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Sample records for quantum theoretical calculations

  1. Theoretical study of enzymatically catalyzed tautomerization of carbon acids in aqueous solution: quantum calculations and steered molecular dynamics simulations.

    PubMed

    Tolosa, Santiago; Hidalgo, Antonio; Sansón, Jorge A

    2016-02-01

    The thermodynamics and kinetics of enzymatically assisted reactions of carbon acids were studied theoretically in this work. Quantum electronic (QE) structure calculations and steered molecular dynamics (SMD) simulations were carried out. Three 3-butenal tautomerization reactions that proceed from the β,γ-unsaturated reactant (R) to the α,β-unsaturated carbon acid product (P) and occur in two elementary steps through an intermediate (I) were studied, ignoring or including the surrounding aqueous medium in the calculations. The Gibbs free energies of activation of the R ⇆ I enolization and I ⇆ P ketonization steps were found to decrease considerably when residues simulating enzymes were introduced into these processes. Although the processes became slightly more favorable thermodynamically when the solution was included in the simulations, they became less favorable kinetically. The results from SMD simulations of these reactions were qualitatively consistent with the values we obtained using QE as well as those found by other authors in similar studies. Our simulations also allowed us to perform a detailed study of these reactions in solution. PMID:26815031

  2. Quantum Chemical Calculations

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W.; Arnold, James O. (Technical Monitor)

    1997-01-01

    The current methods of quantum chemical calculations will be reviewed. The accent will be on the accuracy that can be achieved with these methods. The basis set requirements and computer resources for the various methods will be discussed. The utility of the methods will be illustrated with some examples, which include the calculation of accurate bond energies for SiF$_n$ and SiF$_n^+$ and the modeling of chemical data storage.

  3. Accurate quantum chemical calculations

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Taylor, Peter R.

    1989-01-01

    An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.

  4. Theoretical study of dehydration-carbonation reaction on brucite surface based on ab initio quantum mechanic calculations

    NASA Astrophysics Data System (ADS)

    Churakov, S. V.; Parrinello, M.

    2003-04-01

    The carbonation of brucite (Mg(OH)2) has been considered as a potential technology for cleaning industrial carbon dioxide waste. The kinetics of the reaction Mg(OH)2 + CO2 -> MgCO3 + H2O have been studied experimentally at 573°C by Bearat at al. [1]. Their experiments suggest that the carbonation of magnesium hydroxide proceeds by the reaction Mg(OH)2 -> MgO + H2O followed by the adsorption of CO2 molecules on the dehydrated brucite surface. Due to the large difference in volumes between Mg(OH)2 and MgO, dehydration causes the formation of dislocations and cracks, allowing water molecules to leave the brucite surface and facilitating the advance of the carbonation front in the bulk solid. The detailed mechanism of this process is however unknown. We used the Car-Parrinello ab initio molecular dynamics method to study the structure and dynamics of the (0001), (1-100) and (11-20) surfaces of brucit and calculated the enthalpy and activation barrier of H2O nucleation and dehydration on different surfaces. The results obtained are in agreement with previous studies of brucite dehydration by Masini and Bernasconi [2]. The reactive Car-Parrinello molecular dynamics method [3] has been applied to investigate the detailed mechanism of the dehydration-carbonation reaction at the (1-100) interface of brucite with the gas phase. Based on the results of our MD simulations and the calculated enthalpy of CO2 adsorption on the dehydrated brucite surfaces we propose a mechanism for the dehydration/carbonation reaction. [1] Bearat H, McKelvy MJ, Chizmeshya AVG, Sharma R, Carpenter RW (2002) J. Amer. Ceram. Soc. 85(4):742 [2] Masini P and Bernasconi M (2001) J. Phys. Cond. Mat. 13: 1-12 [3] Iannuzzi M, Laio A and Parrinello M (2003) Phys. Rev. Lett. (submitted)

  5. Theoretical modeling of large molecular systems. Advances in the local self consistent field method for mixed quantum mechanics/molecular mechanics calculations.

    PubMed

    Monari, Antonio; Rivail, Jean-Louis; Assfeld, Xavier

    2013-02-19

    Molecular mechanics methods can efficiently compute the macroscopic properties of a large molecular system but cannot represent the electronic changes that occur during a chemical reaction or an electronic transition. Quantum mechanical methods can accurately simulate these processes, but they require considerably greater computational resources. Because electronic changes typically occur in a limited part of the system, such as the solute in a molecular solution or the substrate within the active site of enzymatic reactions, researchers can limit the quantum computation to this part of the system. Researchers take into account the influence of the surroundings by embedding this quantum computation into a calculation of the whole system described at the molecular mechanical level, a strategy known as the mixed quantum mechanics/molecular mechanics (QM/MM) approach. The accuracy of this embedding varies according to the types of interactions included, whether they are purely mechanical or classically electrostatic. This embedding can also introduce the induced polarization of the surroundings. The difficulty in QM/MM calculations comes from the splitting of the system into two parts, which requires severing the chemical bonds that link the quantum mechanical subsystem to the classical subsystem. Typically, researchers replace the quantoclassical atoms, those at the boundary between the subsystems, with a monovalent link atom. For example, researchers might add a hydrogen atom when a C-C bond is cut. This Account describes another approach, the Local Self Consistent Field (LSCF), which was developed in our laboratory. LSCF links the quantum mechanical portion of the molecule to the classical portion using a strictly localized bond orbital extracted from a small model molecule for each bond. In this scenario, the quantoclassical atom has an apparent nuclear charge of +1. To achieve correct bond lengths and force constants, we must take into account the inner shell of the atom: for an sp(3) carbon atom, we consider the two core 1s electrons and treat that carbon as an atom with three electrons. This results in an LSCF+3 model. Similarly, a nitrogen atom with a lone pair of electrons available for conjugation is treated as an atom with five electrons (LSCF+5). This approach is particularly well suited to splitting peptide bonds and other bonds that include carbon or nitrogen atoms. To embed the induced polarization within the calculation, researchers must use a polarizable force field. However, because the parameters of the usual force fields include an average of the induction effects, researchers typically can obtain satisfactory results without explicitly introducing the polarization. When considering electronic transitions, researchers must take into account the changes in the electronic polarization. One approach is to simulate the electronic cloud of the surroundings by a continuum whose dielectric constant is equal to the square of the refractive index. This Electronic Response of the Surroundings (ERS) methodology allows researchers to model the changes in induced polarization easily. We illustrate this approach by modeling the electronic absorption of tryptophan in human serum albumin (HSA). PMID:23249409

  6. Theoretical Calculations of Atomic Data for Spectroscopy

    NASA Technical Reports Server (NTRS)

    Bautista, Manuel A.

    2000-01-01

    Several different approximations and techniques have been developed for the calculation of atomic structure, ionization, and excitation of atoms and ions. These techniques have been used to compute large amounts of spectroscopic data of various levels of accuracy. This paper presents a review of these theoretical methods to help non-experts in atomic physics to better understand the qualities and limitations of various data sources and assess how reliable are spectral models based on those data.

  7. Hybrid quantum teleportation: A theoretical model

    SciTech Connect

    Takeda, Shuntaro; Mizuta, Takahiro; Fuwa, Maria; Yoshikawa, Jun-ichi; Yonezawa, Hidehiro; Furusawa, Akira

    2014-12-04

    Hybrid quantum teleportation – continuous-variable teleportation of qubits – is a promising approach for deterministically teleporting photonic qubits. We propose how to implement it with current technology. Our theoretical model shows that faithful qubit transfer can be achieved for this teleportation by choosing an optimal gain for the teleporter’s classical channel.

  8. Numerical calculations in quantum field theories

    SciTech Connect

    Rebbi, C.

    1984-01-01

    Four lecture notes are included: (1) motivation for numerical calculations in Quantum Field Theory; (2) numerical simulation methods; (3) Monte Carlo studies of Quantum Chromo Dynamics; and (4) systems with fermions. 23 references. (WHK)

  9. Quantum transport calculations using periodic boundaryconditions

    SciTech Connect

    Wang, Lin-Wang

    2004-06-15

    An efficient new method is presented to calculate the quantum transports using periodic boundary conditions. This method allows the use of conventional ground state ab initio programs without big changes. The computational effort is only a few times of a normal groundstate calculations, thus is makes accurate quantum transport calculations for large systems possible.

  10. Theoretical studies of graphene nanoribbon quantum dot qubits

    NASA Astrophysics Data System (ADS)

    Chen, Chih-Chieh; Chang, Yia-Chung

    Graphene nanoribbon quantum dot qubits have been proposed as promising candidates for quantum computing applications to overcome the spin-decoherence problems associated with typical semiconductor (e.g., GaAs) quantum dot qubits. We perform theoretical studies of the electronic structures of graphene nanoribbon quantum dots by solving the Dirac equation with appropriate boundary conditions. We then evaluate the exchange splitting based on an unrestricted Hartree-Fock method for the Dirac particles. The electronic wave function and long-range exchange coupling due to the Klein tunneling and the Coulomb interaction are calculated for various gate configurations. It is found that the exchange coupling between qubits can be significantly enhanced by the Klein tunneling effect. The implications of our results for practical qubit construction and operation are discussed. This work was supported in part by the Ministry of Science and Technology, Taiwan, under Contract No. MOST 104-2112-M-001-009-MY2.

  11. First principle thousand atom quantum dot calculations

    SciTech Connect

    Wang, Lin-Wang; Li, Jingbo

    2004-03-30

    A charge patching method and an idealized surface passivation are used to calculate the single electronic states of IV-IV, III-V, II-VI semiconductor quantum dots up to a thousand atoms. This approach scales linearly and has a 1000 fold speed-up compared to direct first principle methods with a cost of eigen energy error of about 20 meV. The calculated quantum dot band gaps are parametrized for future references.

  12. Information-theoretic temporal Bell inequality and quantum computation

    SciTech Connect

    Morikoshi, Fumiaki

    2006-05-15

    An information-theoretic temporal Bell inequality is formulated to contrast classical and quantum computations. Any classical algorithm satisfies the inequality, while quantum ones can violate it. Therefore, the violation of the inequality is an immediate consequence of the quantumness in the computation. Furthermore, this approach suggests a notion of temporal nonlocality in quantum computation.

  13. Calculation of Bohmian quantum trajectories for STEM.

    PubMed

    Zhang, M; Ming, Y; Zeng, R G; Ding, Z J

    2015-11-01

    We present in this work the calculation of Bohmian quantum trajectories representing the wave function propagation in a crystal for a focused electron probe in a scanning transmission electron microscope (STEM). The wave function and quantum trajectories are obtained from the calculation of time-dependent Schrödinger equation by fast Fourier transformation multislice algorithm. In our work, the Bohmian quantum trajectories of a scanning probe penetrating a Cu crystal are studied as an example of this calculation scheme. The results help us to better understand the electron diffraction process in a microscopic imaging from a trajectory-based point of view. This Bohmian quantum trajectory method can be used to extend the application of classical Monte Carlo method from the study of electron interaction with amorphous solid to crystalline structure. PMID:26396064

  14. Theoretical analysis of perfect quantum state transfer with superconducting qubits

    NASA Astrophysics Data System (ADS)

    Strauch, Frederick W.; Williams, Carl J.

    2008-09-01

    Superconducting quantum circuits, fabricated with multiple layers, are proposed to implement perfect quantum state transfer between nodes of a hypercube network. For tunable devices such as the phase qubit, each node can transmit quantum information to any other node at a constant rate independent of the distance between qubits. The physical limits of quantum state transfer in this network are theoretically analyzed, including the effects of disorder, decoherence, and higher-order couplings.

  15. Photophysical study and theoretical calculations of an ionic liquid crystal bearing oxadiazole

    NASA Astrophysics Data System (ADS)

    Pedro, Jorge A.; Mora, José R.; Westphal, Eduard; Gallardo, Hugo; Fiedler, Haidi D.; Nome, Faruk

    2012-05-01

    We report a detailed photophysical study of 1-dodecyl-4-[5-(4-dodecyloxyphenyl)-1,3,4-oxadiazole-2-yl]pyridinium bromide (454Do), a cationic amphiphile that behaves as a fluorescent liquid crystal. Excitation and emission spectra of the probe in different environments result in significant changes in quantum yields which are correlated with changes in lifetimes and theoretical calculations.

  16. Theoretical Studies of Classical and Quantum Systems

    NASA Astrophysics Data System (ADS)

    Wu, Jian

    1995-01-01

    Two implementations of the Backward Euler method for simulating molecular fluids are compared with brownian dynamics and molecular dynamics simulations. The four methods are used to compute equilibrium and time-dependent properties of a single diatomic molecule, liquid argon, a single butane molecule and liquid butane. We show that the Backward Euler simulation under-estimates the thermodynamic properties of the liquids, predicts liquid structures which are too solid-like, and incorrectly represents dynamical relaxation processes. Also, we show that any agreement between results from the Backward Euler simulation and quantum mechanics is accidental. Although the Backward Euler method allows longer time-steps to be used in simulations, the time-consuming energy minimization required at every time-step decreases significantly the overall computational efficiency. Even when time-steps more than 20 times larger than that required for energy and momentum conservation are used, neither implementation of the Backward Euler algorithm is more accurate than standard molecular dynamics calculations with the same time-step. We conclude that the new method offers no advantage over more usual methods for simulations and that it often predicts incorrect results. In particular, we see no evidence that the method will allow long-time dynamics of polymers and macromolecules to be simulated either accurately or efficiently. Neural and charged xenon in ^4 He clusters at zero temperature have been studied systematically for clusters of different size, up to a thousand particles, by employing variational and diffusion Monte Carlo methods with different choices of pairwise wave functions to describe the correlation between atoms. The static structure characterizing the atomic impurities is discussed with respect to helium density profiles and energy changes induced by adding helium atoms to a cluster one at a time. The effect of the uncertainty of the interaction potential between impurity and helium atom is also investigated. The location of the impurity is evaluated by comparing a combination of one-body and two-body with only two-body wave functions in the variational calculations. The size dependence of the binding energies of impurities for clusters is estimated for clusters and extrapolated to the bulk limit, which is then compared to results obtained by other works.

  17. Magneto-transport calculations in corrugated quantum wires and square quantum dots

    NASA Astrophysics Data System (ADS)

    Holmberg, Nicholas L.

    1999-11-01

    Nanostructure research is becoming an increasingly valuable tool as semiconductor devices are reduced in dimension. There is an obvious limitation to how far semiconductor devices can be scaled down before their expected behavior becomes erratic. This unpredictability will make itself evident in what is known as quantum phenomena. Classical rules will no longer govern the behavior of today's very large scale integration (VLSI) and ultra large scale integration (ULSI) circuitry. Semiconductor quantum dots and corrugated quantum wires (quantum dot arrays) are devices that are currently being studied to learn more about this transition in classical to quantum behavior. Both devices are studied in this work. Gallium Arsenide/Aluminum Gallium Arsenide square quantum dots of varying dimension (0.2 mum to 2.0 mum) with varying quantum point contact widths are simulated to study the scaling behavior of the periodicities of the magneto-conductance fluctuations and trapped electron orbits within the dot (wavefunction scars). Arrays of quantum dots, similar to the single quantum dots, are simulated to study the effect of backscattering and how it leads to enhanced resistance in a corrugated quantum wire. The simulation tools that have been developed and utilized in this work are discussed extensively. A three-dimensional Poisson solver, a one-dimensional Schrodinger solver, and a stabilized mode matching/two-dimensional Schrodinger solver are the tools of choice in this work. Using the simulation tools, theoretically calculated results are used to develop a magneto-conductance fluctuation 'scaling' theory for the square quantum dots. Additional simulation results for corrugated quantum wires are used to compare existing experimental data to study the backscattering effect that is observable in a doubly-corrugated structure. A self-consistent technique that combines all of the simulation tools is utilized to determine whether the scarring of the electron wavefunction exhibits a feedback effect that prolongs the wavefunction scar over a range of magnetic fields.

  18. Quantum number theoretic transforms on multipartite finite systems.

    PubMed

    Vourdas, A; Zhang, S

    2009-06-01

    A quantum system composed of p-1 subsystems, each of which is described with a p-dimensional Hilbert space (where p is a prime number), is considered. A quantum number theoretic transform on this system, which has properties similar to those of a Fourier transform, is studied. A representation of the Heisenberg-Weyl group in this context is also discussed. PMID:19488175

  19. Information Theoretical Analysis of Quantum Optimal Control

    NASA Astrophysics Data System (ADS)

    Lloyd, S.; Montangero, S.

    2014-07-01

    We study the relations between classical information and the feasibility of accurate manipulation of quantum system dynamics. We show that if an efficient classical representation of the dynamics exists, optimal control problems on many-body quantum systems can be solved efficiently with finite precision. In particular, one-dimensional slightly entangled dynamics can be efficiently controlled. We provide a bound for the minimal time necessary to perform the optimal process given the bandwidth of the control pulse, which is the continuous version of the Solovay-Kitaev theorem. Finally, we quantify how noise affects the presented results.

  20. Quantum mechanical calculations to chemical accuracy

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1991-01-01

    The accuracy of current molecular-structure calculations is illustrated with examples of quantum mechanical solutions for chemical problems. Two approaches are considered: (1) the coupled-cluster singles and doubles (CCSD) with a perturbational estimate of the contribution of connected triple excitations, or CCDS(T); and (2) the multireference configuration-interaction (MRCI) approach to the correlation problem. The MRCI approach gains greater applicability by means of size-extensive modifications such as the averaged-coupled pair functional approach. The examples of solutions to chemical problems include those for C-H bond energies, the vibrational frequencies of O3, identifying the ground state of Al2 and Si2, and the Lewis-Rayleigh afterglow and the Hermann IR system of N2. Accurate molecular-wave functions can be derived from a combination of basis-set saturation studies and full configuration-interaction calculations.

  1. A Universal Operator Theoretic Framework for Quantum Fault Tolerance.

    NASA Astrophysics Data System (ADS)

    Gilbert, Gerald; Calderbank, Robert; Aggarwal, Vaneet; Hamrick, Michael; Weinstein, Yaakov

    2008-03-01

    We introduce a universal operator theoretic framework for quantum fault tolerance. This incorporates a top-down approach that implements a system-level criterion based on specification of the full system dynamics, applied at every level of error correction concatenation. This leads to more accurate determinations of error thresholds than could previously be obtained. The basis for the approach is the Quantum Computer Condition (QCC), an inequality governing the evolution of a quantum computer. In addition to more accurate determination of error threshold values, we show that the QCC provides a means to systematically determine optimality (or non-optimality) of different choices of error correction coding and error avoidance strategies. This is possible because, as we show, all known coding schemes are actually special cases of the QCC. We demonstrate this by introducing a new, operator theoretic form of entanglement assisted quantum error correction.

  2. Field-Theoretical Methods in Quantum Magnetism

    NASA Astrophysics Data System (ADS)

    Cabra, Daniel C.; Pujol, Pierre

    We present a review of different field theory techniques that have proved very useful in the study of quantum magnets in low dimensions We first review the application of the spin-wave analysis and non-linear σ-model techniques in one and two dimensional quantum antiferromagnets. We discuss in particular the emergence of Haldane's conjecture for spin chains and ladders within this formalism. We also present a brief discussion on the non-linear σ-model description for the two-dimensional antiferromagnet in the square lattice. In a second part we review the method of abelian bosonization and its application to the study of the XXZ spin 1/2 chain and its generalizations, such as the dimerized chain. Non-abelian bosonization is used to describe both SU (2) symmetric chains with arbitrary spin S and 2 leg ladders, rederiving Haldane's conjecture within this formalism. The inclusion of charge degrees of freedom leading to a Hubbard or a t—J model is also discussed. Finally, we apply the abelian bosonization approach to the study of N-leg ladders in amagnetic field, which leads to a further extension of Haldane's conjecture.

