We found that due to long range electrostatic forces between the alkali/alkaline adatoms and the graphene monolayer, the adatom-graphene structural and electronic

  20. UV-Vis optoelectronic properties of α-SnWO4: A comparative experimental and density functional theory based study

    KAUST Repository

    Ziani, Ahmed

    2015-09-03

    We report a combined experimental and theoretical study on the optoelectronic properties of α-SnWO4 for UV-Vis excitation. The experimentally measured values for thin films were systematically compared with high-accuracy density functional theory and density functional perturbation theory using the HSE06 functional. The α-SnWO4 material shows an indirect bandgap of 1.52 eV with high absorption coefficient in the visible-light range (>2 × 105 cm−1). The results show relatively high dielectric constant (>30) and weak diffusion properties (large effective masses) of excited carriers.

  1. Diverse carrier mobility of monolayer BNC x : a combined density functional theory and Boltzmann transport theory study.

    Science.gov (United States)

    Wu, Tao; Deng, Kaiming; Deng, Weiqiao; Lu, Ruifeng

    2017-10-19

    BNC x monolayer as a kind of two-dimensional material has numerous chemical atomic ratios and arrangements with different electronic structures. Via calculations on the basis of density functional theory and Boltzmann transport theory under deformation potential approximation, the band structures and carrier mobilities of BNC x (x  =  1,2,3,4) nanosheets are systematically investigated. The calculated results show that BNC 2 -1 is a material with very small band gap (0.02 eV) among all the structures while other BNC x monolayers are semiconductors with band gap ranging from 0.51 eV to 1.32 eV. The carrier mobility of BNC x varies considerably from tens to millions of cm 2 V -1 s -1 . For BNC 2 -1, the hole mobility and electron mobility along both x and y directions can reach 10 5 orders of magnitude, which is similar to the carrier mobility of graphene. Besides, all studied BNC x monolayers obviously have anisotropic hole mobility and electron mobility. In particular, for semiconductor BNC 4 , its hole mobility along the y direction and electron mobility along the x direction unexpectedly reach 10 6 orders of magnitude, even higher than that of graphene. Our findings suggest that BNC x layered materials with the proper ratio and arrangement of carbon atoms will possess desirable charge transport properties, exhibiting potential applications in nanoelectronic devices.

  2. Wavelet-based linear-response time-dependent density-functional theory

    International Nuclear Information System (INIS)

    Natarajan, Bhaarathi; Genovese, Luigi; Casida, Mark E.; Deutsch, Thierry; Burchak, Olga N.

    2012-01-01

    Highlights: ► We has been implemented LR-TD-DFT in the pseudopotential wavelet-based program. ► We have compared the results against all-electron Gaussian-type program. ► Orbital energies converges significantly faster for BigDFT than for DEMON2K. ► We report the X-ray crystal structure of the small organic molecule flugi6. ► Measured and calculated absorption spectrum of flugi6 is also reported. - Abstract: Linear-response time-dependent (TD) density-functional theory (DFT) has been implemented in the pseudopotential wavelet-based electronic structure program BIGDFT and results are compared against those obtained with the all-electron Gaussian-type orbital program DEMON2K for the calculation of electronic absorption spectra of N 2 using the TD local density approximation (LDA). The two programs give comparable excitation energies and absorption spectra once suitably extensive basis sets are used. Convergence of LDA density orbitals and orbital energies to the basis-set limit is significantly faster for BIGDFT than for DEMON2K. However the number of virtual orbitals used in TD-DFT calculations is a parameter in BIGDFT, while all virtual orbitals are included in TD-DFT calculations in DEMON2K. As a reality check, we report the X-ray crystal structure and the measured and calculated absorption spectrum (excitation energies and oscillator strengths) of the small organic molecule N-cyclohexyl-2-(4-methoxyphenyl)imidazo[1, 2-a]pyridin-3-amine.

  3. Correlated electron dynamics and memory in time-dependent density functional theory

    International Nuclear Information System (INIS)

    Thiele, Mark

    2009-01-01

    Time-dependent density functional theory (TDDFT) is an exact reformulation of the time-dependent many-electron Schroedinger equation, where the problem of many interacting electrons is mapped onto the Kohn-Sham system of noninteracting particles which reproduces the exact electronic density. In the Kohn-Sham system all non-classical many-body effects are incorporated in the exchange-correlation potential which is in general unknown and needs to be approximated. It is the goal of this thesis to investigate the connection between memory effects and correlated electron dynamics in strong and weak fields. To this end one-dimensional two-electron singlet systems are studied. At the same time these systems include the onedimensional helium atom model, which is an established system to investigate the crucial effects of correlated electron dynamics in external fields. The studies presented in this thesis show that memory effects are negligible for typical strong field processes. Here the approximation of the spatial nonlocality is of primary importance. For the photoabsorption spectra on the other hand the neglect of memory effects leads to qualitative and quantitative errors, which are shown to be connected to transitions of double excitation character. To develop a better understanding of the conditions under which memory effects become important quantum fluid dynamics has been found to be especially suitable. It represents a further exact reformulation of the quantum mechanic many-body problem which is based on hydrodynamic quantities such as density and velocity. Memory effects are shown to be important whenever the velocity field develops strong gradients and dissipative effects contribute. (orig.)

  4. Correlated electron dynamics and memory in time-dependent density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Thiele, Mark

    2009-07-28

    Time-dependent density functional theory (TDDFT) is an exact reformulation of the time-dependent many-electron Schroedinger equation, where the problem of many interacting electrons is mapped onto the Kohn-Sham system of noninteracting particles which reproduces the exact electronic density. In the Kohn-Sham system all non-classical many-body effects are incorporated in the exchange-correlation potential which is in general unknown and needs to be approximated. It is the goal of this thesis to investigate the connection between memory effects and correlated electron dynamics in strong and weak fields. To this end one-dimensional two-electron singlet systems are studied. At the same time these systems include the onedimensional helium atom model, which is an established system to investigate the crucial effects of correlated electron dynamics in external fields. The studies presented in this thesis show that memory effects are negligible for typical strong field processes. Here the approximation of the spatial nonlocality is of primary importance. For the photoabsorption spectra on the other hand the neglect of memory effects leads to qualitative and quantitative errors, which are shown to be connected to transitions of double excitation character. To develop a better understanding of the conditions under which memory effects become important quantum fluid dynamics has been found to be especially suitable. It represents a further exact reformulation of the quantum mechanic many-body problem which is based on hydrodynamic quantities such as density and velocity. Memory effects are shown to be important whenever the velocity field develops strong gradients and dissipative effects contribute. (orig.)