  3. Limitations on information-theoretically-secure quantum homomorphic encryption

    NASA Astrophysics Data System (ADS)

    Yu, Li; Pérez-Delgado, Carlos A.; Fitzsimons, Joseph F.

    2014-11-01

    Homomorphic encryption is a form of encryption which allows computation to be carried out on the encrypted data without the need for decryption. The success of quantum approaches to related tasks in a delegated computation setting has raised the question of whether quantum mechanics may be used to achieve information-theoretically-secure fully homomorphic encryption. Here we show, via an information localization argument, that deterministic fully homomorphic encryption necessarily incurs exponential overhead if perfect security is required.

  4. Quantum Monte Carlo calculations for carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Luu, Thomas; Lähde, Timo A.

    2016-04-01

    We show how lattice quantum Monte Carlo can be applied to the electronic properties of carbon nanotubes in the presence of strong electron-electron correlations. We employ the path-integral formalism and use methods developed within the lattice QCD community for our numerical work. Our lattice Hamiltonian is closely related to the hexagonal Hubbard model augmented by a long-range electron-electron interaction. We apply our method to the single-quasiparticle spectrum of the (3,3) armchair nanotube configuration, and consider the effects of strong electron-electron correlations. Our approach is equally applicable to other nanotubes, as well as to other carbon nanostructures. We benchmark our Monte Carlo calculations against the two- and four-site Hubbard models, where a direct numerical solution is feasible.

  5. Theoretical Calculation of Stability for NASA Stage 57 Stator

    NASA Astrophysics Data System (ADS)

    Benavides, Efrn M.; Juste, Gregorio L.

    2011-09-01

    The stability of 595 operational points, belonging to 25 different experimental arrangements of the NASA stage 57, is studied by means of a theoretical calculation based on a theorem recently presented in the scientific literature. This large number of tests is used for checking the results of the theory for a wide variation of the operational and the design parameters. This study completes a previous one by adding the calculations for the stator. Both rotor and stator results are related with the stage stability. While only seven test points appear as potentially unstable due to the rotor, nine test points do due to the stator.

  6. Quantum Monte Carlo Calculations Applied to Magnetic Molecules

    SciTech Connect

    Larry Engelhardt

    2006-08-09

    We have calculated the equilibrium thermodynamic properties of Heisenberg spin systems using a quantum Monte Carlo (QMC) method. We have used some of these systems as models to describe recently synthesized magnetic molecules, and-upon comparing the results of these calculations with experimental data-have obtained accurate estimates for the basic parameters of these models. We have also performed calculations for other systems that are of more general interest, being relevant both for existing experimental data and for future experiments. Utilizing the concept of importance sampling, these calculations can be carried out in an arbitrarily large quantum Hilbert space, while still avoiding any approximations that would introduce systematic errors. The only errors are statistical in nature, and as such, their magnitudes are accurately estimated during the course of a simulation. Frustrated spin systems present a major challenge to the QMC method, nevertheless, in many instances progress can be made. In this chapter, the field of magnetic molecules is introduced, paying particular attention to the characteristics that distinguish magnetic molecules from other systems that are studied in condensed matter physics. We briefly outline the typical path by which we learn about magnetic molecules, which requires a close relationship between experiments and theoretical calculations. The typical experiments are introduced here, while the theoretical methods are discussed in the next chapter. Each of these theoretical methods has a considerable limitation, also described in Chapter 2, which together serve to motivate the present work. As is shown throughout the later chapters, the present QMC method is often able to provide useful information where other methods fail. In Chapter 3, the use of Monte Carlo methods in statistical physics is reviewed, building up the fundamental ideas that are necessary in order to understand the method that has been used in this work. With these ideas in hand, we then provide a detailed explanation of the current QMC method in Chapter 4. The remainder of the thesis is devoted to presenting specific results: Chapters 5 and 6 contain articles in which this method has been used to answer general questions that are relevant to broad classes of systems. Then, in Chapter 7, we provide an analysis of four different species of magnetic molecules that have recently been synthesized and studied. In all cases, comparisons between QMC calculations and experimental data allow us to distinguish a viable microscopic model and make predictions for future experiments. In Chapter 8, the infamous ''negative sign problem'' is described in detail, and we clearly indicate the limitations on QMC that are imposed by this obstacle. Finally, Chapter 9 contains a summary of the present work and the expected directions for future research.

  7. Quantum Biological Channel Modeling and Capacity Calculation

    PubMed Central

    Djordjevic, Ivan B.

    2012-01-01

    Quantum mechanics has an important role in photosynthesis, magnetoreception, and evolution. There were many attempts in an effort to explain the structure of genetic code and transfer of information from DNA to protein by using the concepts of quantum mechanics. The existing biological quantum channel models are not sufficiently general to incorporate all relevant contributions responsible for imperfect protein synthesis. Moreover, the problem of determination of quantum biological channel capacity is still an open problem. To solve these problems, we construct the operator-sum representation of biological channel based on codon basekets (basis vectors), and determine the quantum channel model suitable for study of the quantum biological channel capacity and beyond. The transcription process, DNA point mutations, insertions, deletions, and translation are interpreted as the quantum noise processes. The various types of quantum errors are classified into several broad categories: (i) storage errors that occur in DNA itself as it represents an imperfect storage of genetic information, (ii) replication errors introduced during DNA replication process, (iii) transcription errors introduced during DNA to mRNA transcription, and (iv) translation errors introduced during the translation process. By using this model, we determine the biological quantum channel capacity and compare it against corresponding classical biological channel capacity. We demonstrate that the quantum biological channel capacity is higher than the classical one, for a coherent quantum channel model, suggesting that quantum effects have an important role in biological systems. The proposed model is of crucial importance towards future study of quantum DNA error correction, developing quantum mechanical model of aging, developing the quantum mechanical models for tumors/cancer, and study of intracellular dynamics in general. PMID:25371271

  8. Density functional calculation of the structural and electronic properties of germanium quantum dots

    SciTech Connect

    Anas, M. M.; Gopir, G.

    2015-04-24

    We apply first principles density functional computational methods to study the structures, densities of states (DOS), and higher occupied molecular orbital (HOMO) – lowest unoccupied molecular orbital (LUMO) gaps of selected free-standing Ge semiconductor quantum dots up to 1.8nm. Our calculations are performed using numerical atomic orbital approach where linear combination of atomic orbital was applied. The surfaces of the quantum dots was passivized by hydrogen atoms. We find that surface passivation does affect the electronic properties associated with the changes of surface state, electron localization, and the energy gaps of germanium nanocrystals as well as the confinement of electrons inside the quantum dots (QDs). Our study shows that the energy gaps of germanium quantum dots decreases with the increasing dot diameter. The size-dependent variations of the computed HOMO-LUMO gaps in our quantum dots model were found to be consistent with the effects of quantum confinement reported in others theoretical and experimental calculation.

  9. Surface Segregation Energies of BCC Binaries from Ab Initio and Quantum Approximate Calculations

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2003-01-01

    We compare dilute-limit segregation energies for selected BCC transition metal binaries computed using ab initio and quantum approximate energy method. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent parameterization. Quantum approximate segregation energies are computed with and without atomistic relaxation. The ab initio calculations are performed without relaxation for the most part, but predicted relaxations from quantum approximate calculations are used in selected cases to compute approximate relaxed ab initio segregation energies. Results are discussed within the context of segregation models driven by strain and bond-breaking effects. We compare our results with other quantum approximate and ab initio theoretical work, and available experimental results.

  10. Theoretical grounds of relativistic methods for calculation of spin–spin coupling constants in nuclear magnetic resonance spectra

    NASA Astrophysics Data System (ADS)

    Rusakova, I. L.; Rusakov, Yu Yu; Krivdin, L. B.

    2016-04-01

    The theoretical grounds of the modern relativistic methods for quantum chemical calculation of spin–spin coupling constants in nuclear magnetic resonance spectra are considered. Examples and prospects of application of relativistic calculations of these constants in the structural studies of organic and heteroorganic compounds are discussed. Practical recommendations on relativistic calculations of spin–spin coupling constants using the available software are given. The bibliography includes 622 references.

  11. Spectrometric studies and theoretical calculations of some ?-ketonitriles

    NASA Astrophysics Data System (ADS)

    Ruiz, Danila; Giussi, Juan; Albesa, Alberto; Schiavoni, Mercedes; Furlong, Jorge; Allegretti, Patricia

    2010-10-01

    The tautomerism of some ?-ketonitriles is investigated by the analysis of their mass spectra and theoretical calculations performed at the MP2/6-31G(d,p) level. The mass spectra of some ?-ketonitriles can provide valuable information regarding the keto-enol and nitrile-ketenimine equilibria taking place in the gas phase. The predictive value of this methodology is supported by the influence of the nature and size of substituents on tautomeric equilibria and the rather good correlation existing between the abundance ratios of selected fragments. Results show that the tautomeric equilibria of these bifunctional compounds can be evaluated by mass spectrometry.

  12. Spectrometric studies and theoretical calculations of some beta-ketonitriles.

    PubMed

    Ruiz, Danila; Giussi, Juan; Albesa, Alberto; Schiavoni, Mercedes; Furlong, Jorge; Allegretti, Patricia

    2010-10-01

    The tautomerism of some beta-ketonitriles is investigated by the analysis of their mass spectra and theoretical calculations performed at the MP2/6-31G(d,p) level. The mass spectra of some beta-ketonitriles can provide valuable information regarding the keto-enol and nitrile-ketenimine equilibria taking place in the gas phase. The predictive value of this methodology is supported by the influence of the nature and size of substituents on tautomeric equilibria and the rather good correlation existing between the abundance ratios of selected fragments. Results show that the tautomeric equilibria of these bifunctional compounds can be evaluated by mass spectrometry. PMID:20630795

  13. Using the Chebychev expansion in quantum transport calculations

    SciTech Connect

    Popescu, Bogdan; Rahman, Hasan; Kleinekathöfer, Ulrich

    2015-04-21

    Irradiation by laser pulses and a fluctuating surrounding liquid environment can, for example, lead to time-dependent effects in the transport through molecular junctions. From the theoretical point of view, time-dependent theories of quantum transport are still challenging. In one of these existing transport theories, the energy-dependent coupling between molecule and leads is decomposed into Lorentzian functions. This trick has successfully been combined with quantum master approaches, hierarchical formalisms, and non-equilibrium Green’s functions. The drawback of this approach is, however, its serious limitation to certain forms of the molecule-lead coupling and to higher temperatures. Tian and Chen [J. Chem. Phys. 137, 204114 (2012)] recently employed a Chebychev expansion to circumvent some of these latter problems. Here, we report on a similar approach also based on the Chebychev expansion but leading to a different set of coupled differential equations using the fact that a derivative of a zeroth-order Bessel function can again be given in terms of Bessel functions. Test calculations show the excellent numerical accuracy and stability of the presented formalism. The time span for which this Chebychev expansion scheme is valid without any restrictions on the form of the spectral density or temperature can be determined a priori.

  14. Preliminary theoretical acoustic and rf sounding calculations for MILL RACE

    SciTech Connect

    Warshaw, S.I.; Dubois, P.F.

    1981-11-02

    As participant in DOE/ISA's Ionospheric Monitoring Program, LLNL has the responsibility of providing theoretical understanding and calculational support for experimental activities carried out by Los Alamos National Laboratory in using ionospheric sounders to remotely detect violent atmospheric phenomena. We have developed a system of interconnected computer codes which simulate the entire range of atmospheric and ionospheric processes involved in this remote detection procedure. We are able to model the acoustic pulse shape from an atmospheric explosion, the subsequent nonlinear transport of this energy to all parts of the immediate atmosphere including the ionosphere, and the propagation of high-frequency ratio waves through the acoustically perturbed ionosphere. Los Alamos' coverage of DNA's MILL RACE event provided an excellent opportunity to assess the credibility of the calculational system to correctly predict how ionospheric sounders would respond to a surface-based chemical explosion. In this experiment, 600 tons of high explosive were detonated at White Sands Missile Range at 12:35:40 local time on 16 September 1981. Vertical incidence rf phase sounders and bistatic oblique incidence rf sounders fielded by Los Alamos and SRI International throughout New Mexico and southern Colorado detected the ionospheric perturbation that ensued. A brief account of preliminary calculations of the acoustic disturbance and the predicted ionospheric sounder signatures for MILL RACE is presented. (WHK)

  15. Tautomerism in 8-Nitroguanosine Studied by NMR and Theoretical Calculations.

    PubMed

    Barbosa, Thaís M; Rittner, Roberto; Alexander, Katie; Cosstick, Richard; Abraham, Raymond J

    2016-02-01

    The guanine base in DNA, due to its low oxidation potential, is particularly sensitive to chemical modifications. A large number of guanine lesions have been characterized and studied in some detail due to their relationship with tissue inflammations. Nevertheless, one example of these lesions is the formation of 8-nitro-guanosine, but the NMR data of this compound was only partially interpreted. A comprehensive study of the two possible tautomeric forms, through a detailed characterization of this compound, has implications for its base pairing properties. The target compound was obtained through a synthetic sequence of five steps, where all intermediates were fully characterized using spectral data. The analysis of the two tautomers was then evaluated through NMR spectroscopy and theoretical calculations of the chemical shifts and NH coupling constants, which were also compared with the data from guanosine. PMID:26810486

  16. Theoretical calculation of the dielectric constant of a bilayer membrane.

    PubMed Central

    Huang, W; Levitt, D G

    1977-01-01

    The dielectric constant (epsilon) and refractive index (n) of a bilayer lipid membrane is determined from the known values of the polarizabilities of the carbon-carbon and carbon-hydrogen bonds. It is assumed that the hydrocarbon chains are hexagonally arranged in an all-trans conformation perpendicular to the plane of the membrane. The only variable in the calculation is the average separation between the chains and the theory relates epsilon to this separation. The calculation and results differ significantly from those presented in a 1968 publication by Ohki. It is shown that a thin membrane is not homogeneously polarized by the applied field. This effect is analysed and the dependence of epsilon on the membrane thickness is determined. The theoretical results are in good quantitative agreement with experimental measurements on bulk paraffins and on oriented multilayers of saturated fatty acids. The most important conclusion is that the dielectric constant for an applied field perpendicular to the membrane (which is the appropriate value for capacitance measurements) differs by only a few percent from the value for the macroscopic (bulk) liquid hydrocarbon. Thus the dielectric constant of a bilayer membrane can be approximated by the value for the appropriate bulk hydrocarbon. PMID:836931

  17. Magnetic rigid rotor in the quantum regime: Theoretical toolbox

    NASA Astrophysics Data System (ADS)

    Rusconi, Cosimo C.; Romero-Isart, Oriol

    2016-02-01

    We describe the quantum dynamics of a magnetic rigid rotor in the mesoscopic scale where the Einstein-De Haas effect is predominant. In particular, we consider a single-domain magnetic nanoparticle with uniaxial anisotropy in a magnetic trap. Starting from the basic Hamiltonian of the system under the macrospin approximation, we derive a bosonized Hamiltonian describing the center-of-mass motion, the total angular momentum, and the macrospin degrees of freedom of the particle treated as a rigid body. This bosonized Hamiltonian can be approximated by a simple quadratic Hamiltonian that captures the rich physics of a nanomagnet tightly confined in position, nearly not spinning, and with its macrospin antialigned to the magnetic field. The theoretical tools derived and used here can be applied to other quantum mechanical rigid rotors.

  18. Maxwell's demon. (II) A quantum-theoretic exorcism

    NASA Astrophysics Data System (ADS)

    Gyftopoulos, Elias P.

    2002-05-01

    In Part II of this two-part paper we prove that Maxwell's demon is unable to accomplish his task of sorting air molecules into swift and slow because in air in a thermodynamic equilibrium state there are no such molecules. The proof is based on the principles of a unified quantum theory of mechanics and thermodynamics. The key idea of the unified theory is that von Neumann's concept of a homogeneous ensemble of identical systems, identically prepared, is valid not only for a density operator ρ equal to a projector (every member of the ensemble is assigned the same projector, ρi=| ψi> < ψi|= ρi2, or the same wave function ψ i as any other member) but also for a density operator that is not a projector (every member of the ensemble is assigned the same density operator, ρ>ρ 2, as any other member). So, the latter ensemble is not a statistical mixture of projectors. The broadening of the validity of the homogeneous ensemble is consistent with the quantum-theoretic postulates about observables, measurement results, and value of any observable. In the context of the unified theory, among the many novel results is the theorem that each molecule of a system in a thermodynamic equilibrium state has zero value of momentum, that is, each molecule is at a standstill and, therefore, there are no molecules to be sorted as swift and slow. Said differently, if Maxwell were cognizant of quantum theory, he would not have conceived of the idea of the demon. It is noteworthy that the zero value of momentum is not the result of averaging over different momenta of many molecules. Under the specified conditions, it is the quantum-theoretic value of the momentum of any one molecule, and the same result is valid even if the system consists of only one molecule.

  19. Theoretical Investigations of Optical Origins of Fluorescent Graphene Quantum Dots.

    PubMed

    Wang, Jingang; Cao, Shuo; Ding, Yong; Ma, Fengcai; Lu, Wengang; Sun, Mengtao

    2016-01-01

    The optical properties of graphene quantum dots (GQDs) were investigated theoretically. We focused on the photoinduced charge transfer and electron-hole coherence of single-layer graphene in the electronic transitions in the visible regions. Surface functionalization with donor or acceptor groups produced a red shift in the absorption spectrum, and electrons and holes were highly delocalized. The recombination of excited, well-separated electron-hole (e-h) pairs can result in enhanced fluorescence. This fluorescence enhancement by surface functionalization occurs because of the decreased symmetry of the graphene resulting from the roughened structure of the surface-functionalized GQDs. PMID:27094439

  20. Theoretical Investigations of Optical Origins of Fluorescent Graphene Quantum Dots

    NASA Astrophysics Data System (ADS)

    Wang, Jingang; Cao, Shuo; Ding, Yong; Ma, Fengcai; Lu, Wengang; Sun, Mengtao

    2016-04-01

    The optical properties of graphene quantum dots (GQDs) were investigated theoretically. We focused on the photoinduced charge transfer and electron-hole coherence of single-layer graphene in the electronic transitions in the visible regions. Surface functionalization with donor or acceptor groups produced a red shift in the absorption spectrum, and electrons and holes were highly delocalized. The recombination of excited, well-separated electron-hole (e–h) pairs can result in enhanced fluorescence. This fluorescence enhancement by surface functionalization occurs because of the decreased symmetry of the graphene resulting from the roughened structure of the surface-functionalized GQDs.

  1. Theoretical analysis of quantum ghost imaging through turbulence

    SciTech Connect

    Chan, Kam Wai Clifford; Simon, D. S.; Sergienko, A. V.; Hardy, Nicholas D.; Shapiro, Jeffrey H.; Dixon, P. Ben; Howland, Gregory A.; Howell, John C.; Eberly, Joseph H.; O'Sullivan, Malcolm N.; Rodenburg, Brandon; Boyd, Robert W.

    2011-10-15

    Atmospheric turbulence generally affects the resolution and visibility of an image in long-distance imaging. In a recent quantum ghost imaging experiment [P. B. Dixon et al., Phys. Rev. A 83, 051803 (2011)], it was found that the effect of the turbulence can nevertheless be mitigated under certain conditions. This paper gives a detailed theoretical analysis to the setup and results reported in the experiment. Entangled photons with a finite correlation area and a turbulence model beyond the phase screen approximation are considered.