  5. Density functional theory for prediction of far-infrared vibrational frequencies: molecular crystals of astrophysical interest

    Science.gov (United States)

    Ennis, C.; Auchettl, R.; Appadoo, D. R. T.; Robertson, E. G.

    2017-11-01

    Solid-state density functional theory code has been implemented for the structure optimization of crystalline methanol, acetaldehyde and acetic acid and for the calculation of infrared frequencies. The results are compared to thin film spectra obtained from low-temperature experiments performed at the Australian Synchrotron. Harmonic frequency calculations of the internal modes calculated at the B3LYP-D3/m-6-311G(d) level shows higher deviation from infrared experiment than more advanced theory applied to the gas phase. Importantly for the solid-state, the simulation of low-frequency molecular lattice modes closely resembles the observed far-infrared features after application of a 0.92 scaling factor. This allowed experimental peaks to be assigned to specific translation and libration modes, including acetaldehyde and acetic acid lattice features for the first time. These frequency calculations have been performed without the need for supercomputing resources that are required for large molecular clusters using comparable levels of theory. This new theoretical approach will find use for the rapid characterization of intermolecular interactions and bonding in crystals, and the assignment of far-infrared spectra for crystalline samples such as pharmaceuticals and molecular ices. One interesting application may be for the detection of species of prebiotic interest on the surfaces of Kuiper-Belt and Trans-Neptunian Objects. At such locations, the three small organic molecules studied here could reside in their crystalline phase. The far-infrared spectra for their low-temperature solid phases are collected under planetary conditions, allowing us to compile and assign their most intense spectral features to assist future far-infrared surveys of icy Solar system surfaces.

  6. Predicting critical temperatures of iron(II) spin crossover materials: Density functional theory plus U approach

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yachao, E-mail: yczhang@nano.gznc.edu.cn [Guizhou Provincial Key Laboratory of Computational Nano-Material Science, Guizhou Normal College, Guiyang 550018, Guizhou (China)

    2014-12-07

    A first-principles study of critical temperatures (T{sub c}) of spin crossover (SCO) materials requires accurate description of the strongly correlated 3d electrons as well as much computational effort. This task is still a challenge for the widely used local density or generalized gradient approximations (LDA/GGA) and hybrid functionals. One remedy, termed density functional theory plus U (DFT+U) approach, introduces a Hubbard U term to deal with the localized electrons at marginal computational cost, while treats the delocalized electrons with LDA/GGA. Here, we employ the DFT+U approach to investigate the T{sub c} of a pair of iron(II) SCO molecular crystals (α and β phase), where identical constituent molecules are packed in different ways. We first calculate the adiabatic high spin-low spin energy splitting ΔE{sub HL} and molecular vibrational frequencies in both spin states, then obtain the temperature dependent enthalpy and entropy changes (ΔH and ΔS), and finally extract T{sub c} by exploiting the ΔH/T − T and ΔS − T relationships. The results are in agreement with experiment. Analysis of geometries and electronic structures shows that the local ligand field in the α phase is slightly weakened by the H-bondings involving the ligand atoms and the specific crystal packing style. We find that this effect is largely responsible for the difference in T{sub c} of the two phases. This study shows the applicability of the DFT+U approach for predicting T{sub c} of SCO materials, and provides a clear insight into the subtle influence of the crystal packing effects on SCO behavior.

  7. Efficient calculation of nuclear spin-rotation constants from auxiliary density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Zuniga-Gutierrez, Bernardo, E-mail: bzuniga.51@gmail.com [Departamento de Ciencias Computacionales, Universidad de Guadalajara, Blvd. Marcelino García Barragán 1421, C.P. 44430 Guadalajara, Jalisco (Mexico); Camacho-Gonzalez, Monica [Universidad Tecnológica de Tecámac, División A2, Procesos Industriales, Carretera Federal México Pachuca Km 37.5, Col. Sierra Hermosa, C.P. 55740 Tecámac, Estado de México (Mexico); Bendana-Castillo, Alfonso [Universidad Tecnológica de Tecámac, División A3, Tecnologías de la Información y Comunicaciones, Carretera Federal México Pachuca Km 37.5, Col. Sierra Hermosa, C.P. 55740 Tecámac, Estado de México (Mexico); Simon-Bastida, Patricia [Universidad Tecnlógica de Tulancingo, División Electromecánica, Camino a Ahuehuetitla No. 301, Col. Las Presas, C.P. 43642 Tulancingo, Hidalgo (Mexico); Calaminici, Patrizia; Köster, Andreas M. [Departamento de Química, CINVESTAV, Avenida Instituto Politécnico Nacional 2508, A.P. 14-740, México D.F. 07000 (Mexico)

    2015-09-14

    The computation of the spin-rotation tensor within the framework of auxiliary density functional theory (ADFT) in combination with the gauge including atomic orbital (GIAO) scheme, to treat the gauge origin problem, is presented. For the spin-rotation tensor, the calculation of the magnetic shielding tensor represents the most demanding computational task. Employing the ADFT-GIAO methodology, the central processing unit time for the magnetic shielding tensor calculation can be dramatically reduced. In this work, the quality of spin-rotation constants obtained with the ADFT-GIAO methodology is compared with available experimental data as well as with other theoretical results at the Hartree-Fock and coupled-cluster level of theory. It is found that the agreement between the ADFT-GIAO results and the experiment is good and very similar to the ones obtained by the coupled-cluster single-doubles-perturbative triples-GIAO methodology. With the improved computational performance achieved, the computation of the spin-rotation tensors of large systems or along Born-Oppenheimer molecular dynamics trajectories becomes feasible in reasonable times. Three models of carbon fullerenes containing hundreds of atoms and thousands of basis functions are used for benchmarking the performance. Furthermore, a theoretical study of temperature effects on the structure and spin-rotation tensor of the H{sup 12}C–{sup 12}CH–DF complex is presented. Here, the temperature dependency of the spin-rotation tensor of the fluorine nucleus can be used to identify experimentally the so far unknown bent isomer of this complex. To the best of our knowledge this is the first time that temperature effects on the spin-rotation tensor are investigated.