  2. Theoretical Investigations of Optical Origins of Fluorescent Graphene Quantum Dots

    PubMed Central

    Wang, Jingang; Cao, Shuo; Ding, Yong; Ma, Fengcai; Lu, Wengang; Sun, Mengtao

    2016-01-01

    The optical properties of graphene quantum dots (GQDs) were investigated theoretically. We focused on the photoinduced charge transfer and electron-hole coherence of single-layer graphene in the electronic transitions in the visible regions. Surface functionalization with donor or acceptor groups produced a red shift in the absorption spectrum, and electrons and holes were highly delocalized. The recombination of excited, well-separated electron-hole (e–h) pairs can result in enhanced fluorescence. This fluorescence enhancement by surface functionalization occurs because of the decreased symmetry of the graphene resulting from the roughened structure of the surface-functionalized GQDs. PMID:27094439

  3. Role of information theoretic uncertainty relations in quantum theory

    NASA Astrophysics Data System (ADS)

    Jizba, Petr; Dunningham, Jacob A.; Joo, Jaewoo

    2015-04-01

    Uncertainty relations based on information theory for both discrete and continuous distribution functions are briefly reviewed. We extend these results to account for (differential) Rényi entropy and its related entropy power. This allows us to find a new class of information-theoretic uncertainty relations (ITURs). The potency of such uncertainty relations in quantum mechanics is illustrated with a simple two-energy-level model where they outperform both the usual Robertson-Schrödinger uncertainty relation and Shannon entropy based uncertainty relation. In the continuous case the ensuing entropy power uncertainty relations are discussed in the context of heavy tailed wave functions and Schrödinger cat states. Again, improvement over both the Robertson-Schrödinger uncertainty principle and Shannon ITUR is demonstrated in these cases. Further salient issues such as the proof of a generalized entropy power inequality and a geometric picture of information-theoretic uncertainty relations are also discussed.

  4. Role of information theoretic uncertainty relations in quantum theory

    SciTech Connect

    Jizba, Petr; Dunningham, Jacob A.; Joo, Jaewoo

    2015-04-15

    Uncertainty relations based on information theory for both discrete and continuous distribution functions are briefly reviewed. We extend these results to account for (differential) Rényi entropy and its related entropy power. This allows us to find a new class of information-theoretic uncertainty relations (ITURs). The potency of such uncertainty relations in quantum mechanics is illustrated with a simple two-energy-level model where they outperform both the usual Robertson–Schrödinger uncertainty relation and Shannon entropy based uncertainty relation. In the continuous case the ensuing entropy power uncertainty relations are discussed in the context of heavy tailed wave functions and Schrödinger cat states. Again, improvement over both the Robertson–Schrödinger uncertainty principle and Shannon ITUR is demonstrated in these cases. Further salient issues such as the proof of a generalized entropy power inequality and a geometric picture of information-theoretic uncertainty relations are also discussed.

  5. Theoretical performance of wurtzite and zincblende InGaN/GaN quantum well lasers

    NASA Astrophysics Data System (ADS)

    Radtke, R. J.; Waghmare, U.; Ehrenreich, H.; Grein, C. H.

    1998-10-01

    The theoretical gain, radiative and Auger recombination rates, and threshold current densities of ideal wurtzite (WZ) and zincblende (ZB) 20 Å In0.2Ga0.8N/70 Å GaN multiple quantum well laser diodes are compared. We obtain upper bounds on device performance, which are based on reliable calculations for both band structure and recombination dependent features and show (1) that the performance of present devices having the ZB and WZ structures are within 20% of each other in InGaN/GaN, and (2) that present performance of the best currently available devices is only a factor of 3-4 below the theoretical limit. Radiative recombination is far more important than Auger processes. The calculations are performed using a superlattice Kṡp formalism and density functional theory within the local-density approximation. The latter yields bulk zone-center energies, wave functions, and directly calculated momentum matrix elements.

  6. Accurate rotational barrier calculations with diffusion quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Klahm, Sebastian; Lüchow, Arne

    2014-04-01

    Accurate quantum Monte Carlo, MP2, coupled cluster, and DFT calculations of rotational barriers of several small molecules are presented. With the diffusion quantum Monte Carlo method (DMC) excellent agreement with experimental barriers is obtained except for the gauche-gauche barriers of n-butane and ethylmethylether. It is argued that these two experimental values might be erroneous. Additionally, barriers calculated with the more efficient variational quantum Monte Carlo method (VMC) are presented. The VMC barriers are less accurate than the DMC results, but it is demonstrated that accurate barriers can be obtained with sophisticated Jastrow correlation functions.

  7. Macroscopic quantum-type potentials in theoretical systems biology.

    PubMed

    Nottale, Laurent

    2013-01-01

    We review in this paper the use of the theory of scale relativity and fractal space-time as a tool particularly well adapted to the possible development of a future genuine systems theoretical biology. We emphasize in particular the concept of quantum-type potentials, since, in many situations, the effect of the fractality of space-or of the underlying medium-can be reduced to the addition of such a potential energy to the classical equations of motion. Various equivalent representations-geodesic, quantum-like, fluid mechanical, stochastic-of these equations are given, as well as several forms of generalized quantum potentials. Examples of their possible intervention in high critical temperature superconductivity and in turbulence are also described, since some biological processes may be similar in some aspects to these physical phenomena. These potential extra energy contributions could have emerged in biology from the very fractal nature of the medium, or from an evolutive advantage, since they involve spontaneous properties of self-organization, morphogenesis, structuration and multi-scale integration. Finally, some examples of applications of the theory to actual biological-like processes and functions are also provided. PMID:24709901

  8. Macroscopic Quantum-Type Potentials in Theoretical Systems Biology

    PubMed Central

    Nottale, Laurent

    2014-01-01

    We review in this paper the use of the theory of scale relativity and fractal space-time as a tool particularly well adapted to the possible development of a future genuine systems theoretical biology. We emphasize in particular the concept of quantum-type potentials, since, in many situations, the effect of the fractality of space—or of the underlying medium—can be reduced to the addition of such a potential energy to the classical equations of motion. Various equivalent representations—geodesic, quantum-like, fluid mechanical, stochastic—of these equations are given, as well as several forms of generalized quantum potentials. Examples of their possible intervention in high critical temperature superconductivity and in turbulence are also described, since some biological processes may be similar in some aspects to these physical phenomena. These potential extra energy contributions could have emerged in biology from the very fractal nature of the medium, or from an evolutive advantage, since they involve spontaneous properties of self-organization, morphogenesis, structuration and multi-scale integration. Finally, some examples of applications of the theory to actual biological-like processes and functions are also provided. PMID:24709901

  9. Monte-carlo calculations for some problems of quantum mechanics

    SciTech Connect

    Novoselov, A. A. Pavlovsky, O. V.; Ulybyshev, M. V.

    2012-09-15

    The Monte-Carlo technique for the calculations of functional integral in two one-dimensional quantum-mechanical problems had been applied. The energies of the bound states in some potential wells were obtained using this method. Also some peculiarities in the calculation of the kinetic energy in the ground state had been studied.

  10. Molecular conformational stability and Spectroscopic analysis of Parared with experimental techniques and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Srinivasaraghavan, R.; Thamaraikannan, S.; Seshadri, S.; Gnanasambandan, T.

    2015-02-01

    The complete vibrational assignment and analysis of the fundamental modes of Parared was carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically from the optimized geometry of the compound from the DFT-B3LYP gradient calculations employing 6-31G(d,p) and 6-311++G(d,p) basis sets. Thermodynamic properties like entropy, heat capacity and enthalpy have been calculated for the molecule. HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using natural bond orbital (NBO) and natural localized molecular orbital (NLMO) analysis. Important non-linear properties such as electric dipole moment and first hyperpolarizability of Parared have been computed using B3LYP quantum chemical calculations. Finally, the Mulliken population analysis on atomic charges of the title compound has been calculated.

  11. Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

    NASA Technical Reports Server (NTRS)

    Du, Ping

    1993-01-01

    As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

  12. Theoretical Calculation and Validation of the Water Vapor Continuum Absorption

    NASA Technical Reports Server (NTRS)

    Ma, Qiancheng; Tipping, Richard H.

    1998-01-01

    The primary objective of this investigation is the development of an improved parameterization of the water vapor continuum absorption through the refinement and validation of our existing theoretical formalism. The chief advantage of our approach is the self-consistent, first principles, basis of the formalism which allows us to predict the frequency, temperature and pressure dependence of the continuum absorption as well as provide insights into the physical mechanisms responsible for the continuum absorption. Moreover, our approach is such that the calculated continuum absorption can be easily incorporated into satellite retrieval algorithms and climate models. Accurate determination of the water vapor continuum is essential for the next generation of retrieval algorithms which propose to use the combined constraints of multi-spectral measurements such as those under development for EOS data analysis (e.g., retrieval algorithms based on MODIS and AIRS measurements); current Pathfinder activities which seek to use the combined constraints of infrared and microwave (e.g., HIRS and MSU) measurements to improve temperature and water profile retrievals, and field campaigns which seek to reconcile spectrally-resolved and broad-band measurements such as those obtained as part of FIRE. Current widely used continuum treatments have been shown to produce spectrally dependent errors, with the magnitude of the error dependent on temperature and abundance which produces errors with a seasonal and latitude dependence. Translated into flux, current water vapor continuum parameterizations produce flux errors of order 10 W/ml, which compared to the 4 W/m' magnitude of the greenhouse gas forcing and the 1-2 W/m' estimated aerosol forcing is certainly climatologically significant and unacceptably large. While it is possible to tune the empirical formalisms, the paucity of laboratory measurements, especially at temperatures of interest for atmospheric applications, preclude tuning the empirical continuum models over the full spectral range of interest for remote sensing and climate applications. Thus, we propose to further develop and refine our existing far-wing formalism to provide an improved treatment applicable from the near-infrared through the microwave. Based on the results of this investigation, we will provide to the remote sensing/climate modeling community a practical and accurate tabulation of the continuum absorption covering the near-infrared through the microwave region of the spectrum for the range of temperatures and pressures of interest for atmospheric applications.

  13. Theoretical Calculation and Validation of the Water Vapor Continuum Absorption

    NASA Technical Reports Server (NTRS)

    Ma, Qiancheng; Tipping, Richard H.

    1998-01-01

    The primary objective of this investigation is the development of an improved parameterization of the water vapor continuum absorption through the refinement and validation of our existing theoretical formalism. The chief advantage of our approach is the self-consistent, first principles, basis of the formalism which allows us to predict the frequency, temperature and pressure dependence of the continuum absorption as well as provide insights into the physical mechanisms responsible for the continuum absorption. Moreover, our approach is such that the calculated continuum absorption can be easily incorporated into satellite retrieval algorithms and climate models. Accurate determination of the water vapor continuum is essential for the next generation of retrieval algorithms which propose to use the combined constraints of multispectral measurements such as those under development for EOS data analysis (e.g., retrieval algorithms based on MODIS and AIRS measurements); current Pathfinder activities which seek to use the combined constraints of infrared and microwave (e.g., HIRS and MSU) measurements to improve temperature and water profile retrievals, and field campaigns which seek to reconcile spectrally-resolved and broad-band measurements such as those obtained as part of FIRE. Current widely used continuum treatments have been shown to produce spectrally dependent errors, with the magnitude of the error dependent on temperature and abundance which produces errors with a seasonal and latitude dependence. Translated into flux, current water vapor continuum parameterizations produce flux errors of order 10 W/sq m, which compared to the 4 W/sq m magnitude of the greenhouse gas forcing and the 1-2 W/sq m estimated aerosol forcing is certainly climatologically significant and unacceptably large. While it is possible to tune the empirical formalisms, the paucity of laboratory measurements, especially at temperatures of interest for atmospheric applications, preclude tuning, the empirical continuum models over the full spectral range of interest for remote sensing and climate applications. Thus, we propose to further develop and refine our existing, far-wing formalism to provide an improved treatment applicable from the near-infrared through the microwave. Based on the results of this investigation, we will provide to the remote sensing/climate modeling community a practical and accurate tabulation of the continuum absorption covering the near-infrared through the microwave region of the spectrum for the range of temperatures and pressures of interest for atmospheric applications.

  14. Quantum Parallelism as a Tool for Ensemble Spin Dynamics Calculations

    NASA Astrophysics Data System (ADS)

    Álvarez, Gonzalo A.; Danieli, Ernesto P.; Levstein, Patricia R.; Pastawski, Horacio M.

    2008-09-01

    Efficient simulations of quantum evolutions of spin-1/2 systems are relevant for ensemble quantum computation as well as in typical NMR experiments. We propose an efficient method to calculate the dynamics of an observable provided that the initial excitation is “local.” It resorts to a single entangled pure initial state built as a superposition, with random phases, of the pure elements that compose the mixture. This ensures self-averaging of any observable, drastically reducing the calculation time. The procedure is tested for two representative systems: a spin star (cluster with random long range interactions) and a spin ladder.

  15. Detailed discussions and calculations of quantum Regge calculus of Einstein-Cartan theory

    SciTech Connect

    Xue Shesheng

    2010-09-15

    This article presents detailed discussions and calculations of the recent paper 'Quantum Regge calculus of Einstein-Cartan theory' in [9]. The Euclidean space-time is discretized by a four-dimensional simplicial complex. We adopt basic tetrad and spin-connection fields to describe the simplicial complex. By introducing diffeomorphism and local Lorentz invariant holonomy fields, we construct a regularized Einstein-Cartan theory for studying the quantum dynamics of the simplicial complex and fermion fields. This regularized Einstein-Cartan action is shown to properly approach to its continuum counterpart in the continuum limit. Based on the local Lorentz invariance, we derive the dynamical equations satisfied by invariant holonomy fields. In the mean-field approximation, we show that the averaged size of 4-simplex, the element of the simplicial complex, is larger than the Planck length. This formulation provides a theoretical framework for analytical calculations and numerical simulations to study the quantum Einstein-Cartan theory.

  16. 17O and 33S nuclear magnetic shielding of sulfur trioxides from the experimental measurements and theoretical calculations.

    PubMed

    Makulski, Włodzimierz; Tulewicz, Adam; Leś, Andrzej

    2014-03-01

    In a recent (17)O NMR spectra of liquid sulfur trioxide, several unexpected peaks appeared with the temperature-dependent integrated peak ratio. In order to interpret NMR spectra and assign peaks to possible molecular structures, the theoretical quantum mechanical density functional theory and Møller-Plesset second-order perturbation theory calculations were performed. It is suggested that in the liquid sulfur trioxide, apart from monomeric SO3, a significant amount of (SO3)3 cyclic trimers should appear. No theoretical data support hypothesis on (SO3)2 dimers formation. PMID:24446425

  17. Efficient free energy calculations of quantum systems through computer simulations

    NASA Astrophysics Data System (ADS)

    Antonelli, Alex; Ramirez, Rafael; Herrero, Carlos; Hernandez, Eduardo

    2009-03-01

    In general, the classical limit is assumed in computer simulation calculations of free energy. This approximation, however, is not justifiable for a class of systems in which quantum contributions for the free energy cannot be neglected. The inclusion of quantum effects is important for the determination of reliable phase diagrams of these systems. In this work, we present a new methodology to compute the free energy of many-body quantum systems [1]. This methodology results from the combination of the path integral formulation of statistical mechanics and efficient non-equilibrium methods to estimate free energy, namely, the adiabatic switching and reversible scaling methods. A quantum Einstein crystal is used as a model to show the accuracy and reliability the methodology. This new method is applied to the calculation of solid-liquid coexistence properties of neon. Our findings indicate that quantum contributions to properties such as, melting point, latent heat of fusion, entropy of fusion, and slope of melting line can be up to 10% of the calculated values using the classical approximation. [1] R. M. Ramirez, C. P. Herrero, A. Antonelli, and E. R. Hernández, Journal of Chemical Physics 129, 064110 (2008)

  18. Accelerating quantum instanton calculations of the kinetic isotope effects.

    PubMed

    Karandashev, Konstantin; Vaníček, Jiří

    2015-11-21

    Path integral implementation of the quantum instanton approximation currently belongs among the most accurate methods for computing quantum rate constants and kinetic isotope effects, but its use has been limited due to the rather high computational cost. Here, we demonstrate that the efficiency of quantum instanton calculations of the kinetic isotope effects can be increased by orders of magnitude by combining two approaches: The convergence to the quantum limit is accelerated by employing high-order path integral factorizations of the Boltzmann operator, while the statistical convergence is improved by implementing virial estimators for relevant quantities. After deriving several new virial estimators for the high-order factorization and evaluating the resulting increase in efficiency, using ⋅Hα + HβHγ → HαHβ + ⋅ Hγ reaction as an example, we apply the proposed method to obtain several kinetic isotope effects on CH4 + ⋅ H ⇌ ⋅ CH3 + H2 forward and backward reactions. PMID:26590524

  19. Quantum-field-theoretic analysis of inflation dynamics in a (2+1)-dimensional universe

    SciTech Connect

    Samiullah, M. ); Eboli, O. ); Pi, S. )

    1991-10-15

    We reexamine inflationary scenarios based on slow-rollover transitions, which occur under various initial conditions of the inflation-driving scalar field. We examine inflation dynamics using a recently developed calculational technique for studying a quantum-field-theoretic system in an external environment that is itself changing with time. This method, based on the functional Schroedinger picture, uses a self-consistent Gaussian approximation that, unlike ordinary perturbation theory, reflects some of the nonlinearities of the full quantum theory. Our treatment is confined to planar universes, where the approximation techniques do not suffer from well-known problems associated with scalar field self-interactions in four-dimensional space-time. However, for these toy models we can present concrete and explicit results.

  20. Quantum Theoretical Study of Palladium and Silver Clusters

    NASA Astrophysics Data System (ADS)

    Hira, Ajit; Salazar, Justin; Pacheco, Jose

    2013-03-01

    We continue our interest on the chemisorption of different atomic and molecular species on small clusters of metallic elements, by examining the interactions of H, O and F atoms with Pdn and Agn clusters (n = 2 thru 12). Transition-metal clusters can be useful for the study of quantum size effects and for formation of metallic states, and are ideal candidates for catalytic processes. Hybrid ab initio methods of quantum chemistry (particularly the DFT-B3LYP model) are used to derive optimal geometries for the clusters of interest. We compare calculated binding energies, bond-lengths, ionization potentials, electron affinities and HOMO-LUMO gaps for the clusters of the two different metals. Of particular interest are the comparisons of binding strengths at the three important types of sites: edge (E) sites, hollow sites (H) site and on-top (T) sites. Effects of crystal symmetries corresponding to the bulk structures for the two metals will also be investigated. The implications for the molecular dissociation of the H2 and O2 species will be considered.

  1. Simulation of Quantum-Mechanical Measurements with Programmable Pocket Calculators.

    ERIC Educational Resources Information Center

    Sauer, G.