  8. Surface tension of droplets and Tolman lengths of real substances and mixtures from density functional theory

    Science.gov (United States)

    Rehner, Philipp; Gross, Joachim

    2018-04-01

    The curvature dependence of interfacial properties has been discussed extensively over the last decades. After Tolman published his work on the effect of droplet size on surface tension, where he introduced the interfacial property now known as Tolman length, several studies were performed with varying results. In recent years, however, some consensus has been reached about the sign and magnitude of the Tolman length of simple model fluids. In this work, we re-examine Tolman's equation and how it relates the Tolman length to the surface tension and we apply non-local classical density functional theory (DFT) based on the perturbed chain statistical associating fluid theory (PC-SAFT) to characterize the curvature dependence of the surface tension of real fluids as well as mixtures. In order to obtain a simple expression for the surface tension, we use a first-order expansion of the Tolman length as a function of droplet radius Rs, as δ(Rs) = δ0 + δ1/Rs, and subsequently expand Tolman's integral equation for the surface tension, whereby a second-order expansion is found to give excellent agreement with the DFT result. The radius-dependence of the surface tension of increasingly non-spherical substances is studied for n-alkanes, up to icosane. The infinite diameter Tolman length is approximately δ0 = -0.38 Å at low temperatures. For more strongly non-spherical substances and for temperatures approaching the critical point, however, the infinite diameter Tolman lengths δ0 turn positive. For mixtures, even if they contain similar molecules, the extrapolated Tolman length behaves strongly non-ideal, implying a qualitative change of the curvature behavior of the surface tension of the mixture.

  9. Efficient calculation of nuclear spin-rotation constants from auxiliary density functional theory

    International Nuclear Information System (INIS)

    Zuniga-Gutierrez, Bernardo; Camacho-Gonzalez, Monica; Bendana-Castillo, Alfonso; Simon-Bastida, Patricia; Calaminici, Patrizia; Köster, Andreas M.

    2015-01-01

    The computation of the spin-rotation tensor within the framework of auxiliary density functional theory (ADFT) in combination with the gauge including atomic orbital (GIAO) scheme, to treat the gauge origin problem, is presented. For the spin-rotation tensor, the calculation of the magnetic shielding tensor represents the most demanding computational task. Employing the ADFT-GIAO methodology, the central processing unit time for the magnetic shielding tensor calculation can be dramatically reduced. In this work, the quality of spin-rotation constants obtained with the ADFT-GIAO methodology is compared with available experimental data as well as with other theoretical results at the Hartree-Fock and coupled-cluster level of theory. It is found that the agreement between the ADFT-GIAO results and the experiment is good and very similar to the ones obtained by the coupled-cluster single-doubles-perturbative triples-GIAO methodology. With the improved computational performance achieved, the computation of the spin-rotation tensors of large systems or along Born-Oppenheimer molecular dynamics trajectories becomes feasible in reasonable times. Three models of carbon fullerenes containing hundreds of atoms and thousands of basis functions are used for benchmarking the performance. Furthermore, a theoretical study of temperature effects on the structure and spin-rotation tensor of the H 12 C– 12 CH–DF complex is presented. Here, the temperature dependency of the spin-rotation tensor of the fluorine nucleus can be used to identify experimentally the so far unknown bent isomer of this complex. To the best of our knowledge this is the first time that temperature effects on the spin-rotation tensor are investigated

  10. Efficient calculation of nuclear spin-rotation constants from auxiliary density functional theory.

    Science.gov (United States)

    Zuniga-Gutierrez, Bernardo; Camacho-Gonzalez, Monica; Bendana-Castillo, Alfonso; Simon-Bastida, Patricia; Calaminici, Patrizia; Köster, Andreas M

    2015-09-14

    The computation of the spin-rotation tensor within the framework of auxiliary density functional theory (ADFT) in combination with the gauge including atomic orbital (GIAO) scheme, to treat the gauge origin problem, is presented. For the spin-rotation tensor, the calculation of the magnetic shielding tensor represents the most demanding computational task. Employing the ADFT-GIAO methodology, the central processing unit time for the magnetic shielding tensor calculation can be dramatically reduced. In this work, the quality of spin-rotation constants obtained with the ADFT-GIAO methodology is compared with available experimental data as well as with other theoretical results at the Hartree-Fock and coupled-cluster level of theory. It is found that the agreement between the ADFT-GIAO results and the experiment is good and very similar to the ones obtained by the coupled-cluster single-doubles-perturbative triples-GIAO methodology. With the improved computational performance achieved, the computation of the spin-rotation tensors of large systems or along Born-Oppenheimer molecular dynamics trajectories becomes feasible in reasonable times. Three models of carbon fullerenes containing hundreds of atoms and thousands of basis functions are used for benchmarking the performance. Furthermore, a theoretical study of temperature effects on the structure and spin-rotation tensor of the H(12)C-(12)CH-DF complex is presented. Here, the temperature dependency of the spin-rotation tensor of the fluorine nucleus can be used to identify experimentally the so far unknown bent isomer of this complex. To the best of our knowledge this is the first time that temperature effects on the spin-rotation tensor are investigated.

  11. UV-Vis optoelectronic properties of α-SnWO4: A comparative experimental and density functional theory based study

    KAUST Repository

    Ziani, Ahmed; Harb, Moussab; Noureldine, Dalal; Takanabe, Kazuhiro

    2015-01-01

    and density functional perturbation theory using the HSE06 functional. The α-SnWO4 material shows an indirect bandgap of 1.52 eV with high absorption coefficient in the visible-light range (>2 × 105 cm−1). The results show relatively high dielectric constant

  12. Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

    KAUST Repository

    Van Regemorter, Tanguy; Guillaume, Maxime; Sini, Gjergji; Sears, John S.; Geskin, Victor; Bré das, Jean-Luc; Beljonne, David; Cornil, Jé rô me

    2012-01-01

    In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

  13. Acetate and phosphate anion adsorption linear sweep voltammograms simulated using density functional theory

    KAUST Repository

    Savizi, Iman Shahidi Pour

    2011-04-01

    Specific adsorption of anions to electrode surfaces may alter the rates of electrocatalytic reactions. Density functional theory (DFT) methods are used to predict the adsorption free energy of acetate and phosphate anions as a function of Pt(1 1 1) electrode potential. Four models of the electrode potential are used including a simple vacuum slab model, an applied electric field model with and without the inclusion of a solvating water bi-layer, and the double reference model. The linear sweep voltammogram (LSV) due to anion adsorption is simulated using the DFT results. The inclusion of solvation at the electrochemical interface is necessary for accurately predicting the adsorption peak position. The Langmuir model is sufficient for predicting the adsorption peak shape, indicating coverage effects are minor in altering the LSV for acetate and phosphate adsorption. Anion adsorption peak positions are determined for solution phase anion concentrations present in microbial fuel cells and microbial electrolysis cells and discussion is provided as to the impact of anion adsorption on oxygen reduction and hydrogen evolution reaction rates in these devices. © 2011 Elsevier Ltd. All rights reserved.

  14. Rare earth substitutional impurities in germanium: A hybrid density functional theory study

    Science.gov (United States)

    Igumbor, E.; Omotoso, E.; Tunhuma, S. M.; Danga, H. T.; Meyer, W. E.

    2017-10-01

    The Heyd, Scuseria, and Ernzerhof (HSE06) hybrid functional by means of density functional theory has been used to model the electronic and structural properties of rare earth (RE) substitutional impurities in germanium (REGe) . The formation and charge state transition energies for the REGe (RE = Ce, Pr, Er and Eu) were calculated. The energy of formation for the neutral charge state of the REGe lies between -0.14 and 3.13 eV. The formation energy result shows that the Pr dopant in Ge (PrGe) has the lowest formation energy of -0.14 eV, and is most energetically favourable under equilibrium conditions. The REGe induced charge state transition levels within the band gap of Ge. Shallow acceptor levels were induced by both the Eu (EuGe) and Pr (PrGe) dopants in Ge. The CeGe and ErGe exhibited properties of negative-U ordering with effective-U values of -0.85 and -1.07 eV, respectively.

  15. Critical temperature for shape transition in hot nuclei within covariant density functional theory

    Science.gov (United States)

    Zhang, W.; Niu, Y. F.

    2018-05-01

    Prompted by the simple proportional relation between critical temperature for pairing transition and pairing gap at zero temperature, we investigate the relation between critical temperature for shape transition and ground-state deformation by taking even-even Cm-304286 isotopes as examples. The finite-temperature axially deformed covariant density functional theory with BCS pairing correlation is used. Since the Cm isotopes are the newly proposed nuclei with octupole correlations, we studied in detail the free energy surface, the Nilsson single-particle (s.p.) levels, and the components of s.p. levels near the Fermi level in 292Cm. Through this study, the formation of octupole equilibrium is understood by the contribution coming from the octupole driving pairs with Ω [N ,nz,ml] and Ω [N +1 ,nz±3 ,ml] for single-particle levels near the Fermi surfaces as it provides a good manifestation of the octupole correlation. Furthermore, the systematics of deformations, pairing gaps, and the specific heat as functions of temperature for even-even Cm-304286 isotopes are discussed. Similar to the relation between the critical pairing transition temperature and the pairing gap at zero temperature Tc=0.6 Δ (0 ) , a proportional relation between the critical shape transition temperature and the deformation at zero temperature Tc=6.6 β (0 ) is found for both octupole shape transition and quadrupole shape transition for the isotopes considered.

  16. Prediction of Reduction Potentials of Copper Proteins with Continuum Electrostatics and Density Functional Theory.

    Science.gov (United States)

    Fowler, Nicholas J; Blanford, Christopher F; Warwicker, Jim; de Visser, Sam P

    2017-11-02

    Blue copper proteins, such as azurin, show dramatic changes in Cu 2+ /Cu + reduction potential upon mutation over the full physiological range. Hence, they have important functions in electron transfer and oxidation chemistry and have applications in industrial biotechnology. The details of what determines these reduction potential changes upon mutation are still unclear. Moreover, it has been difficult to model and predict the reduction potential of azurin mutants and currently no unique procedure or workflow pattern exists. Furthermore, high-level computational methods can be accurate but are too time consuming for practical use. In this work, a novel approach for calculating reduction potentials of azurin mutants is shown, based on a combination of continuum electrostatics, density functional theory and empirical hydrophobicity factors. Our method accurately reproduces experimental reduction potential changes of 30 mutants with respect to wildtype within experimental error and highlights the factors contributing to the reduction potential change. Finally, reduction potentials are predicted for a series of 124 new mutants that have not yet been investigated experimentally. Several mutants are identified that are located well over 10 Å from the copper center that change the reduction potential by more than 85 mV. The work shows that secondary coordination sphere mutations mostly lead to long-range electrostatic changes and hence can be modeled accurately with continuum electrostatics. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

  17. Electrostatic solvation free energies of charged hard spheres using molecular dynamics with density functional theory interactions

    Science.gov (United States)

    Duignan, Timothy T.; Baer, Marcel D.; Schenter, Gregory K.; Mundy, Chistopher J.

    2017-10-01

    Determining the solvation free energies of single ions in water is one of the most fundamental problems in physical chemistry and yet many unresolved questions remain. In particular, the ability to decompose the solvation free energy into simple and intuitive contributions will have important implications for models of electrolyte solution. Here, we provide definitions of the various types of single ion solvation free energies based on different simulation protocols. We calculate solvation free energies of charged hard spheres using density functional theory interaction potentials with molecular dynamics simulation and isolate the effects of charge and cavitation, comparing to the Born (linear response) model. We show that using uncorrected Ewald summation leads to unphysical values for the single ion solvation free energy and that charging free energies for cations are approximately linear as a function of charge but that there is a small non-linearity for small anions. The charge hydration asymmetry for hard spheres, determined with quantum mechanics, is much larger than for the analogous real ions. This suggests that real ions, particularly anions, are significantly more complex than simple charged hard spheres, a commonly employed representation.

  18. Density functional theory + U modeling of polarons in organohalide lead perovskites

    Directory of Open Access Journals (Sweden)

    Eric Welch

    2016-12-01

    Full Text Available We investigate the possible formation of polarons in four organic perovskites (CH3NH3PbI3, CH3NH3PbBr3, CH3NH3PbCl3, and CH3NH3PbI2Cl1 using a density functional theory (DFT calculations with local potentials and hybrid functionals. We show that DFT+U method with U = 8 eV predicts a correct band-gap and matches the forces on ions from hybrid calculations. We then use the DFT + U approach to study the effect of polarons, i.e. to search the configuration space and locate the lowest energy localized band gap state self-trapped hole (STH. STH configurations were found for three pure halides and one mixed halide system. Spin orbit coupling (SOC was also taken into account and the results may be found in the supplementary material. This study focuses on the +U method; however, SOC corrections added to the DFT+U calculations also resulted in STH states in all four systems.