    1979-01-01

    Described is a method for the illustration of the statistical nature of measurements in quantum physics by means of simulation with pocket calculators. The application to examples like the double-slit experiment, Mott scattering, and the demonstration of the uncertainty relation is discussed. (Author/HM)

  2. Calculating Potential Energy Curves with Quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Powell, Andrew D.; Dawes, Richard

    2014-06-01

    Quantum Monte Carlo (QMC) is a computational technique that can be applied to the electronic Schrödinger equation for molecules. QMC methods such as Variational Monte Carlo (VMC) and Diffusion Monte Carlo (DMC) have demonstrated the capability of capturing large fractions of the correlation energy, thus suggesting their possible use for high-accuracy quantum chemistry calculations. QMC methods scale particularly well with respect to parallelization making them an attractive consideration in anticipation of next-generation computing architectures which will involve massive parallelization with millions of cores. Due to the statistical nature of the approach, in contrast to standard quantum chemistry methods, uncertainties (error-bars) are associated with each calculated energy. This study focuses on the cost, feasibility and practical application of calculating potential energy curves for small molecules with QMC methods. Trial wave functions were constructed with the multi-configurational self-consistent field (MCSCF) method from GAMESS-US.[1] The CASINO Monte Carlo quantum chemistry package [2] was used for all of the DMC calculations. An overview of our progress in this direction will be given. References: M. W. Schmidt et al. J. Comput. Chem. 14, 1347 (1993). R. J. Needs et al. J. Phys.: Condensed Matter 22, 023201 (2010).

  3. An experimental and theoretical mechanistic study of biexciton quantum yield enhancement in single quantum dots near gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Dey, Swayandipta; Zhou, Yadong; Tian, Xiangdong; Jenkins, Julie A.; Chen, Ou; Zou, Shengli; Zhao, Jing

    2015-04-01

    In this work, we systematically investigated the plasmonic effect on blinking, photon antibunching behavior and biexciton emission of single CdSe/CdS core/shell quantum dots (QDs) near gold nanoparticles (NPs) with a silica shell (Au@SiO2). In order to obtain a strong interaction between the plasmons and excitons, the Au@SiO2 NPs and CdSe/CdS QDs of appropriate sizes were chosen so that the plasmon resonance overlaps with the absorption and emission of the QDs. We observed that in the regime of a low excitation power, the photon antibunching and blinking properties of single QDs were modified significantly when the QDs were on the Au@SiO2 substrates compared to those on glass. Most significantly, second-order photon intensity correlation data show that the presence of plasmons increases the ratio of the biexciton quantum yield over the exciton quantum yield (QYBX/QYX). An electrodynamics model was developed to quantify the effect of plasmons on the lifetime, quantum yield, and emission intensity of the biexcitons for the QDs. Good agreement was obtained between the experimentally measured and calculated changes in QYBX/QYX due to Au@SiO2 NPs, showing the validity of the developed model. The theoretical studies also indicated that the relative position of the QDs to the Au NPs and the orientation of the electric field are important factors that regulate the emission properties of the excitons and biexcitons of QDs. The study suggests that the multiexciton emission efficiency in QD systems can be manipulated by employing properly designed plasmonic structures.In this work, we systematically investigated the plasmonic effect on blinking, photon antibunching behavior and biexciton emission of single CdSe/CdS core/shell quantum dots (QDs) near gold nanoparticles (NPs) with a silica shell (Au@SiO2). In order to obtain a strong interaction between the plasmons and excitons, the Au@SiO2 NPs and CdSe/CdS QDs of appropriate sizes were chosen so that the plasmon resonance overlaps with the absorption and emission of the QDs. We observed that in the regime of a low excitation power, the photon antibunching and blinking properties of single QDs were modified significantly when the QDs were on the Au@SiO2 substrates compared to those on glass. Most significantly, second-order photon intensity correlation data show that the presence of plasmons increases the ratio of the biexciton quantum yield over the exciton quantum yield (QYBX/QYX). An electrodynamics model was developed to quantify the effect of plasmons on the lifetime, quantum yield, and emission intensity of the biexcitons for the QDs. Good agreement was obtained between the experimentally measured and calculated changes in QYBX/QYX due to Au@SiO2 NPs, showing the validity of the developed model. The theoretical studies also indicated that the relative position of the QDs to the Au NPs and the orientation of the electric field are important factors that regulate the emission properties of the excitons and biexcitons of QDs. The study suggests that the multiexciton emission efficiency in QD systems can be manipulated by employing properly designed plasmonic structures. Electronic supplementary information (ESI) available: The calculation of , SEM and extinction of the Au@SiO2-5 nm substrate, g(2)(τ) distribution and PL decay of QD Au@SiO2-5 nm, additional blinking traces and g(2)(τ) measurements of single QDs on glass, Au@SiO2-5 nm and Au@SiO2-10 nm substrates, and the calculated |E|2, PL intensity, lifetimes and QYs of single QDs on Au NPs. See DOI: 10.1039/c5nr00274e

  4. Efficient method for the calculation of dissipative quantum transport in quantum cascade lasers.

    PubMed

    Greck, Peter; Birner, Stefan; Huber, Bernhard; Vogl, Peter

    2015-03-01

    We present a novel and very efficient method for calculating quantum transport in quantum cascade lasers (QCLs). It follows the nonequilibrium Green's function (NEGF) framework but sidesteps the calculation of lesser self-energies by replacing them by a quasi-equilibrium expression. This method generalizes the phenomenological Büttiker probe model by taking into account individual scattering mechanisms. It is orders of magnitude more efficient than a fully self-consistent NEGF calculation for realistic devices. We apply this method to a new THz QCL design which works up to 250 K - according to our calculations. PMID:25836876

  5. Theoretical calculations and vibrational potential energy surface of 4-silaspiro(3,3)heptane

    SciTech Connect

    Ocola, Esther J.; Medders, Cross; Laane, Jaan; Meinander, Niklas

    2014-04-28

    Theoretical computations have been carried out on 4-silaspiro(3,3)heptane (SSH) in order to calculate its molecular structure and conformational energies. The molecule has two puckered four-membered rings with dihedral angles of 34.2° and a tilt angle of 9.4° between the two rings. Energy calculations were carried out for different conformations of SSH. These results allowed the generation of a two-dimensional ring-puckering potential energy surface (PES) of the form V = a(x{sub 1}{sup 4} + x{sub 2}{sup 4}) – b(x{sub 1}{sup 2} + x{sub 2}{sup 2}) + cx{sub 1}{sup 2}x{sub 2}{sup 2}, where x{sub 1} and x{sub 2} are the ring-puckering coordinates for the two rings. The presence of sufficiently high potential energy barriers prevents the molecule from undergoing pseudorotation. The quantum states, wave functions, and predicted spectra resulting from the PESs were calculated.

  6. Efficient hybrid-symbolic methods for quantum mechanical calculations

    NASA Astrophysics Data System (ADS)

    Scott, T. C.; Zhang, Wenxing

    2015-06-01

    We present hybrid symbolic-numerical tools to generate optimized numerical code for rapid prototyping and fast numerical computation starting from a computer algebra system (CAS) and tailored to any given quantum mechanical problem. Although a major focus concerns the quantum chemistry methods of H. Nakatsuji which has yielded successful and very accurate eigensolutions for small atoms and molecules, the tools are general and may be applied to any basis set calculation with a variational principle applied to its linear and non-linear parameters.

  7. Theoretical calculation of the phase behavior of colloidal membranes

    NASA Astrophysics Data System (ADS)

    Yang, Yasheng; Hagan, Michael F.

    2011-11-01

    We formulate a density functional theory that describes the phase behavior of hard rods and depleting polymers, as realized in recent experiments on suspensions of fd virus and nonadsorbing polymer. The theory predicts the relative stability of nematic droplets, stacked smectic columns, and a recently discovered phase of isolated monolayers of rods, or colloidal membranes. We find that a minimum rod aspect ratio is required for stability of colloidal membranes and that collective protrusion undulations are the dominant effect that stabilizes this phase. The theoretical predictions are shown to be qualitatively consistent with experimental and computational results.

  8. Vibrational Spectra of the MLCl{_2} Complex from Theoretical Calculations

    NASA Astrophysics Data System (ADS)

    Catikkas, Berna

    2012-06-01

    The geometric and vibrational parameters (harmonic and anharmonic frequencies) of the MLCl{_2} [M= Mn, Fe, Co, Ni, Cu, Zn, Cd, Hg; L= Ethylenediamine (en)] donor-acceptor complexes have been studied by using HF and MPW1PW91+iop(3/76=00572004280)/gen methods. Binding, reorganization, atomization, HOMO-LUMO and ionization potential energies have also been calculated with the same method. SQM calculations have been performed by using anharmonic frequencies and experimental data. The obtained results were found to be in good agreement with the corresponding experimental findings.

  9. A quantum-information theoretic analysis of three-flavor neutrino oscillations. Quantum entanglement, nonlocal and nonclassical features of neutrinos

    NASA Astrophysics Data System (ADS)

    Banerjee, Subhashish; Alok, Ashutosh Kumar; Srikanth, R.; Hiesmayr, Beatrix C.

    2015-10-01

    Correlations exhibited by neutrino oscillations are studied via quantum-information theoretic quantities. We show that the strongest type of entanglement, genuine multipartite entanglement, is persistent in the flavor changing states. We prove the existence of Bell-type nonlocal features, in both its absolute and genuine avatars. Finally, we show that a measure of nonclassicality, dissension, which is a generalization of quantum discord to the tripartite case, is nonzero for almost the entire range of time in the evolution of an initial electron-neutrino. Via these quantum-information theoretic quantities, capturing different aspects of quantum correlations, we elucidate the differences between the flavor types, shedding light on the quantum-information theoretic aspects of the weak force.

  10. Potential theoretic methods for far field sound radiation calculations

    NASA Technical Reports Server (NTRS)

    Hariharan, S. I.; Stenger, Edward J.; Scott, J. R.

    1995-01-01

    In the area of computational acoustics, procedures which accurately predict the far-field sound radiation are much sought after. A systematic development of such procedures are found in a sequence of papers by Atassi. The method presented here is an alternate approach to predicting far field sound based on simple layer potential theoretic methods. The main advantages of this method are: it requires only a simple free space Green's function, it can accommodate arbitrary shapes of Kirchoff surfaces, and is readily extendable to three-dimensional problems. Moreover, the procedure presented here, though tested for unsteady lifting airfoil problems, can easily be adapted to other areas of interest, such as jet noise radiation problems. Results are presented for lifting airfoil problems and comparisons are made with the results reported by Atassi. Direct comparisons are also made for the flat plate case.

  11. Infinite variance in fermion quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Shi, Hao; Zhang, Shiwei

    2016-03-01

    For important classes of many-fermion problems, quantum Monte Carlo (QMC) methods allow exact calculations of ground-state and finite-temperature properties without the sign problem. The list spans condensed matter, nuclear physics, and high-energy physics, including the half-filled repulsive Hubbard model, the spin-balanced atomic Fermi gas, and lattice quantum chromodynamics calculations at zero density with Wilson Fermions, and is growing rapidly as a number of problems have been discovered recently to be free of the sign problem. In these situations, QMC calculations are relied on to provide definitive answers. Their results are instrumental to our ability to understand and compute properties in fundamental models important to multiple subareas in quantum physics. It is shown, however, that the most commonly employed algorithms in such situations have an infinite variance problem. A diverging variance causes the estimated Monte Carlo statistical error bar to be incorrect, which can render the results of the calculation unreliable or meaningless. We discuss how to identify the infinite variance problem. An approach is then proposed to solve the problem. The solution does not require major modifications to standard algorithms, adding a "bridge link" to the imaginary-time path integral. The general idea is applicable to a variety of situations where the infinite variance problem may be present. Illustrative results are presented for the ground state of the Hubbard model at half-filling.

  12. Information-theoretical meaning of quantum-dynamical entropy

    NASA Astrophysics Data System (ADS)

    Alicki, Robert

    2002-11-01

    The theories of noncommutative dynamical entropy and quantum symbolic dynamics for quantum-dynamical systems are analyzed from the point of view of quantum information theory. Using a general quantum-dynamical system as a communication channel, one can define different classical capacities depending on the character of resources applied for encoding and decoding procedures and on the type of information sources. It is shown that for Bernoulli sources, the entanglement-assisted classical capacity, which is the largest one, is bounded from above by the quantum-dynamical entropy defined in terms of operational partitions of unity. Stronger results are proved for the particular class of quantum-dynamical systems-quantum Bernoulli shifts. Different classical capacities are exactly computed and the entanglement-assisted one is equal to the dynamical entropy in this case.

  13. An experimental and theoretical mechanistic study of biexciton quantum yield enhancement in single quantum dots near gold nanoparticles.

    PubMed

    Dey, Swayandipta; Zhou, Yadong; Tian, Xiangdong; Jenkins, Julie A; Chen, Ou; Zou, Shengli; Zhao, Jing

    2015-04-21

    In this work, we systematically investigated the plasmonic effect on blinking, photon antibunching behavior and biexciton emission of single CdSe/CdS core/shell quantum dots (QDs) near gold nanoparticles (NPs) with a silica shell (Au@SiO2). In order to obtain a strong interaction between the plasmons and excitons, the Au@SiO2 NPs and CdSe/CdS QDs of appropriate sizes were chosen so that the plasmon resonance overlaps with the absorption and emission of the QDs. We observed that in the regime of a low excitation power, the photon antibunching and blinking properties of single QDs were modified significantly when the QDs were on the Au@SiO2 substrates compared to those on glass. Most significantly, second-order photon intensity correlation data show that the presence of plasmons increases the ratio of the biexciton quantum yield over the exciton quantum yield (QYBX/QYX). An electrodynamics model was developed to quantify the effect of plasmons on the lifetime, quantum yield, and emission intensity of the biexcitons for the QDs. Good agreement was obtained between the experimentally measured and calculated changes in QYBX/QYX due to Au@SiO2 NPs, showing the validity of the developed model. The theoretical studies also indicated that the relative position of the QDs to the Au NPs and the orientation of the electric field are important factors that regulate the emission properties of the excitons and biexcitons of QDs. The study suggests that the multiexciton emission efficiency in QD systems can be manipulated by employing properly designed plasmonic structures. PMID:25806486

  14. Plasmon spectroscopy: Theoretical and numerical calculations, and optimization techniques

    NASA Astrophysics Data System (ADS)

    Rodríguez-Oliveros, Rogelio; Paniagua-Domínguez, Ramón; Sánchez-Gil, José A.; Macías, Demetrio

    2016-02-01

    We present an overview of recent advances in plasmonics, mainly concerning theoretical and numerical tools required for the rigorous determination of the spectral properties of complex-shape nanoparticles exhibiting strong localized surface plasmon resonances (LSPRs). Both quasistatic approaches and full electrodynamic methods are described, providing a thorough comparison of their numerical implementations. Special attention is paid to surface integral equation formulations, giving examples of their performance in complicated nanoparticle shapes of interest for their LSPR spectra. In this regard, complex (single) nanoparticle configurations (nanocrosses and nanorods) yield a hierarchy of multiple-order LSPR s with evidence of a rich symmetric or asymmetric (Fano-like) LSPR line shapes. In addition, means to address the design of complex geometries to retrieve LSPR spectra are commented on, with special interest in biologically inspired algorithms. Thewealth of LSPRbased applications are discussed in two choice examples, single-nanoparticle surface-enhanced Raman scattering (SERS) and optical heating, and multifrequency nanoantennas for fluorescence and nonlinear optics.

  15. Theoretical calculation of spectra of dibutyl phthalate and dioctyl phthalate

    NASA Astrophysics Data System (ADS)

    Du, Jian-Bin; Tang, Yan-Lin; Long, Zheng-Wen; Hu, Shuang-Hui; Li, Tao

    2014-05-01

    Dibutyl phthalate DBP and dioctyl phthalate DOP are the main components of the plasticizers. In order to investigate their molecular structure, chemical bond and spectrum, the geometrical parameters of the ground state and infrared (IR) spectrum are calculated using the density functional theory B3LYP method at the level of 6-311++G( d, p). On this basis, the first twenty-six excited states and the UV-Vis absorption spectra of DBP and DOP are studied using the time-dependent density functional theory (TDDFT) in the same fundamental group and compared with the ultraviolet absorption peak of the molecules measured with UNICO UV-Vis spectrophotometer. The two kinds of molecular spectra are then classified and compared with that in reference. The results show that the strong absorption of IR spectra of DOP and DBP are produced by C-H bending in-plane vibration and C=O telescopic vibration producing. The most absorption of UV-Vis absorption spectra appears in the end absorption belt from n to σ* transition, and the stronger absorption in the E belt of benzene electronic transition from π to π*. There are blue shift for DOP end absorption belt from n to σ* transition and red shift for DOP E absorption belt from π to π* transition relative to that of DBP. This calculation results are better in accord with the spectral data measured by UNICO ultraviolet and visible spectrophotometer.

  16. How to find conductance tensors of quantum multiwire junctions through static calculations: application to an interacting Y junction.

    PubMed

    Rahmani, Armin; Hou, Chang-Yu; Feiguin, Adrian; Chamon, Claudio; Affleck, Ian

    2010-11-26

    Conductance is related to dynamical correlation functions which can be calculated with time-dependent methods. Using boundary conformal field theory, we relate the conductance tensors of quantum junctions of multiple wires to static correlation functions in a finite system. We then propose a general method for determining the conductance through time-independent calculations alone. Applying the method to a Y junction of interacting quantum wires, we numerically verify the theoretical prediction for the conductance of the chiral fixed point of the Y junction and then calculate the thus far unknown conductance of its M fixed point with the time-independent density matrix renormalization group method. PMID:21231412

  17. Quantum MonteCarlo Calculations of Symmetric Nuclear Matter

    NASA Astrophysics Data System (ADS)

    Gandolfi, Stefano; Pederiva, Francesco; Fantoni, Stefano; Schmidt, Kevin E.

    2007-03-01

    We present an accurate numerical study of the equation of state of nuclear matter based on realistic nucleon-nucleon interactions by means of auxiliary field diffusion Monte Carlo (AFDMC) calculations. The AFDMC method samples the spin and isospin degrees of freedom allowing for quantum simulations of large nucleonic systems and represents an important step forward towards a quantitative understanding of problems in nuclear structure and astrophysics.

  18. Quantum Monte Carlo Calculations in Solids with Downfolded Hamiltonians.

    PubMed

    Ma, Fengjie; Purwanto, Wirawan; Zhang, Shiwei; Krakauer, Henry

    2015-06-01

    We present a combination of a downfolding many-body approach with auxiliary-field quantum Monte Carlo (AFQMC) calculations for extended systems. Many-body calculations operate on a simpler Hamiltonian which retains material-specific properties. The Hamiltonian is systematically improvable and allows one to dial, in principle, between the simplest model and the original Hamiltonian. As a by-product, pseudopotential errors are essentially eliminated using frozen orbitals constructed adaptively from the solid environment. The computational cost of the many-body calculation is dramatically reduced without sacrificing accuracy. Excellent accuracy is achieved for a range of solids, including semiconductors, ionic insulators, and metals. We apply the method to calculate the equation of state of cubic BN under ultrahigh pressure, and determine the spin gap in NiO, a challenging prototypical material with strong electron correlation effects. PMID:26196632

  19. Theoretical analysis of the transmission phase shift of a quantum dot in the presence of Kondo correlations.

    PubMed

    Jerez, A; Vitushinsky, P; Lavagna, M

    2005-09-16

    We study the effects of Kondo correlations on the transmission phase shift of a quantum dot coupled to two leads in comparison with the experimental determinations made by Aharonov-Bohm (AB) quantum interferometry. We propose here a theoretical interpretation of these results based on scattering theory combined with Bethe ansatz calculations. We show that there is a factor of 2 difference between the phase of the S-matrix responsible for the shift in the AB oscillations and the one controlling the conductance. Quantitative agreement is obtained with experimental results for two different values of the coupling to the leads. PMID:16197103

  20. A Quantum Theoretical Explanation for Probability Judgment Errors

    ERIC Educational Resources Information Center

    Busemeyer, Jerome R.; Pothos, Emmanuel M.; Franco, Riccardo; Trueblood, Jennifer S.