  19. Density functional theory for the description of charge-transfer processes at TTF/TCNQ interfaces

    KAUST Repository

    Van Regemorter, Tanguy

    2012-09-15

    In the field of organic electronics, a central issue is to assess how the frontier electronic levels of two adjacent organic layers align with respect to one another at the interface. This alignment can be driven by the presence of a partial charge transfer and the formation of an interface dipole; it plays a key role for instance in determining the rates of exciton dissociation or exciton formation in organic solar cells or light-emitting diodes, respectively. Reliably modeling the processes taking place at these interfaces remains a challenge for the computational chemistry community. Here, we review our recent theoretical work on the influence of the choice of density functional theory (DFT) methodology on the description of the charge-transfer character in the ground state of TTF/ TCNQ model complexes and interfaces. Starting with the electronic properties of the isolated TTF and TCNQ molecules and then considering the charge transfer and resulting interface dipole in TTF/TCNQ donor-acceptor stacks and bilayers, we examine the impact of the choice of DFT functional in describing the interfacial electronic structure. Finally, we employ computations based on periodic boundary conditions to highlight the impact of depolarization effects on the interfacial dipole moment. © Springer-Verlag 2012.

  20. Electrochemical specific adsorption of halides on Cu 111, 100, and 211: A Density Functional Theory study

    International Nuclear Information System (INIS)

    McCrum, Ian T.; Akhade, Sneha A.; Janik, Michael J.

    2015-01-01

    The specific adsorption of ions onto electrode surfaces can affect electrocatalytic reactions. Density functional theory is used to investigate the specific adsorption of aqueous F − , Cl − , Br − , and I − onto Cu (111), (100), and (211) surfaces. The adsorption is increasingly favorable in the order of F − < Cl − < Br − < I − . The adsorption has a weak dependence on the surface facet, with adsorption most favorable on Cu (100) and least favorable on Cu (111). Potential ranges where specific adsorption would be expected on each facet are reported. The thermodynamics of bulk copper halide (CuX, CuX 2 ) formation are also investigated as a function of potential. CuX formation occurs at potentials slightly more positive of halide specific adsorption and of copper oxidation in aqueous electrolytes. Specifically adsorbed halides and bulk CuX may be present during a variety of electrochemical reactions carried out over a Cu electrode in halide containing electrolyte solutions

  1. Simulation of X-ray absorption spectra with orthogonality constrained density functional theory.

    Science.gov (United States)

    Derricotte, Wallace D; Evangelista, Francesco A

    2015-06-14

    Orthogonality constrained density functional theory (OCDFT) [F. A. Evangelista, P. Shushkov and J. C. Tully, J. Phys. Chem. A, 2013, 117, 7378] is a variational time-independent approach for the computation of electronic excited states. In this work we extend OCDFT to compute core-excited states and generalize the original formalism to determine multiple excited states. Benchmark computations on a set of 13 small molecules and 40 excited states show that unshifted OCDFT/B3LYP excitation energies have a mean absolute error of 1.0 eV. Contrary to time-dependent DFT, OCDFT excitation energies for first- and second-row elements are computed with near-uniform accuracy. OCDFT core excitation energies are insensitive to the choice of the functional and the amount of Hartree-Fock exchange. We show that OCDFT is a powerful tool for the assignment of X-ray absorption spectra of large molecules by simulating the gas-phase near-edge spectrum of adenine and thymine.

  2. New Methods of Esterification of Nanodiamonds in Fighting Breast Cancer—A Density Functional Theory Approach

    Directory of Open Access Journals (Sweden)

    Linda-Lucila Landeros-Martinez

    2017-10-01

    Full Text Available The use of nanodiamonds as anticancer drug delivery vehicles has received much attention in recent years. In this theoretical paper, we propose using different esterification methods for nanodiamonds. The monomers proposed are 2-hydroxypropanal, polyethylene glycol, and polyglicolic acid. Specifically, the hydrogen bonds, infrared (IR spectra, molecular polar surface area, and reactivity parameters are analyzed. The monomers proposed for use in esterification follow Lipinski’s rule of five, meaning permeability is good, they have good permeation, and their bioactivity is high. The results show that the complex formed between tamoxifen and nanodiamond esterified with polyglicolic acid presents the greatest number of hydrogen bonds and a good amount of molecular polar surface area. Calculations concerning the esterified nanodiamond and reactivity parameters were performed using Density Functional Theory with the M06 functional and the basis set 6–31G (d; for the esterified nanodiamond–Tamoxifen complexes, the semi-empirical method PM6 was used. The solvent effect has been taken into account by using implicit modelling and the conductor-like polarizable continuum model.

  3. Optical excitation and electron relaxation dynamics at semiconductor surfaces: a combined approach of density functional and density matrix theory applied to the silicon (001) surface

    Energy Technology Data Exchange (ETDEWEB)

    Buecking, N

    2007-11-05

    In this work a new theoretical formalism is introduced in order to simulate the phononinduced relaxation of a non-equilibrium distribution to equilibrium at a semiconductor surface numerically. The non-equilibrium distribution is effected by an optical excitation. The approach in this thesis is to link two conventional, but approved methods to a new, more global description: while semiconductor surfaces can be investigated accurately by density-functional theory, the dynamical processes in semiconductor heterostructures are successfully described by density matrix theory. In this work, the parameters for density-matrix theory are determined from the results of density-functional calculations. This work is organized in two parts. In Part I, the general fundamentals of the theory are elaborated, covering the fundamentals of canonical quantizations as well as the theory of density-functional and density-matrix theory in 2{sup nd} order Born approximation. While the formalism of density functional theory for structure investigation has been established for a long time and many different codes exist, the requirements for density matrix formalism concerning the geometry and the number of implemented bands exceed the usual possibilities of the existing code in this field. A special attention is therefore attributed to the development of extensions to existing formulations of this theory, where geometrical and fundamental symmetries of the structure and the equations are used. In Part II, the newly developed formalism is applied to a silicon (001)surface in a 2 x 1 reconstruction. As first step, density-functional calculations using the LDA functional are completed, from which the Kohn-Sham-wave functions and eigenvalues are used to calculate interaction matrix elements for the electron-phonon-coupling an the optical excitation. These matrix elements are determined for the optical transitions from valence to conduction bands and for electron-phonon processes inside the

  4. Extension of the Kohn-Sham formulation of density functional theory to finite temperature

    Science.gov (United States)

    Gonis, A.; Däne, M.

    2018-05-01

    Based on Mermin's extension of the Hohenberg and Kohn theorems to non-zero temperature, the Kohn-Sham formulation of density functional theory (KS-DFT) is generalized to finite temperature. We show that present formulations are inconsistent with Mermin's functional containing expressions, in particular describing the Coulomb energy, that defy derivation and are even in violation of rules of logical inference. More; current methodology is in violation of fundamental laws of both quantum and classical mechanics. Based on this feature, we demonstrate the impossibility of extending the KS formalism to finite temperature through the self-consistent solutions of the single-particle Schrödinger equation of T > 0. Guided by the form of Mermin's functional that depends on the eigenstates of a Hamiltonian, determined at T = 0, we base our extension of KS-DFT on the determination of the excited states of a non-interacting system at the zero of temperature. The resulting formulation is consistent with that of Mermin constructing the free energy at T > 0 in terms of the excited states of a non-interacting Hamiltonian (system) that, within the KS formalism, are described by Slater determinants. To determine the excited states at T = 0 use is made of the extension of the Hohenberg and Kohn theorems to excited states presented in previous work applied here to a non-interacting collection of replicas of a non-interacting N-particle system, whose ground state density is taken to match that of K non-interacting replicas of an interacting N-particle system at T = 0 . The formalism allows for an ever denser population of the excitation spectrum of a Hamiltonian, within the KS approximation. The form of the auxiliary potential, (Kohn-Sham potential), is formally identical to that in the ground state formalism with the contribution of the Coulomb energy provided by the derivative of the Coulomb energy in all excited states taken into account. Once the excited states are determined, the

  5. Density Functional Theory applied to magnetic materials: Mn{sub 3}O{sub 4} at different hybrid functionals

    Energy Technology Data Exchange (ETDEWEB)

    Ribeiro, R.A.P. [Department of Chemistry, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil); Lazaro, S.R. de, E-mail: srlazaro@upeg.br [Department of Chemistry, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil); Pianaro, S.A. [Department of Materials Engineering, State University of Ponta Grossa, Av. General Carlos Cavalcanti, 4748, 84030-900 Ponta Grossa, PR (Brazil)

    2015-10-01

    Antiferromagnetic Mn{sub 3}O{sub 4} in spinel structure was investigated employing the Density Functional Theory at different hybrid functionals with default HF exchange percentage. Structural, electronic and magnetic properties were examined. Structural results were in agreement with experimental and Hartree–Fock results showing that the octahedral site was distorted by the Jahn–Teller effect, which changed the electron density distribution. Band-gap results for B3LYP and B3PW hybrid functionals were closer to the experimental when compared to PBE0. Mulliken Population Analysis revealed magnetic moments very close to ideal d{sup 4} and d{sup 5} electron configurations of Mn{sup 3+} and Mn{sup 2+}, respectively. Electron density maps are useful to determine that oxygen atoms mediate the electron transfer between octahedral and tetrahedral clusters. Magnetic properties were investigated from theoretical results for exchange coupling constants. Intratetrahedral and tetra-octahedral interactions were observed to be antiferromagnetic, whereas, octahedral sites presented antiferromagnetic interactions in the same layer and ferromagnetic in adjacent layers. Results showed that only default B3LYP was successful to describe magnetic properties of antiferromagnetic materials in agreement with experimental results. - Highlights: • We study structural, electronic and magnetic properties of antiferromagnetic Mn{sub 3}O{sub 4}. • B3LYP, B3PW and PBE0 hybrid functionals are compared. • B3LYP and B3PW hybrid functionals are better to band-gap calculations. • Only default B3LYP was successful to describe exchange interactions for Mn{sub 3}O{sub 4}.

  6. Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals

    DEFF Research Database (Denmark)

    Hammer, Bjørk; Hansen, Lars Bruno; Nørskov, Jens Kehlet

    1999-01-01

    A simple formulation of a generalized gradient approximation for the exchange and correlation energy of electrons has been proposed by Perdew, Burke, and Ernzerhof (PBE) [Phys. Rev. Lett. 77, 3865 (1996)]. Subsequently Zhang and Yang [Phys. Rev. Lett. 80, 890 (1998)] have shown that a slight...... revision of the PBE functional systematically improves the atomization energies for a large database of small molecules. In the present work, we show that the Zhang and Yang functional (revPBE) also improves the chemisorption energetics of atoms and molecules on transition-metal surfaces. Our test systems...

  7. Relativistic Adiabatic Time-Dependent Density Functional Theory Using Hybrid Functionals and Noncollinear Spin Magnetization

    DEFF Research Database (Denmark)

    Bast, Radovan; Jensen, Hans Jørgen Aagaard; Saue, Trond

    2009-01-01

    into reduction of algebra from quaternion to complex or real. For hybrid GGAs with noncollinear spin magnetization we derive a new computationally advantageous equation for the full second variational derivatives of such exchange-correlation functionals. We apply our implementation to calculations on the ns2...... → ns1np1 excitation energies in the Zn, Cd, and Hg atoms (n = 4-6) and (vertical) excitation energies of UO2+ 2 ; and we test the performance of various functionals by comparison with experimental data (group 12 atoms) or higher-level computational results (UO2+2 ). The results indicate...

  8. Periodic Density Functional Theory Study of the Structure, Raman Spectrum, and Mechanical Properties of Schoepite Mineral.

    Science.gov (United States)

    Colmenero, Francisco; Cobos, Joaquín; Timón, Vicente

    2018-04-16

    The structure and Raman spectrum of schoepite mineral, [(UO 2 ) 8 O 2 (OH) 12 ]·12H 2 O, was studied by means of theoretical calculations. The computations were carried out by using density functional theory with plane waves and pseudopotentials. A norm-conserving pseudopotential specific for the U atom developed in a previous work was employed. Because it was not possible to locate H atoms directly from X-ray diffraction (XRD) data by structure refinement in previous experimental studies, all of the positions of the H atoms in the full unit cell were determined theoretically. The structural results, including the lattice parameters, bond lengths, bond angles, and powder XRD pattern, were found to be in good agreement with their experimental counterparts. However, the calculations performed using the unit cell designed by Ostanin and Zeller in 2007, involving half of the atoms of the full unit cell, led to significant errors in the computed powder XRD pattern. Furthermore, Ostanin and Zeller's unit cell contains hydronium ions, H 3 O + , which are incompatible with the experimental information. Therefore, while the use of this schoepite model may be a very useful approximation requiring a much smaller amount of computational effort, the full unit cell should be used to study this mineral accurately. The Raman spectrum was also computed by means of density functional perturbation theory and compared with the experimental spectrum. The results were also in agreement with the experimental data. A normal-mode analysis of the theoretical spectra was performed to assign the main bands of the Raman spectrum. This assignment significantly improved the current empirical assignment of the bands of the Raman spectrum of schoepite mineral. In addition, the equation of state and elastic properties of this mineral were determined. The crystal structure of schoepite was found to be stable mechanically and dynamically. Schoepite can be described as a brittle material exhibiting

  9. Restoring the consistency with the contact density theorem of a classical density functional theory of ions at a planar electrical double layer.