    2011-01-01

    A quantum probability model is introduced and used to explain human probability judgment errors including the conjunction and disjunction fallacies, averaging effects, unpacking effects, and order effects on inference. On the one hand, quantum theory is similar to other categorization and memory models of cognition in that it relies on vector…

  1. A Quantum Theoretical Explanation for Probability Judgment Errors

    ERIC Educational Resources Information Center

    Busemeyer, Jerome R.; Pothos, Emmanuel M.; Franco, Riccardo; Trueblood, Jennifer S.

    2011-01-01

    A quantum probability model is introduced and used to explain human probability judgment errors including the conjunction and disjunction fallacies, averaging effects, unpacking effects, and order effects on inference. On the one hand, quantum theory is similar to other categorization and memory models of cognition in that it relies on vector

  2. Structure and excited-state dynamics of anthracene: ultrahigh-resolution spectroscopy and theoretical calculation.

    PubMed

    Baba, Masaaki; Saitoh, Motohisa; Taguma, Kunio; Shinohara, Keisuke; Yoshida, Kazuto; Semba, Yosuke; Kasahara, Shunji; Nakayama, Naofumi; Goto, Hitoshi; Ishimoto, Takayoshi; Nagashima, Umpei

    2009-04-01

    Rotationally resolved ultrahigh-resolution spectra of the S(1) (1)B(2u)<--S(0) (1)A(g) transition of anthracene-h(10) and anthracene-d(10) have been observed using a single-mode UV laser and a collimated supersonic jet. We have determined rotational constants of the zero-vibrational levels of the S(0) and S(1) states by analyzing the precisely calibrated transition wavenumbers of rotational lines. We measured Zeeman splitting of each rotational line in the external magnetic field, of which the magnitude was small and strongly dependent on the rotational quantum numbers. We have shown that the magnetic moment in the S(1) (1)B(2u) state arises from J-L coupling with the S(2) (1)B(3u) state and that mixing with the triplet state is negligibly small. We concluded that the main radiationless transition in the S(1) state of anthracene is not intersystem crossing to the triplet state but internal conversion to the ground state. We also examined methods of ab initio theoretical calculation to determine which method most closely yielded the same values of rotational constants as the experimentally obtained ones. Moller-Plesset second-order perturbation method with a 6-31G(d,p) basis set yielded approximately the same values for the S(0) (1)A(g) state with an error of less than 0.04%. Geometrical structure in the S(0) (1)A(g) state of the isolated anthracene molecule has been accurately determined by this calculation. However, configurational-interaction with single excitations, time-dependent Hartree-Fock, and time-dependent density-function-theory methods did not yield satisfactory results for the excitation energy of the S(1) (1)B(2u) state. Symmetry-adapted-cluster configuration-interaction calculation was sufficiently good for the excitation energy and rotational constants. PMID:19355740

  3. New Look on 3-Hydroxyiminoflavanone and Its Palladium(II) Complex: Crystallographic and Spectroscopic Studies, Theoretical Calculations and Cytotoxic Activity.

    PubMed

    Kasprzak, Maria; Fabijańska, Małgorzata; Chęcińska, Lilianna; Szmigiero, Leszek; Ochocki, Justyn

    2016-01-01

    This work presents the synthesis, spectroscopic properties and single-crystal X-ray examination of the structure of 3-hydroxyiminoflavanone and its palladium complex. It presents the results of NMR (Nuclear Magnetic Resonance) spectroscopy, electron-density studies based on X-ray wavefunction refinement and theoretical calculations combined with QTAIM (Quantum Theory of Atoms in Molecules) and ELI-D (Electron Localizability Indicator) analyses. These offer an interesting new insight into the structures and behavior of flavanone and its complex, in solid state and in solution. The study also examines the cytotoxicity of the ligand and its complex against three human ovarian and lung cancer cell lines. PMID:27089313

  4. Quantum-mechanical DFT calculation supported Raman spectroscopic study of some amino acids in bovine insulin

    NASA Astrophysics Data System (ADS)

    Tah, Bidisha; Pal, Prabir; Roy, Sourav; Dutta, Debodyuti; Mishra, Sabyashachi; Ghosh, Manash; Talapatra, G. B.

    2014-08-01

    In this article Quantum mechanical (QM) calculations by Density Functional Theory (DFT) have been performed of all amino acids present in bovine insulin. Simulated Raman spectra of those amino acids are compared with their experimental spectra and the major bands are assigned. The results are in good agreement with experiment. We have also verified the DFT results with Quantum mechanical molecular mechanics (QM/MM) results for some amino acids. QM/MM results are very similar with the DFT results. Although the theoretical calculation of individual amino acids are feasible, but the calculated Raman spectrum of whole protein molecule is difficult or even quite impossible task, since it relies on lengthy and costly quantum-chemical computation. However, we have tried to simulate the Raman spectrum of whole protein by adding the proportionate contribution of the Raman spectra of each amino acid present in this protein. In DFT calculations, only the contributions of disulphide bonds between cysteines are included but the contribution of the peptide and hydrogen bonds have not been considered. We have recorded the Raman spectra of bovine insulin using micro-Raman set up. The experimental spectrum is found to be very similar with the resultant simulated Raman spectrum with some exceptions.

  5. [Terahertz Absorption Spectra Simulation of Glutamine Based on Quantum-Chemical Calculation].

    PubMed

    Zhang, Tian-yao; Zhang, Zhao-hui; Zhao, Xiao-yan; Zhang, Han; Yan, Fang; Qian, Ping

    2015-08-01

    With simulation of absorption spectra in THz region based on quantum-chemical calculation, the THz absorption features of target materials can be assigned with theoretical normal vibration modes. This is necessary for deeply understanding the origin of THz absorption spectra. The reliabilities of simulation results mainly depend on the initial structures and theoretical methods used throughout the calculation. In our study, we utilized THz-TDS to obtain the THz absorption spectrum of solid-state L-glutamine. Then three quantum-chemical calculation schemes with different initial structures commonly used in previous studies were proposed to study the inter-molecular interactions' contribution to the THz absorption of glutamine, containing monomer structure, dimer structure and crystal unit cell structure. After structure optimization and vibration modes' calculation based on density functional theory, the calculation results were converted to absorption spectra by Lorentzian line shape function for visual comparison with experimental spectra. The result of dimmer structure is better than monomer structure in number of absorption features while worse than crystal unit cell structure in position of absorption peaks. With the most reliable simulation result from crystal unit cell calculation, we successfully assigned all three experimental absorption peaks of glutamine ranged from 0.3 to 2.6 THz with overall vibration modes. Our study reveals that the crystal unit cell should be used as initial structure during theoretical simulation of solid-state samples' THz absorption spectrum which comprehensively considers not only the intra-molecular interactions but also inter-molecular interactions. PMID:26672269

  6. Delay time calculation for dual-wavelength quantum cascade lasers

    SciTech Connect

    Hamadou, A.; Lamari, S.; Thobel, J.-L.

    2013-11-28

    In this paper, we calculate the turn-on delay (t{sub th}) and buildup (Δt) times of a midinfrared quantum cascade laser operating simultaneously on two laser lines having a common upper level. The approach is based on the four-level rate equations model describing the variation of the electron number in the states and the photon number present within the cavity. We obtain simple analytical formulae for the turn-on delay and buildup times that determine the delay times and numerically apply our results to both the single and bimode states of a quantum cascade laser, in addition the effects of current injection on t{sub th} and Δt are explored.

  7. The actual content of quantum theoretical kinematics and mechanics

    NASA Technical Reports Server (NTRS)

    Heisenberg, W.

    1983-01-01

    First, exact definitions are supplied for the terms: position, velocity, energy, etc. (of the electron, for instance), such that they are valid also in quantum mechanics. Canonically conjugated variables are determined simultaneously only with a characteristic uncertainty. This uncertainty is the intrinsic reason for the occurrence of statistical relations in quantum mechanics. Mathematical formulation is made possible by the Dirac-Jordan theory. Beginning from the basic principles thus obtained, macroscopic processes are understood from the viewpoint of quantum mechanics. Several imaginary experiments are discussed to elucidate the theory.

  8. A theoretical study of blue phosphorene nanoribbons based on first-principles calculations

    SciTech Connect

    Xie, Jiafeng; Si, M. S. Yang, D. Z.; Zhang, Z. Y.; Xue, D. S.

    2014-08-21

    Based on first-principles calculations, we present a quantum confinement mechanism for the band gaps of blue phosphorene nanoribbons (BPNRs) as a function of their widths. The BPNRs considered have either armchair or zigzag shaped edges on both sides with hydrogen saturation. Both the two types of nanoribbons are shown to be indirect semiconductors. An enhanced energy gap of around 1 eV can be realized when the ribbon's width decreases to ∼10 Å. The underlying physics is ascribed to the quantum confinement effect. More importantly, the parameters to describe quantum confinement are obtained by fitting the calculated band gaps with respect to their widths. The results show that the quantum confinement in armchair nanoribbons is stronger than that in zigzag ones. This study provides an efficient approach to tune the band gap in BPNRs.

  9. Quantum Chemistry and Non-Equilibrium Thermodynamics: Does Chaos Play a Role in Quantum Chemical Calculations?

    NASA Astrophysics Data System (ADS)

    Andr, J.-M.; Andr, M.-Cl.; Fripiat, J. G.; Lambert, C.

    2007-12-01

    The theory of solitons in polyacetylene chains is reviewed with the emphasis on the force that drives the phenomenon. Then, the origin of bifurcation schemes in non-equilibrium thermodynamics is summarized. Examples of bifurcations schemes and of chaotic behaviors in quantum chemical calculations are given.

  10. The Nature of Infinity in Quantum Field Calculations

    NASA Astrophysics Data System (ADS)

    Kriske, Richard

    2011-05-01

    In many textbooks on Quantum Field Theory it has been noted that an infinity is taken a circle and the flux is calculated from the A field in that manner. There are of course many such examples of this sort of calculation using infinity as a circle. This author would like to point out that if the three dimensions of space are curved and the one dimension of time is not, in say a four space, infinity is the horizon, which is not a circle but rather a sphere; as long as space-time is curved uniformly, smoothly and has positive curvature. This author believes the math may be in error, since maps of the CMBR seem to indicate a ``Swiss-Cheese'' type of topology, wherein the Sphere at infinity (the Horizon of the Universe), has holes in it that can readily be seen. This author believes that these irregularities most certainly have a calculable effect on QED, QCD and Quantum Field Theory.

  11. The successful merger of theoretical thermochemistry with fragment-based methods in quantum chemistry.

    PubMed

    Ramabhadran, Raghunath O; Raghavachari, Krishnan

    2014-12-16

    CONSPECTUS: Quantum chemistry and electronic structure theory have proven to be essential tools to the experimental chemist, in terms of both a priori predictions that pave the way for designing new experiments and rationalizing experimental observations a posteriori. Translating the well-established success of electronic structure theory in obtaining the structures and energies of small chemical systems to increasingly larger molecules is an exciting and ongoing central theme of research in quantum chemistry. However, the prohibitive computational scaling of highly accurate ab initio electronic structure methods poses a fundamental challenge to this research endeavor. This scenario necessitates an indirect fragment-based approach wherein a large molecule is divided into small fragments and is subsequently reassembled to compute its energy accurately. In our quest to further reduce the computational expense associated with the fragment-based methods and overall enhance the applicability of electronic structure methods to large molecules, we realized that the broad ideas involved in a different area, theoretical thermochemistry, are transferable to the area of fragment-based methods. This Account focuses on the effective merger of these two disparate frontiers in quantum chemistry and how new concepts inspired by theoretical thermochemistry significantly reduce the total number of electronic structure calculations needed to be performed as part of a fragment-based method without any appreciable loss of accuracy. Throughout, the generalized connectivity based hierarchy (CBH), which we developed to solve a long-standing problem in theoretical thermochemistry, serves as the linchpin in this merger. The accuracy of our method is based on two strong foundations: (a) the apt utilization of systematic and sophisticated error-canceling schemes via CBH that result in an optimal cutting scheme at any given level of fragmentation and (b) the use of a less expensive second layer of electronic structure method to recover all the missing long-range interactions in the parent large molecule. Overall, the work featured here dramatically decreases the computational expense and empowers the execution of very accurate ab initio calculations (gold-standard CCSD(T)) on large molecules and thereby facilitates sophisticated electronic structure applications to a wide range of important chemical problems. PMID:25393551

  12. Quantum chemistry calculation of resveratrol and related stilbenes

    NASA Astrophysics Data System (ADS)

    Del Nero, J.; de Melo, C. P.

    2003-01-01

    We report a semiempirical investigation of the first excited states and of the spectroscopic properties of resveratrol, a phytoalexin with well-known antioxidative properties, and of structurally related stilbenes. The analysis of the calculated bond length and charge rearrangements resulting from the photoexcitation and of the corresponding theoretical spectra gives us some insight of how chemical modifications of these molecules could affect the possible physiological properties of resveratrol.

  13. Theoretical prediction of the vibrational spectrum, geometry, and scaled quantum mechanical force field for phenylacetylene

    SciTech Connect

    Csaszar, A.G.; Fogarasi, G. ); Boggs, J.E. )

    1989-11-02

    The optimized geometry and the complete harmonic force field of phenylacetylene have been determined by ab initio Hartree-Fock calculations, using a 4-21 Gaussian basis set. Systematic errors in the bond lengths, characteristic at this level of theory, were corrected by empirical offset values. Only at the ipso position does the equilibrium geometry obtained in this way differ significantly from the experimental one (MW; r{sub g}). A detailed analysis suggests that while the experimental ipso CCC angle may be correct, the ipso CC distance should be reconsidered. The force field was evaluated at the above geometry as a reference. To remove systematic deficiencies, the final scaled quantum mechanical (SQM) force field was obtained by applying scale factors optimized previously for benzene and acetylene. All force constants that occur both in phenylacetylene and in the isoelectronic molecule benzonitrile are very nearly the same. Frequencies calculated from the SQM force field of phenylacetylene confirm, with only a few exceptions, the published experimental assignments for all four isotopomers investigated. When the C-H (and C-D) stretching frequencies, perturbed by anharmonicity, are not considered, the average deviation between the observed and calculated frequencies is below 10 cm{sup {minus}1}. Theoretical dipole moment derivatives are discussed, and infrared intensities are presented. Quartic centrifugal distortion constants, calculated also from the SQM force field, agree well with the results of an incomplete experimental study.

  14. Importance of parametrizing constraints in quantum-mechanical variational calculations

    NASA Technical Reports Server (NTRS)

    Chung, Kwong T.; Bhatia, A. K.

    1992-01-01

    In variational calculations of quantum mechanics, constraints are sometimes imposed explicitly on the wave function. These constraints, which are deduced by physical arguments, are often not uniquely defined. In this work, the advantage of parametrizing constraints and letting the variational principle determine the best possible constraint for the problem is pointed out. Examples are carried out to show the surprising effectiveness of the variational method if constraints are parameterized. It is also shown that misleading results may be obtained if a constraint is not parameterized.

  15. Predicting Crystal Structures with Data Mining of Quantum Calculations

    NASA Astrophysics Data System (ADS)

    Curtarolo, Stefano; Morgan, Dane; Persson, Kristin; Rodgers, John; Ceder, Gerbrand

    2003-09-01

    Predicting and characterizing the crystal structure of materials is a key problem in materials research and development. It is typically addressed with highly accurate quantum mechanical computations on a small set of candidate structures, or with empirical rules that have been extracted from a large amount of experimental information, but have limited predictive power. In this Letter, we transfer the concept of heuristic rule extraction to a large library of abinitio calculated information, and we demonstrate that this can be developed into a tool for crystal structure prediction.

  16. TOPICAL REVIEW: Recent advances in jointed quantum mechanics and molecular mechanics calculations of biological macromolecules: schemes and applications coupled to ab initio calculations

    NASA Astrophysics Data System (ADS)

    Hagiwara, Yohsuke; Tateno, Masaru

    2010-10-01

    We review the recent research on the functional mechanisms of biological macromolecules using theoretical methodologies coupled to ab initio quantum mechanical (QM) treatments of reaction centers in proteins and nucleic acids. Since in most cases such biological molecules are large, the computational costs of performing ab initio calculations for the entire structures are prohibitive. Instead, simulations that are jointed with molecular mechanics (MM) calculations are crucial to evaluate the long-range electrostatic interactions, which significantly affect the electronic structures of biological macromolecules. Thus, we focus our attention on the methodologies/schemes and applications of jointed QM/MM calculations, and discuss the critical issues to be elucidated in biological macromolecular systems.

  17. Quantum cognition: a new theoretical approach to psychology.

    PubMed

    Bruza, Peter D; Wang, Zheng; Busemeyer, Jerome R

    2015-07-01

    What type of probability theory best describes the way humans make judgments under uncertainty and decisions under conflict? Although rational models of cognition have become prominent and have achieved much success, they adhere to the laws of classical probability theory despite the fact that human reasoning does not always conform to these laws. For this reason we have seen the recent emergence of models based on an alternative probabilistic framework drawn from quantum theory. These quantum models show promise in addressing cognitive phenomena that have proven recalcitrant to modeling by means of classical probability theory. This review compares and contrasts probabilistic models based on Bayesian or classical versus quantum principles, and highlights the advantages and disadvantages of each approach. PMID:26058709

  18. Automatic generation of active coordinates for quantum dynamics calculations: Application to the dynamics of benzene photochemistry

    SciTech Connect

    Lasorne, Benjamin; Sicilia, Fabrizio; Bearpark, Michael J.; Robb, Michael A.; Worth, Graham A.; Blancafort, Lluis

    2008-03-28

    A new practical method to generate a subspace of active coordinates for quantum dynamics calculations is presented. These reduced coordinates are obtained as the normal modes of an analytical quadratic representation of the energy difference between excited and ground states within the complete active space self-consistent field method. At the Franck-Condon point, the largest negative eigenvalues of this Hessian correspond to the photoactive modes: those that reduce the energy difference and lead to the conical intersection; eigenvalues close to 0 correspond to bath modes, while modes with large positive eigenvalues are photoinactive vibrations, which increase the energy difference. The efficacy of quantum dynamics run in the subspace of the photoactive modes is illustrated with the photochemistry of benzene, where theoretical simulations are designed to assist optimal control experiments.

  19. Nuclear-magnetic-resonance quantum calculations of the Jones polynomial

    PubMed Central

    Marx, Raimund; Fahmy, Amr; Kauffman, Louis; Lomonaco, Samuel; Spörl, Andreas; Pomplun, Nikolas; Schulte-Herbrüggen, Thomas; Myers, John M.; Glaser, Steffen J.

    2011-01-01

    The repertoire of problems theoretically solvable by a quantum computer recently expanded to include the approximate evaluation of knot invariants, specifically the Jones polynomial. The experimental implementation of this evaluation, however, involves many known experimental challenges. Here we present experimental results for small-scale approximate evaluation of the Jones polynomial by nuclear magnetic resonance (NMR); in addition, we show how to escape from the limitations of NMR approaches that employ pseudopure states. Specifically, we use two spin-1/2 nuclei of natural abundance chloroform and apply a sequence of unitary transforms representing the trefoil knot, the figure-eight knot, and the Borromean rings. After measuring the nuclear spin state of the molecule in each case, we are able to estimate the value of the Jones polynomial for each of the knots. PMID:21461143

  20. Self-consistent calculations of optical properties of type I and type II quantum heterostructures

    NASA Astrophysics Data System (ADS)

    Shuvayev, Vladimir A.

    In this Thesis the self-consistent computational methods are applied to the study of the optical properties of semiconductor nanostructures with one- and two-dimensional quantum confinements. At first, the self-consistent Schrodinger-Poisson system of equations is applied to the cylindrical core-shell structure with type II band alignment without direct Coulomb interaction between carriers. The electron and hole states and confining potential are obtained from a numerical solution of this system. The photoluminescence kinetics is theoretically analyzed, with the nanostructure size dispersion taken into account. The results are applied to the radiative recombination in the system of ZnTe/ZnSe stacked quantum dots. A good agreement with both continuous wave and time-resolved experimental observations is found. It is shown that size distribution results in the photoluminescence decay that has essentially non-exponential behavior even at the tail of the decay where the carrier lifetime is almost the same due to slowly changing overlap of the electron and hole wavefunctions. Also, a model situation applicable to colloidal core-shell nanowires is investigated and discussed. With respect to the excitons in type I quantum wells, a new computationally efficient and flexible approach of calculating the characteristics of excitons, based on a self-consistent variational treatment of the electron-hole Coulomb interaction, is developed. In this approach, a system of self-consistent equations describing the motion of an electron-hole pair is derived. The motion in the growth direction of the quantum well is separated from the in-plane motion, but each of them occurs in modified potentials found self-consistently. This approach is applied to a shallow quantum well with the delta-potential profile, for which analytical expressions for the exciton binding energy and the ground state eigenfunctions are obtained, and to the quantum well with the square potential profile with several different well and barrier materials. The numerical results yield lower exciton binding energies in comparison to standard variational calculations, while the iterative scheme used to calculate the energies and respective wavefunctions is stable, rapidly convergent and requires reduced computational effort. Thus, the method can be an important computational tool in computing exciton characteristics in quantum wells exceeding currently existing approaches in accuracy and efficiency. The method can also be naturally generalized for quantum wires and dots.

  1. Theoretical simulation of carrier capture and relaxation rates in quantum-dot semiconductor optical amplifiers

    SciTech Connect

    Wu, Yunhu; Zhang, Guoping; Guo, Ling; Qi, Guoqun; Li, Xiaoming

    2014-06-14

    Based on Auger scattering mechanism, carrier-carrier scattering dynamics between the two-dimensional carrier reservoir (also called wetting layer, i.e., WL) and the confined quantum dot ground and first excited state in quantum-dot semiconductor optical amplifiers (QD-SOAs) are investigated theoretically in this paper. The scattering rates for independent electron and hole densities are calculated. The results show an ultra-fast carrier capture (relaxation) rate up to 1 ps{sup −1}, and there is a complex dependence of the Coulomb scattering rates on the WL electron and hole densities. In addition, due to the different effective mass and the level distribution, the scattering rates for electron and hole are very different. Finally, in order to provide a direction to control (increase or decrease) the input current in realistic QD-SOA systems, a simple method is proposed to determine the trends of the carrier recovery rates with the WL carrier densities in the vicinity of the steady-state.

  2. Theoretical simulation of carrier capture and relaxation rates in quantum-dot semiconductor optical amplifiers

    NASA Astrophysics Data System (ADS)

    Wu, Yunhu; Zhang, Guoping; Guo, Ling; Li, Xiaoming; Qi, Guoqun

    2014-06-01

    Based on Auger scattering mechanism, carrier-carrier scattering dynamics between the two-dimensional carrier reservoir (also called wetting layer, i.e., WL) and the confined quantum dot ground and first excited state in quantum-dot semiconductor optical amplifiers (QD-SOAs) are investigated theoretically in this paper. The scattering rates for independent electron and hole densities are calculated. The results show an ultra-fast carrier capture (relaxation) rate up to 1 ps-1, and there is a complex dependence of the Coulomb scattering rates on the WL electron and hole densities. In addition, due to the different effective mass and the level distribution, the scattering rates for electron and hole are very different. Finally, in order to provide a direction to control (increase or decrease) the input current in realistic QD-SOA systems, a simple method is proposed to determine the trends of the carrier recovery rates with the WL carrier densities in the vicinity of the steady-state.

  3. A Concise Theoretical Method for Profile-Drag Calculation; Advance Report

    NASA Technical Reports Server (NTRS)

    Nitzberg, Gerald E.

    1944-01-01

    In this report a method is presented for the calculation of the profile drag of airfoil sections. The method requlres only a knowledge of the theoretical velocity distribution and can be applied readily once this dlstribution is ascertained. Comparison of calculated and experimental drag characteristics for several airfoils shows a satisfactory agreement. Sample calculatlons are included.

  4. Comparison of molecular energies calculation using simulated quantum algorithm and classical computer methods

    NASA Astrophysics Data System (ADS)

    Lesniak, Joseph; Behrman, Elizabeth; Zandler, Melvin; Kumar, Preethika

    2008-03-01

    Very few quantum algorithms are currently useable today. When calculating molecular energies, using a quantum algorithm takes advantage of the quantum nature of the algorithm and calculation. A few small molecules have been used to show that this method is possible. This method will be applied to larger molecules and compared to classical computer methods.

  5. First-principles anharmonic quantum calculations for peptide spectroscopy: VSCF calculations and comparison with experiments.

    PubMed

    Roy, Tapta Kanchan; Sharma, Rahul; Gerber, R Benny

    2016-01-21

    First-principles quantum calculations for anharmonic vibrational spectroscopy of three protected dipeptides are carried out and compared with experimental data. Using hybrid HF/MP2 potentials, the Vibrational Self-Consistent Field with Second-Order Perturbation Correction (VSCF-PT2) algorithm is used to compute the spectra without any ad hoc scaling or fitting. All of the vibrational modes (135 for the largest system) are treated quantum mechanically and anharmonically using full pair-wise coupling potentials to represent the interaction between different modes. In the hybrid potential scheme the MP2 method is used for the harmonic part of the potential and a modified HF method is used for the anharmonic part. The overall agreement between computed spectra and experiment is very good and reveals different signatures for different conformers. This study shows that first-principles spectroscopic calculations of good accuracy are possible for dipeptides hence it opens possibilities for determination of dipeptide conformer structures by comparison of spectroscopic calculations with experiment. PMID:26673682

  6. Crystal structure and theoretical calculations of Julocrotine, a natural product with antileishmanial activity

    NASA Astrophysics Data System (ADS)

    Moreira, Rafael Y. O.; Brasil, Davi S. B.; Alves, Cláudio N.; Guilhon, Giselle M. S. P.; Santos, Lourivaldo S.; Arruda, Mara S. P.; Müller, Adolfo H.; Barbosa, Patrícia S.; Abreu, Alcicley S.; Silva, Edilene O.; Rumjanek, Victor M.; Souza, Jaime, Jr.; da Silva, Albérico B. F.; Santos, Regina H. De A.

    Julocrotine, N-(2,6-dioxo-1-phenethyl-piperidin-3-yl)-2-methyl-butyramide, is a potent antiproliferative agent against the promastigote and amastigote forms of Leishmania amazonensis (L.). In this work, the crystal structure of Julocrotine was solved by X-ray diffraction, and its geometrical parameters were compared with theoretical calculations at the B3LYP and HF level of theory. IR and NMR spectra also have been obtained and compared with theoretical calculations. IR absorptions calculated with the B3LYP level of theory employed together with the 6-311G+(d,p) basis set, are close to those observed experimentally. Theoretical NMR calculations show little deviation from experimental results. The results show that the theory is in accordance with the experimental data.0

  7. Determination of absolute configuration of natural products: theoretical calculation of electronic circular dichroism as a tool

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Determination of absolute configuration (AC) is one of the most challenging features in the structure elucidation of chiral natural products, especially those with complex structures. With revolutionary advancements in the area of quantum chemical calculations of chiroptical spectroscopy over the pa...

  8. Protonation studies of modified adenine and adenine nucleotides by theoretical calculations and (15)N NMR.

    PubMed

    Major, Dan T; Laxer, Avital; Fischer, Bilha

    2002-02-01

    The acid/base character of nucleobases affects phenomena such as self-association, interaction with metal ions, molecular recognition by proteins, and nucleic acid base-pairing. Therefore, the investigation of proton-transfer equilibria of natural and synthetic nucleos(t)ides is of great importance to obtain a deeper understanding of these phenomena. For this purpose, a set of ATP prototypes was investigated using (15)N NMR spectroscopy, and the corresponding adenine bases were investigated by theoretical calculations. (15)N NMR measurements provided not only acidity constants but also information on the protonation site(s) on the adenine ring and regarding the ratio of the singly protonated species in equilibrium. Substituents of different nature and position on the adenine ring did not change the preferred protonation site, which remained N1. However, for 2-thioether-ATP derivatives a mixed population of N1 and N7 singly protonated species was observed. Reduction of basicity of 0.4-1 pK(a) units relative to ATP was also observed for all evaluated ATP derivatives, except for 2-Cl-ATP, for which K(a) was ca. 10,000-fold lower. To explain the substitution-dependent variations in the experimental pK(a) values of the ATP analogues, gas-phase proton affinities (PA), Delta Delta G(hyd), and pK(a) values of the corresponding adenine bases were calculated using quantum mechanical methods. The computed PA and Delta Delta G(hyd) values successfully explained the experimental pK(a) values. A computational procedure for the prediction of accurate pK(a) values was developed using density functional theory and polarizable continuum model calculations. In this procedure, we developed a set of parameters for the polarizable continuum model that was fitted to reproduce experimental pK(a) values of nitrogen heterocycles. This method is proposed for the prediction of pK(a) values and protonation site(s) of purine analogues that have not been synthesized or analyzed. PMID:11856021

  9. Open Quantum Dynamics Calculations with the Hierarchy Equations of Motion on Parallel Computers

    PubMed Central

    Strümpfer, Johan; Schulten, Klaus

    2012-01-01

    Calculating the evolution of an open quantum system, i.e., a system in contact with a thermal environment, has presented a theoretical and computational challenge for many years. With the advent of supercomputers containing large amounts of memory and many processors, the computational challenge posed by the previously intractable theoretical models can now be addressed. The hierarchy equations of motion present one such model and offer a powerful method that remained under-utilized so far due to its considerable computational expense. By exploiting concurrent processing on parallel computers the hierarchy equations of motion can be applied to biological-scale systems. Herein we introduce the quantum dynamics software PHI, that solves the hierarchical equations of motion. We describe the integrator employed by PHI and demonstrate PHI’s scaling and efficiency running on large parallel computers by applying the software to the calculation of inter-complex excitation transfer between the light harvesting complexes 1 and 2 of purple photosynthetic bacteria, a 50 pigment system. PMID:23105920

  10. Open Quantum Dynamics Calculations with the Hierarchy Equations of Motion on Parallel Computers.

    PubMed

    Strmpfer, Johan; Schulten, Klaus

    2012-08-14

    Calculating the evolution of an open quantum system, i.e., a system in contact with a thermal environment, has presented a theoretical and computational challenge for many years. With the advent of supercomputers containing large amounts of memory and many processors, the computational challenge posed by the previously intractable theoretical models can now be addressed. The hierarchy equations of motion present one such model and offer a powerful method that remained under-utilized so far due to its considerable computational expense. By exploiting concurrent processing on parallel computers the hierarchy equations of motion can be applied to biological-scale systems. Herein we introduce the quantum dynamics software PHI, that solves the hierarchical equations of motion. We describe the integrator employed by PHI and demonstrate PHI's scaling and efficiency running on large parallel computers by applying the software to the calculation of inter-complex excitation transfer between the light harvesting complexes 1 and 2 of purple photosynthetic bacteria, a 50 pigment system. PMID:23105920

  11. A quantum theoretical approach to information processing in neural networks

    NASA Astrophysics Data System (ADS)

    Barahona da Fonseca, José; Barahona da Fonseca, Isabel; Suarez Araujo, Carmen Paz; Simões da Fonseca, José

    2000-05-01

    A reinterpretation of experimental data on learning was used to formulate a law on data acquisition similar to the Hamiltonian of a mechanical system. A matrix of costs in decision making specifies values attributable to a barrier that opposed to hypothesis formation about decision making. The interpretation of the encoding costs as frequencies of oscillatory phenomena leads to a quantum paradigm based in the models of photoelectric effect as well as of a particle against a potential barrier. Cognitive processes are envisaged as complex phenomena represented by structures linked by valence bounds. This metaphor is used to find some prerequisites to certain types of conscious experience as well as to find an explanation for some pathological distortions of cognitive operations as they are represented in the context of the isolobal model. Those quantum phenomena are understood as representing an analogue programming for specific special purpose computations. The formation of complex chemical structures within the context of isolobal theory is understood as an analog quantum paradigm for complex cognitive computations.

  12. Pseudopotentials for quantum Monte Carlo calculations of transition metal oxides

    NASA Astrophysics Data System (ADS)

    Krogel, Jaron; Santana, Juan; Kent, Paul; Reboredo, Fernando

    2015-03-01

    Quantum Monte Carlo calculations of transition metal oxides are partially limited by the availability of high quality pseudopotentials that are both accurate in QMC and compatible with major electronic structure codes, e.g. by not being overly hard in the standard planewave basis. Following insight gained from recent GW calculations, a set of neon core pseudopotentials with small cutoff radii have been created for the early transition metal elements Sc to Zn within the local density approximation of DFT. The pseudopotentials have been tested for energy consistency within QMC by calculating the first through fourth ionization potentials of the isolated transition metal (TM) atoms and the binding curve of each TM-O dimer. The vast majority of the ionization potentials fall within 0.3 eV of the experimental values, with exceptions occurring mainly for atoms with multiple unpaired d electrons where multireference effects are the strongest. The equilibrium bond lengths of the dimers are within 1% of experimental values and the binding energy errors are typically less than 0.3 eV. Given the uniform treatment of the core, the larger deviations occasionally observed may primarily reflect the limitations of a Slater-Jastrow trial wavefunction. This work is supported by the Materials Sciences & Engineering Division of the Office of Basic Energy Sciences, U.S. DOE. Research by PRCK was conducted at the Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

  13. Molecular thermodynamics of metabolism: quantum thermochemical calculations for key metabolites.

    PubMed

    Hadadi, N; Ataman, M; Hatzimanikatis, V; Panayiotou, C

    2015-04-28

    The present work is the first of a series of papers aiming at a coherent and unified development of the thermodynamics of metabolism and the rationalization of feasibility analysis of metabolic pathways. The focus in this part is on high-level quantum chemical calculations of the thermochemical quantities of relatively heavy metabolites such as amino acids/oligopeptides, nucleosides, saccharides and their derivatives in the ideal gas state. The results of this study will be combined with the corresponding hydration/solvation results in subsequent parts of this work in order to derive the desired thermochemical quantities in aqueous solutions. The above metabolites exist in a vast conformational/isomerization space including rotational conformers, tautomers or anomers exhibiting often multiple or cooperative intramolecular hydrogen bonding. We examine the challenges posed by these features for the reliable estimation of thermochemical quantities. We discuss conformer search, conformer distribution and averaging processes. We further consider neutral metabolites as well as protonated and deprotonated metabolites. In addition to the traditional presentation of gas-phase acidities, basicities and proton affinities, we also examine heats and free energies of ionic species. We obtain simple linear relations between the thermochemical quantities of ions and the formation quantities of their neutral counterparts. Furthermore, we compare our calculations with reliable experimental measurements and predictive calculations from the literature, when available. Finally, we discuss the next steps and perspectives for this work. PMID:25799954

  14. Performance of quantum Monte Carlo for calculating molecular bond lengths.

    PubMed

    Cleland, Deidre M; Per, Manolo C

    2016-03-28

    This work investigates the accuracy of real-space quantum Monte Carlo (QMC) methods for calculating molecular geometries. We present the equilibrium bond lengths of a test set of 30 diatomic molecules calculated using variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods. The effect of different trial wavefunctions is investigated using single determinants constructed from Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals with LDA, PBE, and B3LYP functionals, as well as small multi-configurational self-consistent field (MCSCF) multi-determinant expansions. When compared to experimental geometries, all DMC methods exhibit smaller mean-absolute deviations (MADs) than those given by HF, DFT, and MCSCF. The most accurate MAD of 3 ± 2 × 10(-3) Å is achieved using DMC with a small multi-determinant expansion. However, the more computationally efficient multi-determinant VMC method has a similar MAD of only 4.0 ± 0.9 × 10(-3) Å, suggesting that QMC forces calculated from the relatively simple VMC algorithm may often be sufficient for accurate molecular geometries. PMID:27036428

  15. Performance of quantum Monte Carlo for calculating molecular bond lengths

    NASA Astrophysics Data System (ADS)

    Cleland, Deidre M.; Per, Manolo C.

    2016-03-01

    This work investigates the accuracy of real-space quantum Monte Carlo (QMC) methods for calculating molecular geometries. We present the equilibrium bond lengths of a test set of 30 diatomic molecules calculated using variational Monte Carlo (VMC) and diffusion Monte Carlo (DMC) methods. The effect of different trial wavefunctions is investigated using single determinants constructed from Hartree-Fock (HF) and Density Functional Theory (DFT) orbitals with LDA, PBE, and B3LYP functionals, as well as small multi-configurational self-consistent field (MCSCF) multi-determinant expansions. When compared to experimental geometries, all DMC methods exhibit smaller mean-absolute deviations (MADs) than those given by HF, DFT, and MCSCF. The most accurate MAD of 3 ± 2 × 10-3 Å is achieved using DMC with a small multi-determinant expansion. However, the more computationally efficient multi-determinant VMC method has a similar MAD of only 4.0 ± 0.9 × 10-3 Å, suggesting that QMC forces calculated from the relatively simple VMC algorithm may often be sufficient for accurate molecular geometries.

  16. Double Exponential Relativity Theory Coupled Theoretically with Quantum Theory?

    SciTech Connect

    Montero Garcia, Jose de la Luz; Novoa Blanco, Jesus Francisco

    2007-04-28

    Here the problem of special relativity is analyzed into the context of a new theoretical formulation: the Double Exponential Theory of Special Relativity with respect to which the current Special or Restricted Theory of Relativity (STR) turns to be a particular case only.

  17. Vibrational spectra and quantum mechanical calculations of antiretroviral drugs: Nevirapine

    NASA Astrophysics Data System (ADS)

    Ayala, A. P.; Siesler, H. W.; Wardell, S. M. S. V.; Boechat, N.; Dabbene, V.; Cuffini, S. L.

    2007-02-01

    Nevirapine (11-cyclopropyl-5,11-dihydro-4-methyl-6H-dipyrido[3,2-b:2',3'e][1,4]diazepin-6-one) is an antiretroviral drug belonging to the class of the non-nucleoside inhibitors of the HIV-1 virus reverse transcriptase. As most of this kind of antiretroviral drugs, nevirapine displays a butterfly-like conformation which is preserved in complexes with the HIV-1 reverse transcriptase. In this work, we present a detailed vibrational spectroscopy investigation of nevirapine by using mid-infrared, near-infrared, and Raman spectroscopies. These data are supported by quantum mechanical calculations, which allow us to characterize completely the vibrational spectra of this compound. Based on these results, we discuss the correlation between the vibrational modes and the crystalline structure of the most stable form of nevirapine.