    Science.gov (United States)

    Gillespie, Dirk

    2014-11-01

    Classical density functional theory (DFT) of fluids is a fast and efficient theory to compute the structure of the electrical double layer in the primitive model of ions where ions are modeled as charged, hard spheres in a background dielectric. While the hard-core repulsive component of this ion-ion interaction can be accurately computed using well-established DFTs, the electrostatic component is less accurate. Moreover, many electrostatic functionals fail to satisfy a basic theorem, the contact density theorem, that relates the bulk pressure, surface charge, and ion densities at their distances of closest approach for ions in equilibrium at a smooth, hard, planar wall. One popular electrostatic functional that fails to satisfy the contact density theorem is a perturbation approach developed by Kierlik and Rosinberg [Phys. Rev. A 44, 5025 (1991)PLRAAN1050-294710.1103/PhysRevA.44.5025] and Rosenfeld [J. Chem. Phys. 98, 8126 (1993)JCPSA60021-960610.1063/1.464569], where the full free-energy functional is Taylor-expanded around a bulk (homogeneous) reference fluid. Here, it is shown that this functional fails to satisfy the contact density theorem because it also fails to satisfy the known low-density limit. When the functional is corrected to satisfy this limit, a corrected bulk pressure is derived and it is shown that with this pressure both the contact density theorem and the Gibbs adsorption theorem are satisfied.

  10. Virial theorem in the Kohn-Sham density-functional theory formalism: Accurate calculation of the atomic quantum theory of atoms in molecules energies

    NARCIS (Netherlands)

    Rodriguez, A.; Ayers, P.W.; Gotz, A.W.; Castillo-Alvarado, F.L.

    2009-01-01

    A new approach for computing the atom-in-molecule [quantum theory of atoms in molecule (QTAIM)] energies in Kohn-Sham density-functional theory is presented and tested by computing QTAIM energies for a set of representative molecules. In the new approach, the contribution for the correlation-kinetic

  11. Harris functional and related methods for calculating total energies in density-functional theory

    International Nuclear Information System (INIS)

    Averill, F.W.; Painter, G.S.

    1990-01-01

    The simplified energy functional of Harris has given results of useful accuracy for systems well outside the limits of weakly interacting fragments for which the method was originally proposed. In the present study, we discuss the source of the frequent good agreement of the Harris energy with full Kohn-Sham self-consistent results. A procedure is described for extending the applicability of the scheme to more strongly interacting systems by going beyond the frozen-atom fragment approximation. A gradient-force expression is derived, based on the Harris functional, which accounts for errors in the fragment charge representation. Results are presented for some diatomic molecules, illustrating the points of this study

  12. Infrared spectroscopy and density functional theory investigation of calcite, chalk, and coccoliths-do we observe the mineral surface?

    DEFF Research Database (Denmark)

    Andersson, Martin Peter; Hem, Caroline Piper; Schultz, Logan Nicholas

    2014-01-01

    broadening from macroscopic dielectric effects. We detect water adsorbed on the high surface area synthetic calcite, which permits observation of the chemistry of thin liquid films on calcite using transmission infrared spectroscopy. The combination of infrared spectroscopy and density functional theory also...... asymmetric for the coccoliths and the synthetic calcite prepared using the carbonation method. It can be very well fitted by two peaks: a narrow Lorenzian at lower frequency and a broader Gaussian at higher frequency. These two samples both have a high specific surface area. Density functional theory...

  13. Density Functional Theory Simulations of Semiconductors for Photovoltaic Applications: Hybrid Organic-Inorganic Perovskites and III/V Heterostructures

    Directory of Open Access Journals (Sweden)

    Jacky Even

    2014-01-01

    Full Text Available Potentialities of density functional theory (DFT based methodologies are explored for photovoltaic materials through the modeling of the structural and optoelectronic properties of semiconductor hybrid organic-inorganic perovskites and GaAs/GaP heterostructures. They show how the properties of these bulk materials, as well as atomistic relaxations, interfaces, and electronic band-lineups in small heterostructures, can be thoroughly investigated. Some limitations of available standard DFT codes are discussed. Recent improvements able to treat many-body effects or based on density-functional perturbation theory are also reviewed in the context of issues relevant to photovoltaic technologies.

  14. Role of physisorption states in molecular scattering: a semilocal density-functional theory study on O2/Ag(111).

    Science.gov (United States)

    Goikoetxea, I; Meyer, J; Juaristi, J I; Alducin, M; Reuter, K

    2014-04-18

    We simulate the scattering of O2 from Ag(111) with classical dynamics simulations performed on a six-dimensional potential energy surface calculated within semilocal density-functional theory. The enigmatic experimental trends that originally required the conjecture of two types of repulsive walls, arising from a physisorption and chemisorption part of the interaction potential, are fully reproduced. Given the inadequate description of the physisorption properties in semilocal density-functional theory, our work casts severe doubts on the prevalent notion to use molecular scattering data as indirect evidence for the existence of such states.

  15. Adsorption of short-chain fluids at solid substrates from density functional theory

    International Nuclear Information System (INIS)

    Bryk, P.; Bucior, K.; Sokolowski, S.; Zukocinski, G.

    2005-01-01

    We use microscopic density functional theory to investigate the adsorption of short-chains at solid surfaces. The fluid is modeled as freely-jointed tangent spheres that interact via a short-ranged attractive potential. Within the framework of fundamental measure theory we study how the structure and surface phase behaviour of adsorbed fluid changes when the chain length is increased. We observe that the wetting temperature rescaled by the bulk critical temperature decreases with an increase of the chain length. For longer chains this temperature reaches a plateau. For the surface critical temperature an inverse effect is observed, i.e. the surface critical temperature increases with the chain length and then attains a plateau. Furthermore, we analyze how the layering transitions change with the change of the chain length and with relative strength of the fluid-solid interaction. The critical temperature of the first layering transition, rescaled by the bulk critical temperature increases slightly with an increase of the chain length. We have found that for longer chains the layering transitions within consecutive layers are shifted towards very low temperatures and that their sequence is finally replaced by a single transition. Finally we investigate capillary condensation of chain fluid in slit-like pores. We find that for a fluid of chains consisting of a larger number of segments we observe an inversion effect. Namely, the critical temperature of capillary condensation decreases with increasing pore width for a certain interval of values of the pore width. This anomalous behavior is also influenced by the interaction between molecules and pore walls. (author)

  16. Toxicity prediction of ionic liquids based on Daphnia magna by using density functional theory

    Science.gov (United States)

    Nu’aim, M. N.; Bustam, M. A.

    2018-04-01

    By using a model called density functional theory, the toxicity of ionic liquids can be predicted and forecast. It is a theory that allowing the researcher to have a substantial tool for computation of the quantum state of atoms, molecules and solids, and molecular dynamics which also known as computer simulation method. It can be done by using structural feature based quantum chemical reactivity descriptor. The identification of ionic liquids and its Log[EC50] data are from literature data that available in Ismail Hossain thesis entitled “Synthesis, Characterization and Quantitative Structure Toxicity Relationship of Imidazolium, Pyridinium and Ammonium Based Ionic Liquids”. Each cation and anion of the ionic liquids were optimized and calculated. The geometry optimization and calculation from the software, produce the value of highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO). From the value of HOMO and LUMO, the value for other toxicity descriptors were obtained according to their formulas. The toxicity descriptor that involves are electrophilicity index, HOMO, LUMO, energy gap, chemical potential, hardness and electronegativity. The interrelation between the descriptors are being determined by using a multiple linear regression (MLR). From this MLR, all descriptors being analyzed and the descriptors that are significant were chosen. In order to develop the finest model equation for toxicity prediction of ionic liquids, the selected descriptors that are significant were used. The validation of model equation was performed with the Log[EC50] data from the literature and the final model equation was developed. A bigger range of ionic liquids which nearly 108 of ionic liquids can be predicted from this model equation.

  17. Development of an exchange–correlation functional with uncertainty quantification capabilities for density functional theory

    Energy Technology Data Exchange (ETDEWEB)

    Aldegunde, Manuel, E-mail: M.A.Aldegunde-Rodriguez@warwick.ac.uk; Kermode, James R., E-mail: J.R.Kermode@warwick.ac.uk; Zabaras, Nicholas

    2016-04-15

    This paper presents the development of a new exchange–correlation functional from the point of view of machine learning. Using atomization energies of solids and small molecules, we train a linear model for the exchange enhancement factor using a Bayesian approach which allows for the quantification of uncertainties in the predictions. A relevance vector machine is used to automatically select the most relevant terms of the model. We then test this model on atomization energies and also on bulk properties. The average model provides a mean absolute error of only 0.116 eV for the test points of the G2/97 set but a larger 0.314 eV for the test solids. In terms of bulk properties, the prediction for transition metals and monovalent semiconductors has a very low test error. However, as expected, predictions for types of materials not represented in the training set such as ionic solids show much larger errors.

  18. A model for the electrical double layer combining integral equation techniques with quantum density functional theory

    International Nuclear Information System (INIS)

    Luque, N.B.; Woelki, S.; Henderson, D.; Schmickler, W.

    2011-01-01

    Highlights: · We augment a double-layer model based on integral equations by calculating the interaction parameters with the electrode from quantum density functional theory · Explicit model calculations for Ag(1 1 1) in aqueous solutions give at least qualitatively good results for the particle profiles · Ours is the only method which allows the calculation of capacity-charge characteristics. · We obtain reasonable values for the Helmholtz (inner-layer) capacity. - Abstract: We have complemented the singlet reference interaction site model for the electric double layer by quantum chemical calculations for the interaction of ions and solvents with an electrode. Specific calculations have been performed for an aqueous solution of NaCl in contact with a Ag(1 1 1) electrode. The particle profiles near the electrode show the specific adsorption of Cl - ions, but not of Na + , and are at least in qualitative agreement with those obtained by molecular dynamics. Including the electronic response of the silver surface into the model results in reasonable capacity-charge characteristics.

  19. Simulating Excitons in MoS2 with Time-Dependent Density Functional Theory

    Science.gov (United States)

    Flamant, Cedric; Kolesov, Grigory; Kaxiras, Efthimios

    Monolayer molybdenum disulfide, owing to its graphene-like two-dimensional geometry whilst still having a finite bandgap, is a material of great interest in condensed matter physics and for potential application in electronic devices. In particular, MoS2 exhibits significant excitonic effects, a desirable quality for fundamental many-body research. Time-dependent density functional theory (TD-DFT) allows us to simulate dynamical effects as well as temperature-based effects in a natural way given the direct treatment of the time evolution of the system. We present a TD-DFT study of monolayer MoS2 exciton dynamics, examining various qualitative and quantitative predictions in pure samples and in the presence of defects. In particular, we generate an absorption spectrum through simulated pulse excitation for comparison to experiment and also analyze the response of the exciton in an external electric field.In this work we also discuss the electronic structure of the exciton in MoS2 with and without vacancies.

  20. Counterintuitive electron localisation from density-functional theory with polarisable solvent models

    Energy Technology Data Exchange (ETDEWEB)

    Dale, Stephen G., E-mail: sdale@ucmerced.edu [Chemistry and Chemical Biology, School of Natural Sciences, University of California, Merced, 5200 North Lake Road, Merced, California 95343 (United States); Johnson, Erin R., E-mail: erin.johnson@dal.ca [Department of Chemistry, Dalhousie University, 6274 Coburg Road, Halifax, Nova Scotia B3H 4R2 (Canada)

    2015-11-14

    Exploration of the solvated electron phenomena using density-functional theory (DFT) generally results in prediction of a localised electron within an induced solvent cavity. However, it is well known that DFT favours highly delocalised charges, rendering the localisation of a solvated electron unexpected. We explore the origins of this counterintuitive behaviour using a model Kevan-structure system. When a polarisable-continuum solvent model is included, it forces electron localisation by introducing a strong energetic bias that favours integer charges. This results in the formation of a large energetic barrier for charge-hopping and can cause the self-consistent field to become trapped in local minima thus converging to stable solutions that are higher in energy than the ground electronic state. Finally, since the bias towards integer charges is caused by the polarisable continuum, these findings will also apply to other classical polarisation corrections, as in combined quantum mechanics and molecular mechanics (QM/MM) methods. The implications for systems beyond the solvated electron, including cationic DNA bases, are discussed.