  18. Fragment quantum mechanical calculation of proteins and its applications.

    PubMed

    He, Xiao; Zhu, Tong; Wang, Xianwei; Liu, Jinfeng; Zhang, John Z H

    2014-09-16

    Conspectus The desire to study molecular systems that are much larger than what the current state-of-the-art ab initio or density functional theory methods could handle has naturally led to the development of novel approximate methods, including semiempirical approaches, reduced-scaling methods, and fragmentation methods. The major computational limitation of ab initio methods is the scaling problem, because the cost of ab initio calculation scales nth power or worse with system size. In the past decade, the fragmentation approach based on chemical locality has opened a new door for developing linear-scaling quantum mechanical (QM) methods for large systems and for applications to large molecular systems such as biomolecules. The fragmentation approach is highly attractive from a computational standpoint. First, the ab initio calculation of individual fragments can be conducted almost independently, which makes it suitable for massively parallel computations. Second, the electron properties, such as density and energy, are typically combined in a linear fashion to reproduce those for the entire molecular system, which makes the overall computation scale linearly with the size of the system. In this Account, two fragmentation methods and their applications to macromolecules are described. They are the electrostatically embedded generalized molecular fractionation with conjugate caps (EE-GMFCC) method and the automated fragmentation quantum mechanics/molecular mechanics (AF-QM/MM) approach. The EE-GMFCC method is developed from the MFCC approach, which was initially used to obtain accurate protein-ligand QM interaction energies. The main idea of the MFCC approach is that a pair of conjugate caps (concaps) is inserted at the location where the subsystem is divided by cutting the chemical bond. In addition, the pair of concaps is fused to form molecular species such that the overcounted effect from added concaps can be properly removed. By introducing the electrostatic embedding field in each fragment calculation and two-body interaction energy correction on top of the MFCC approach, the EE-GMFCC method is capable of accurately reproducing the QM molecular properties (such as the dipole moment, electron density, and electrostatic potential), the total energy, and the electrostatic solvation energy from full system calculations for proteins. On the other hand, the AF-QM/MM method was used for the efficient QM calculation of protein nuclear magnetic resonance (NMR) parameters, including the chemical shift, chemical shift anisotropy tensor, and spin-spin coupling constant. In the AF-QM/MM approach, each amino acid and all the residues in its vicinity are automatically assigned as the QM region through a distance cutoff for each residue-centric QM/MM calculation. Local chemical properties of the central residue can be obtained from individual QM/MM calculations. The AF-QM/MM approach precisely reproduces the NMR chemical shifts of proteins in the gas phase from full system QM calculations. Furthermore, via the incorporation of implicit and explicit solvent models, the protein NMR chemical shifts calculated by the AF-QM/MM method are in excellent agreement with experimental values. The applications of the AF-QM/MM method may also be extended to more general biological systems such as DNA/RNA and protein-ligand complexes. PMID:24851673

  19. SusyMath: A Mathematica package for quantum superfield calculations

    NASA Astrophysics Data System (ADS)

    Ferrari, A. F.

    2007-03-01

    SusyMath is a Mathematica package for quantum superfield calculations. It defines a standard form to translate the correction to the effective action corresponding to a given supergraph into a Mathematica expression, which is then evaluated and simplified. Several functions for manipulations of these expressions are provided, and the package also has the ability to save the outcomes of its calculations in ? form. Program summaryTitle of program: SusyMath Catalogue identifier:ADYQ_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/ADYQ_v1_0 Program obtainable from: CPC Program Library, Queen's University of Belfast, N. Ireland, also at http://fma.if.usp.br/~alysson/SusyMath Licensing provisions: LGPL, CPC non-profit use license Programming language: Mathematica Platform: Any platform supporting Mathematica 4.0 or higher Computer tested on: PC (Athlon64 X2 +3800); 1 GB RAM Operating system under which the program has been tested: Linux (Debian 4.0); XOrg 7.0.22; Mathematica 5.2 No. of lines in distributed program, including test data, etc.:42 472 No. of bytes in distributed program, including test data, etc.:471 596 Distribution format:tar.gz Nature of the problem: Evaluate quantum corrections to the effective action of supersymmetric field theories, formulated in the superfield formalism, both in three- and four-spacetime dimensions. Solution method: A set of procedures for integration by parts, application of the algebra of covariant derivatives and Grassman integration, along with several auxiliary functions, is introduced. Restrictions: At the moment, the background field method is not implemented, but the system is designed to be further generalized. Running time: Depends on the complexity of the problem. From seconds for simpler one-loop diagrams to several hours for simple two-loop graphs.

  20. A theoretical estimation of orientational quantum effects in polar fluids

    NASA Astrophysics Data System (ADS)

    Woodward, C. E.; Nordholm, Sture

    Thermodynamic properties of classical polar fluids can be estimated from those of a simple fluid wherein the central pair potential has been chosen to account for pairwise orientational correlations. This mapping of polar to simple fluids has been extended to account for the quantization of rotational motion and the corresponding damping of orientational correlations. Choosing the model parameters to reflect HCl, HBr and HI we find large rotational quantum effects on the phase diagram and second virial coefficients if dispersion forces are neglected but only very minor such effects when the dominant dispersion forces are included.

  1. The information-theoretical entropy of some quantum oscillators

    NASA Astrophysics Data System (ADS)

    Popov, D.; Pop, N.; Popov, M.; imon, S.

    2014-11-01

    The Wehrl entropy or the "classical" entropy associated with a quantum system is the entropy of the probability distribution in phase space, corresponding to the Husimi Q-function in terms of coherent states. In the present paper, we shall focus our attention on the examination of the Wehrl entropy for both the pure and the mixed (thermal) states of the pseudoharmonic oscillator (PHO). The choice of the PHO is interesting because this oscillator is an intermediate between the ideal one-dimensional harmonic oscillator (HO-1D) and the more practical anharmonicone.

  2. The information-theoretical entropy of some quantum oscillators

    SciTech Connect

    Popov, D. Pop, N.; Popov, M.

    2014-11-24

    The Wehrl entropy or the 'classical' entropy associated with a quantum system is the entropy of the probability distribution in phase space, corresponding to the Husimi Q-function in terms of coherent states. In the present paper, we shall focus our attention on the examination of the Wehrl entropy for both the pure and the mixed (thermal) states of the pseudoharmonic oscillator (PHO). The choice of the PHO is interesting because this oscillator is an intermediate between the ideal one-dimensional harmonic oscillator (HO-1D) and the more practical anharmonicone.

  3. Theoretical modeling and experimental characterization of InAs/InGaAs quantum dots in a well detector

    SciTech Connect

    Amtout, A.; Raghavan, S.; Rotella, P.; Winckel, G. von; Stintz, A.; Krishna, S.

    2004-10-01

    Theoretical modeling and experimental characterization of InGaAs/GaAs quantum dots-in-a-well (DWELL) intersubband heterostructures, grown by molecular beam epitaxy are reported. In this heterostructure, the self-assembled dots are confined to the top half of a 110 A InGaAs well which in turn is placed in a GaAs matrix. Using transmission electron microscopy, the quantum dots are found to be pyramidal in shape with a base dimension of 110 A and height of 65 A. The band structure for the above mentioned DWELL heterostructure was theoretically modeled using a Bessel function expansion of the wave function. The energy levels of the three lowest states of the conduction band of the quantum dot are calculated as a function of the electric field. Intersubband n-i-n detectors were fabricated using a ten layer DWELL heterostructure. The spectral response of the detector is measured at a temperature between 30 and 50 K and compared with the prediction of our theoretical model.

  4. [Theoretical calculation and experimental study of membrane thickness of alginate-(poly-L-lysine)-alginate microcapsules].

    PubMed

    Sun, Duoxian; Chen, Yiqing; Yang, Jun; Su, Jing; Sun, Anthony M

    2002-12-01

    Alginate-(Poly-L-Lysine)-Alginate(APA) microcapsules were prepared by Electrostatic Droplet Generator(EDG) technique and the thickness of microcapsule membrane, which was composed by polyelectrolyte complex, were studied in this paper. The theoretical formula was given for the measurement of membrane thickness of APA microcapsules by element analysis of membrane and calculation. The membrane thickness was 7-10 microns by theoretical calculation. On the other hand, the thickness of membrane was measured by SEM and optical microscopy and the results were 7 microns and 12 microns, respectively. The results showed that theoretical calculation is in good accordance with experimental determoination of mermbrane thickness and the membrane thickness of APA microcapsule is about 7-10 microns. The optical microscopy is an easy way to measure membrane thickness. PMID:12561369

  5. Quantum chemical calculations, vibrational studies, HOMO-LUMO and NBO/NLMO analysis of 2-bromo-5-nitrothiazole.

    PubMed

    Gobinath, E; Xavier, R John

    2013-03-01

    The complete vibrational assignment and analysis of the fundamental modes of 2-bromo-5-nitrothiazole (BNT) was carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The observed vibrational data were compared with the wavenumbers derived theoretically for the optimized geometry of the compound from the ab initio HF and DFT-B3LYP gradient calculations employing 6-311++G(d,p) basis set. Thermodynamic properties like entropy, heat capacity and zero point energy have been calculated for the molecule. HOMO-LUMO energy gap has been calculated. The intramolecular contacts have been interpreted using Natural Bond Orbital (NBO) and Natural Localized Molecular Orbital (NLMO) analysis. Important non-linear properties such as electric dipole moment and first hyperpolarizability of BNT have been computed using B3LYP quantum chemical calculation. PMID:23274373

  6. Calculated quantum yield of photosynthesis of phytoplankton in the Marine Light-Mixed Layers (59 deg N, 21 deg W)

    NASA Technical Reports Server (NTRS)

    Carder, K. L.; Lee, Z. P.; Marra, John; Steward, R. G.; Perry, M. J.

    1995-01-01

    The quantum yield of photosynthesis (mol C/mol photons) was calculated at six depths for the waters of the Marine Light-Mixed Layer (MLML) cruise of May 1991. As there were photosynthetically available radiation (PAR) but no spectral irradiance measurements for the primary production incubations, three ways are presented here for the calculation of the absorbed photons (AP) by phytoplankton for the purpose of calculating phi. The first is based on a simple, nonspectral model; the second is based on a nonlinear regression using measured PAR values with depth; and the third is derived through remote sensing measurements. We show that the results of phi calculated using the nonlinear regreesion method and those using remote sensing are in good agreement with each other, and are consistent with the reported values of other studies. In deep waters, however, the simple nonspectral model may cause quantum yield values much higher than theoretically possible.

  7. Correlation of Calculated Excited-state Energies and Experimental Quantum Yields of Luminescent Tb(III) ?-diketonates

    SciTech Connect

    De Silva, Channa R.; Li, Jun; Zheng, Zhiping; Corrales, Louis R.

    2008-05-22

    Theoretical calculations employing time dependent density functional theory (TDDFT) are used to characterize the excited states of Tb(III) ?-diketonate complexes. Calculated results are compared directly with experimental results that together show a correlation between relative quantum yields and the excited-state energies that depend on the electronic properties of the p,p- substituent group associated with the coordinating N-donor neutral ligand. It is found that changes in the electron donating nature of the neutral ligand structure leads to shifts in the lowest triplet energy level of the complex that consequently changes the relative quantum yield. Thus providing critical direction for the synthesis of high quantum yield terbium complexes.

  8. Synthesis, structure, theoretical calculations and biological activity of sulfonate active ester new derivatives

    NASA Astrophysics Data System (ADS)

    Ghazzali, Mohamed; Khattab, Sherine A. N.; Elnakady, Yasser A.; Al-Mekhlafi, Fahd A.; Al-Farhan, Khalid; El-Faham, Ayman

    2013-08-01

    A series of naphthyl and tolyl sulfonate ester were synthesized and characterized by H NMR. X-ray single crystal diffraction experiments established the molecular structure of three new sulfonate esters derivatives, and spectral data agree with these in solution. The observed hydrogen bonding is discussed on the basis of crystal structural analyses and DFT/MP2 geometry optimization quantum calculations. Antimicrobial activities were screened for selected compounds against three human cancer cell lines and Mosquito Culex pipiens larvae.

  9. Efficiency and power loss in d. c. chopper circuits. [Theoretical calculation

    SciTech Connect

    Beck, M.O.

    1981-01-01

    The object of this paper was to investigate the efficiency and source of power losses of various classes of dc chopper circuits. The study involved a theoretical calculation of the power losses, supported by a considerable amount of practical work on full power-rated traction motor test bed. 3 refs.

  10. Complex Calculators in the Classroom: Theoretical and Practical Reflections on Teaching Pre-Calculus.

    ERIC Educational Resources Information Center

    LaGrange, Jean-Baptiste

    1999-01-01

    Reviews tasks and techniques to help students develop an appropriate instrumental genesis for algebra and functions to prepare for calculus. Focuses on the potential of the calculator to connect enactive representations and theoretical calculus. Discusses strategies to help students experiment with symbolic concepts in calculus. (Contains 32…

  11. Theoretical Calculation of Electronic Circular Dichroism of a Hexahydroxydiphenoyl-Containing Flavanone Glycoside

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Time-dependent density functional theory (TDDFT) was employed for theoretical calculation of electronic circular dichroism (ECD) of a hexahydroxydiphenoyl (HHDP)-containing flavanone glycoside, mattucinol-7-O-[4'',6''-O-(aS)-hexahydroxydiphenoyl]-ß-d-glucopyranoside (2). It identified the roles of t...

  12. Quantum Monte Carlo calculations for point defects in semiconductors

    NASA Astrophysics Data System (ADS)

    Hennig, Richard

    2010-03-01

    Point defects in silicon have been studied extensively for many years. Nevertheless the mechanism for self diffusion in Si is still debated. Direct experimental measurements of the selfdiffusion in silicon are complicated by the lack of suitable isotopes. Formation energies are either obtained from theory or indirectly through the analysis of dopant and metal diffusion experiments. Density functional calculations predict formation energies ranging from 3 to 5 eV depending on the approximations used for the exchange-correlation functional [1]. Analysis of dopant and metal diffusion experiments result in similar broad range of diffusion activation energies of 4.95 [2], 4.68 [3], 2.4 eV [4]. Assuming a migration energy barrier of 0.1-0.3 eV [5], the resulting experimental interstitial formation energies range from 2.1 - 4.9 eV. To answer the question of the formation energy of Si interstitials we resort to a many-body description of the wave functions using quantum Monte Carlo (QMC) techniques. Previous QMC calculations resulted in formation energies for the interstitials of around 5 eV [1,6]. We present a careful analysis of all the controlled and uncontrolled approximations that affect the defect formation energies in variational and diffusion Monte Carlo calculations. We find that more accurate trial wave functions for QMC using improved Jastrow expansions and most importantly a backflow transformation for the electron coordinates significantly improve the wave functions. Using zero-variance extrapolation, we predict interstitial formation energies in good agreement with hybrid DFT functionals [1] and recent GW calculations [7]. [4pt] [1] E. R. Batista, J. Heyd, R. G. Hennig, B. P. Uberuaga, R. L. Martin, G. E. Scuseria, C. J. Umrigar, and J. W. Wilkins. Phys. Rev. B 74, 121102(R) (2006).[0pt] [2] H. Bracht, E. E. Haller, and R. Clark-Phelps, Phys. Rev. Lett. 81, 393 (1998). [0pt] [3] A. Ural, P. B. Griffin, and J. D. Plummer, Phys. Rev. Lett. 83, 3454 (1999). [0pt] [4] R. Vaidyanathan, M. Y. L. Jung, and E. G. Seebauer, Phys. Rev. B 75, 195209 (2007). [0pt] [5] P. G. Coleman and C. P. Burrows, Phys. Rev. Lett. 98, 265502 (2007). [0pt] [6] W. K. Leung, R. J. Needs, G. Rajagopal, S. Itoh, and S. Ihara, Phys. Rev. Lett. 83, 2351 (1999). [0pt] [7] P. Rinke, A. Janotti, M. Scheffler, and C. G. Van de Walle, Phys. Rev. Lett. 102, 026402 (2009).

  13. The rigorous stochastic matrix multiplication scheme for the calculations of reduced equilibrium density matrices of open multilevel quantum systems

    SciTech Connect

    Chen, Xin

    2014-04-21

    Understanding the roles of the temporary and spatial structures of quantum functional noise in open multilevel quantum molecular systems attracts a lot of theoretical interests. I want to establish a rigorous and general framework for functional quantum noises from the constructive and computational perspectives, i.e., how to generate the random trajectories to reproduce the kernel and path ordering of the influence functional with effective Monte Carlo methods for arbitrary spectral densities. This construction approach aims to unify the existing stochastic models to rigorously describe the temporary and spatial structure of Gaussian quantum noises. In this paper, I review the Euclidean imaginary time influence functional and propose the stochastic matrix multiplication scheme to calculate reduced equilibrium density matrices (REDM). In addition, I review and discuss the Feynman-Vernon influence functional according to the Gaussian quadratic integral, particularly its imaginary part which is critical to the rigorous description of the quantum detailed balance. As a result, I establish the conditions under which the influence functional can be interpreted as the average of exponential functional operator over real-valued Gaussian processes for open multilevel quantum systems. I also show the difference between the local and nonlocal phonons within this framework. With the stochastic matrix multiplication scheme, I compare the normalized REDM with the Boltzmann equilibrium distribution for open multilevel quantum systems.

  14. The rigorous stochastic matrix multiplication scheme for the calculations of reduced equilibrium density matrices of open multilevel quantum systems

    NASA Astrophysics Data System (ADS)

    Chen, Xin

    2014-04-01

    Understanding the roles of the temporary and spatial structures of quantum functional noise in open multilevel quantum molecular systems attracts a lot of theoretical interests. I want to establish a rigorous and general framework for functional quantum noises from the constructive and computational perspectives, i.e., how to generate the random trajectories to reproduce the kernel and path ordering of the influence functional with effective Monte Carlo methods for arbitrary spectral densities. This construction approach aims to unify the existing stochastic models to rigorously describe the temporary and spatial structure of Gaussian quantum noises. In this paper, I review the Euclidean imaginary time influence functional and propose the stochastic matrix multiplication scheme to calculate reduced equilibrium density matrices (REDM). In addition, I review and discuss the Feynman-Vernon influence functional according to the Gaussian quadratic integral, particularly its imaginary part which is critical to the rigorous description of the quantum detailed balance. As a result, I establish the conditions under which the influence functional can be interpreted as the average of exponential functional operator over real-valued Gaussian processes for open multilevel quantum systems. I also show the difference between the local and nonlocal phonons within this framework. With the stochastic matrix multiplication scheme, I compare the normalized REDM with the Boltzmann equilibrium distribution for open multilevel quantum systems.

  15. Quantum Monte Carlo Algorithms for Diagrammatic Vibrational Structure Calculations

    NASA Astrophysics Data System (ADS)

    Hermes, Matthew; Hirata, So

    2015-06-01

    Convergent hierarchies of theories for calculating many-body vibrational ground and excited-state wave functions, such as Møller-Plesset perturbation theory or coupled cluster theory, tend to rely on matrix-algebraic manipulations of large, high-dimensional arrays of anharmonic force constants, tasks which require large amounts of computer storage space and which are very difficult to implement in a parallel-scalable fashion. On the other hand, existing quantum Monte Carlo (QMC) methods for vibrational wave functions tend to lack robust techniques for obtaining excited-state energies, especially for large systems. By exploiting analytical identities for matrix elements of position operators in a harmonic oscillator basis, we have developed stochastic implementations of the size-extensive vibrational self-consistent field (MC-XVSCF) and size-extensive vibrational Møller-Plesset second-order perturbation (MC-XVMP2) theories which do not require storing the potential energy surface (PES). The programmable equations of MC-XVSCF and MC-XVMP2 take the form of a small number of high-dimensional integrals evaluated using Metropolis Monte Carlo techniques. The associated integrands require independent evaluations of only the value, not the derivatives, of the PES at many points, a task which is trivial to parallelize. However, unlike existing vibrational QMC methods, MC-XVSCF and MC-XVMP2 can calculate anharmonic frequencies directly, rather than as a small difference between two noisy total energies, and do not require user-selected coordinates or nodal surfaces. MC-XVSCF and MC-XVMP2 can also directly sample the PES in a given approximation without analytical or grid-based approximations, enabling us to quantify the errors induced by such approximations.

  16. Quantum field theoretical study of an effective spin model in coupled optical cavity arrays

    NASA Astrophysics Data System (ADS)

    Sarkar, Sujit

    2012-01-01

    Atoms trapped in micro-cavities and interacting through the exchange of virtual photons can be modeled as an anisotropic Heisenberg spin-1/2 lattice. We do the quantum field theoretical study of such a system using the Abelian bosonization method followed by the renormalization group analysis. An infinite order Berezinskii-Kosterliz-Thouless transition is replaced by second order XY transition even when an infinitesimal anisotropy in exchange coupling is introduced. We predict a quantum phase transition between the photonic Coulomb blocked induce Mott insulating and photonic superfluid phases due to detuning between the cavity and laser frequency. A large detuning favors the photonic superfluid phase. We also perform the analysis of Jaynes and Cumming Hamiltonian to support the results of quantum field theoretical study.

  17. Theoretical methods for the calculation of Bragg curves and 3D distributions of proton beams

    NASA Astrophysics Data System (ADS)

    Ulmer, W.; Matsinos, E.

    2010-12-01

    The well-known Bragg-Kleeman rule RCSDA = A ṡ E has become a pioneer work in radiation physics of charged particles and is still a useful tool to estimate the range RCSDA of approximately monoenergetic protons with initial energy E0 in a homogeneous medium. The rule is based on the continuous-slowing-down-approximation (CSDA). It results from a generalized (nonrelativistic) Langevin equation and a modification of the phenomenological friction term. The complete integration of this equation provides information about the residual energy E(z) and dE(z)/dz at each position z(0 ≦ z ≦ RCSDA). A relativistic extension of the generalized Langevin equation yields the formula RCSDA = A ṡ (E0 + E/2M ṡ c2)p. The initial energy of therapeutic protons satisfies E0 ≪ 2M ṡ c2(M ṡ c2 = 938.276 MeV), which enables us to consider the relativistic contributions as correction terms. Besides this phenomenological starting-point, a complete integration of the Bethe-Bloch equation (BBE) is developed, which also provides the determination of RCSDA, E(z) and dE(z)/dz and uses only those parameters given by the BBE itself (i.e., without further empirical parameters like modification of friction). The results obtained in the context of the aforementioned methods are compared with Monte-Carlo calculations (GEANT4); this Monte-Carlo code is also used with regard to further topics such as lateral scatter, nuclear interactions, and buildup effects. In the framework of the CSDA, the energy transfer from protons to environmental atomic electrons does not account for local fluctuations. Based on statistical quantum mechanics, an analysis of the Gaussian convolution and the Landau-Vavilov distribution function is carried out to describe these fluctuations. The Landau tail is derived as Hermite polynomial corrections of a Gaussian convolution. It is experimentally confirmed that proton Bragg curves with E0 ≧ 120 MeV show a buildup, which increases with the proton energy. This buildup is explained by a theoretical analysis of impinging proton beamlets. In order to obtain a complete dose calculation model for proton treatment planning, some further aspects have to be accounted for: the decrease of the fluence of the primary protons due to nuclear interactions, the transport of released secondary protons, the dose contribution of heavy recoil nuclei, the inclusion of lateral scatter of the primary and secondary protons based on Molière's multiple-scatter theory, and the scatter contributions of collimators. This study also presents some results which go beyond proton dose calculation models; namely, the application of the relativistic generalization of the Bragg-Kleeman rule to electrons and, in an appendix, a method to determine inelastic cross-sections of therapeutic protons in media of therapeutic interest.

  18. Heats of Segregation of BCC Binaries from ab Initio and Quantum Approximate Calculations

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2004-01-01

    We compare dilute-limit heats of segregation for selected BCC transition metal binaries computed using ab initio and quantum approximate energy methods. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent LMTO-based parameters. Quantum approximate segregation energies are computed with and without atomistic relaxation, while the ab initio calculations are performed without relaxation. Results are discussed within the context of a segregation model driven by strain and bond-breaking effects. We compare our results with full-potential quantum calculations and with available experimental results.

  19. Synthesis, characterization, spectroscopic properties, theoretical calculation, and antimicrobial activity of new aryldisulfonamides

    NASA Astrophysics Data System (ADS)

    Alyar, Saliha; Zengin, Hüseyin; Özbek, Neslihan; Karacan, Nurcan

    2011-04-01

    New aryldisulfonamides were synthesized and characterized by FTIR, 1H NMR, 13C NMR, HETCOR, COSY, LC-MS and elemental analysis techniques. The compounds gave intense emissions, where λmax = 405, 379 and 402 nm, upon irradiation by Ultra-Violet light. The photoluminescence quantum yields and long excited-state lifetimes of the compounds were calculated and were found to have photoluminescence quantum yields 39 ± 1.8%, 45 ± 2.2% and 34 ± 1.4% and long excited-state lifetimes of 3.65 ± 0.16, 4.17 ± 0.20 and 3.15 ± 0.12 ns, respectively. The photoluminescence intensities and quantum yields of compounds varied with the position of substituent on the ring and the chain length between aromatic rings. These novel compounds may be of interest as organic emitting materials for electroluminescent devices. The visible absorption maxima were calculated using time-depended density-functional theory (TD-DFT) and Zerner's intermediate neglect of differential overlap/spectroscopic (ZINDO/S) method in the gas phase. Further, the compounds were evaluated for in vitro antimicrobial activity against various microorganisms by microdilution and disk diffusion methods.

  20. Quantum critical scaling in beta-YbAlB4 and theoretical implications

    NASA Astrophysics Data System (ADS)

    Nevidomskyy, Andriy

    2012-02-01

    Emergent phenomena in quantum materials are subject of intense experimental and theoretical research at present. A wonderful example thereof are the sister phases of YbAlB4 - a newly discovered heavy fermion material [1]. While one phase (α-YbAlB4) is a heavy Fermi liquid, its sibling β-YbAlB4 is quantum critical, supporting an unconventional superconductivity with a tiny transition temperature of ˜80 mK. Latest experiments [2] uncover the quantum critical T/B-scaling in β-YbAlB4 and prove that superconductivity emerges from a strange metal governed by an extremely fragile quantum criticality, which apparently occurs at zero field, without any external tuning. Here, we will present a theoretical perspective on the quantum critical scaling in β-YbAlB4 and will show that the critical exponents can be derived from the nodal structure of the hybridization matrix between Yb f-band and the conduction electrons. It follows that the free energy at low temperatures can be written in a scaling form F[(kBT)^2 + (gμBB)^2]^3/4, which predicts the divergent Sommerfeld coefficient γ and quasi-particle effective mass as B->0: γ˜m^*/m B-1/2. This is indeed observed in the experiment [1,2], which places a tiny upper bound on the critical magnetic field Bc<0.2 mT. We will discuss theoritical implications of this fragile intrinsic quantum criticality in β-YbAlB4 and discuss the possibility of a quantum critical phase, rather than a quantum critical point, in this material. [1] S. Nakatsuji et al., Nature Physics 4, 603 (2008). [2] Y. Matsumoto, S. Nakatsuji, K. Kuga, Y. Karaki, Y. Shimura, T. Sakakibara, A. H. Nevidomskyy, and P. Coleman, Science 331, 316 (2011).

  1. Theoretical analysis of on-chip linear quantum optical information processing networks

    NASA Astrophysics Data System (ADS)

    Hach, Edwin E.; Preble, Stefan F.; Steidle, Jeffrey A.

    2015-05-01

    We present a quantum optical analysis of waveguides directionally coupled to ring resonators, an architecture realizable using silicon nanophotonics. The innate scalability of the silicon platform allows for the possibility of "on-chip" quantum computation and information processing. In this paper, we briefly review a comprehensive method for analyzing the quantum mechanical output of such a network for an arbitrary input state of the quantized, traveling electromagnetic field in the continuous wave (cw) limit. Specifically, we briefly review a recent theoretical result identifying a particular device topology that yields, via Passive Quantum Optical Feedback (PQOF), dramatic and unexpected enhancements of the Hong-Ou-Mandel Effect, an effect central to the operation of many quantum information processing systems. Next, we extend the analysis to our proposal for a scalable, on-chip realization of the Nonlinear Sign (NS) shifter essential for implementation of the Knill-Laflamme-Milburn (KLM) protocol for Linear Optical Quantum Computing (LOQC). Finally, we discuss generalizations to arbitrary networks of directionally coupled ring resonators along with possible applications is the areas of quantum metrology and sensitive photon detection.

  2. Mass spectrometry and theoretical calculations about the loss of methyl radical from methoxilated coumarins

    NASA Astrophysics Data System (ADS)

    Borkowski, Eduardo J.; Cecati, Francisco M.; Suvire, Fernando D.; Ruiz, Diego M.; Ardanaz, Carlos E.; Romanelli, Gustavo P.; Enriz, Ricardo D.

    2015-08-01

    In this study we have performed CID mass spectrometry measurements and theoretical calculations in a selected series of coumarins. Our theoretical and experimental results indicate that there is room for reasonable doubts about the fragmentation way previously proposed by Shapiro and Djerassi (1965). A complementary explanation about the fragmentation way of the methyl loss from methoxy coumarins has been reported in this work. Our results demonstrated that different theoretical models are very useful to explain the fragmentation occurred in MS, supporting the usual rules of fragmentation. Although the QTAIM analysis gives a good correlation in order to explain the formation of p-quinoid resonance forms; however, the best correlation has been obtained using the NBO approximation as well as from the Wiberg indexes.

  3. Hyperon Puzzle: Hints from Quantum Monte Carlo Calculations

    NASA Astrophysics Data System (ADS)

    Lonardoni, Diego; Lovato, Alessandro; Gandolfi, Stefano; Pederiva, Francesco

    2015-03-01

    The onset of hyperons in the core of neutron stars and the consequent softening of the equation of state have been questioned for a long time. Controversial theoretical predictions and recent astrophysical observations of neutron stars are the grounds for the so-called hyperon puzzle. We calculate the equation of state and the neutron star mass-radius relation of an infinite systems of neutrons and Λ particles by using the auxiliary field diffusion Monte Carlo algorithm. We find that the three-body hyperon-nucleon interaction plays a fundamental role in the softening of the equation of state and for the consequent reduction of the predicted maximum mass. We have considered two different models of three-body force that successfully describe the binding energy of medium mass hypernuclei. Our results indicate that they give dramatically different results on the maximum mass of neutron stars, not necessarily incompatible with the recent observation of very massive neutron stars. We conclude that stronger constraints on the hyperon-neutron force are necessary in order to properly assess the role of hyperons in neutron stars.

  4. Hyperon puzzle: hints from quantum Monte Carlo calculations.

    PubMed

    Lonardoni, Diego; Lovato, Alessandro; Gandolfi, Stefano; Pederiva, Francesco

    2015-03-01

    The onset of hyperons in the core of neutron stars and the consequent softening of the equation of state have been questioned for a long time. Controversial theoretical predictions and recent astrophysical observations of neutron stars are the grounds for the so-called hyperon puzzle. We calculate the equation of state and the neutron star mass-radius relation of an infinite systems of neutrons and Λ particles by using the auxiliary field diffusion Monte Carlo algorithm. We find that the three-body hyperon-nucleon interaction plays a fundamental role in the softening of the equation of state and for the consequent reduction of the predicted maximum mass. We have considered two different models of three-body force that successfully describe the binding energy of medium mass hypernuclei. Our results indicate that they give dramatically different results on the maximum mass of neutron stars, not necessarily incompatible with the recent observation of very massive neutron stars. We conclude that stronger constraints on the hyperon-neutron force are necessary in order to properly assess the role of hyperons in neutron stars. PMID:25793808

  5. Nuclear radii calculations in various theoretical approaches for nucleus-nucleus interactions

    SciTech Connect

    Merino, C.; Novikov, I. S.; Shabelski, Yu.

    2009-12-15

    The information about sizes and nuclear density distributions in unstable (radioactive) nuclei is usually extracted from the data on interaction of radioactive nuclear beams with a nuclear target. We show that in the case of nucleus-nucleus collisions the values of the parameters depend somewhat strongly on the considered theoretical approach and on the assumption about the parametrization of the nuclear density distribution. The obtained values of root-mean-square radii (R{sub rms}) for stable nuclei with atomic weights A=12-40 vary by approximately 0.1 fm when calculated in the optical approximation, in the rigid target approximation, and using the exact expression of the Glauber theory. We present several examples of R{sub rms} radii calculations using these three theoretical approaches and compare these results with the data obtained from electron-nucleus scattering.

  6. Theoretical calculation of the interannual variability of the Earth's insolation with daily resolution

    NASA Astrophysics Data System (ADS)

    Fedorov, V. M.

    2016-05-01

    Based on the astronomical ephemerides DE-406, theoretical calculations have been performed of the interannual variability of the Earth's insolation related to celestial-mechanical processes for 365 points of a tropical year in the time period from 1900 to 2050. It has been determined that the average amplitude of variations of the interannual insolation is 0.310 W/m2 (0.023% of the solar constant). The calculated variations are characterized by strict periodicity that corresponds with the length of a synodic month. Connection between the extreme values of the calculated insolation variability and syzygies has been defined. The average amplitude of the calculated variability exceeds by 1.7 times (0.01% of the solar constant) the amplitude of the interannual variability in the 11-year variation of the total Earth's insolation.

  7. Numerical and theoretical study of Bernstein modes in a magnetized quantum plasma

    SciTech Connect

    Eliasson, Bengt; Shukla, Padma K.

    2008-10-15

    A numerical and theoretical study is presented for the propagation of electron Bernstein modes in a magnetized quantum plasma. The dispersion relation for electrostatic waves is derived, using a semiclassical Vlasov model for Fermi-Dirac distributed electrons. The dispersion relation is checked numerically with direct Vlasov simulations, where the wave energy is concentrated to the Bernstein modes as well as to the zero-frequency convective mode. Dispersion relations in the long wavelength limit are derived, including the upper hybrid dispersion relation for a degenerate quantum plasma.

  8. A combined study based on experimental analyses and theoretical calculations on properties of poly (lactic acid) under annealing treatment

    NASA Astrophysics Data System (ADS)

    Loued, W.; Wéry, J.; Dorlando, A.; Alimi, K.

    2015-02-01

    In this paper, the significance of annealing, in two different atmospheres (air and vacuum), on the surface characteristics of poly (lactic acid) (PLA) films was investigated. X-ray diffraction (XRD) measurements correlated to atomic force microscopy (AFM) observations of the cast PLA films show that thermal treatment under air atmosphere is responsible for a significant increase of crystallinity with the increase of temperature. However, band gap energy of the title compound is slightly affected by annealing at different temperatures. As for the untreated PLA, the molecular geometry was optimized using density functional theory (DFT/B3LYP) method with 6-31g (d) basis set in ground state. From the optimized geometry, HOMO and LUMO energies and quantum chemical parameters were performed at B3LYP/6-31g (d). The theoretical results, applied to simulated optical spectra of the compound, were compared to the observed ones. On the basis of theoretical vibrational analyses, the thermodynamic properties were calculated at different temperatures, revealing the correlation between internal energy (U), enthalpy (H), entropy (S), Free energy (G) and temperatures.

  9. Heats of Segregation of BCC Binaries from Ab Initio and Quantum Approximate Calculations

    NASA Technical Reports Server (NTRS)

    Good, Brian S.

    2003-01-01

    We compare dilute-limit segregation energies for selected BCC transition metal binaries computed using ab initio and quantum approximate energy methods. Ab initio calculations are carried out using the CASTEP plane-wave pseudopotential computer code, while quantum approximate results are computed using the Bozzolo-Ferrante-Smith (BFS) method with the most recent parameters. Quantum approximate segregation energies are computed with and without atomistic relaxation. Results are discussed within the context of segregation models driven by strain and bond-breaking effects. We compare our results with full-potential quantum calculations and with available experimental results.

  10. Interaction effects on topological phase transitions via numerically exact quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Hung, Hsiang-Hsuan; Chua, Victor; Wang, Lei; Fiete, Gregory A.

    2014-06-01

    We theoretically study topological phase transitions in four generalized versions of the Kane-Mele-Hubbard model with up to 2×182 sites. All models are free of the fermion-sign problem allowing numerically exact quantum Monte Carlo (QMC) calculations to be performed to extremely low temperatures. We numerically compute the Z2 invariant and spin Chern number Cσ directly from the zero-frequency single-particle Green's functions, and study the topological phase transitions driven by the tight-binding parameters at different on-site interaction strengths. The Z2 invariant and spin Chern number, which are complementary to each another, characterize the topological phases and identify the critical points of topological phase transitions. Although the numerically determined phase boundaries are nearly identical for different system sizes, we find strong system-size dependence of the spin Chern number, where quantized values are only expected upon approaching the thermodynamic limit. For the Hubbard models we considered, the QMC results show that correlation effects lead to shifts in the phase boundaries relative to those in the noninteracting limit, without any spontaneously symmetry breaking. The interaction-induced shift is nonperturbative in the interactions and cannot be captured within a "simple" self-consistent calculation either, such as Hartree-Fock. Furthermore, our QMC calculations suggest that quantum fluctuations from interactions stabilize topological phases in systems where the one-body terms preserve the D3 symmetry of the lattice, and destabilize topological phases when the one-body terms break the D3 symmetry.

  11. Advanced Quantum Mechanical Calculation of Superheavy Ions: Energy Levels, Radiation and Finite Nuclear Size Effects

    NASA Astrophysics Data System (ADS)

    Glushkov, Alexander V.; Gurnitskaya, E. P.; Loboda, A. V.

    2005-10-01

    Advanced quantum approach to calculation of spectra for superheavy ions with an account of relativistic, correlation, nuclear, radiative effects is developed and based on the gauge invariant quantum electrodynamics (QED) perturbation theory (PT). The Lamb shift polarization part is calculated in the Ueling approximation, self-energy part is defined within a new non-PT procedure of Ivanov-Ivanova. Calculation results for energy levels, hyperfine structure parameters of some heavy elements ions are presented.

  12. Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides

    NASA Astrophysics Data System (ADS)

    Sharma, Vinit; Krogel, Jaron T.; Kent, P. R. C.; Reboredo, Fernando A.

    One of the critical scientific challenges of contemporary research is to obtain an accurate theoretical description of the electronic properties of strongly correlated systems such as transition metal oxides and rare-earth compounds, since state-of-art ab-initio methods based on approximate density functionals are not always sufficiently accurate. Quantum Monte Carlo (QMC) methods, which use statistical sampling to evaluate many-body wave functions, have the potential to answer this challenge. Owing to the few fundamental approximations made and the direct treatment of electron correlation, QMC methods are among the most accurate electronic structure methods available to date. We assess the accuracy of the diffusion Monte Carlo method in the case of rocksalt manganese oxide (MnO). We study the electronic properties of this strongly-correlated oxide, which has been identified as a suitable candidate for many applications ranging from catalysts to electronic devices. ``This work was supported by the U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Sciences and Engineering Division.'' Ab initio quantum Monte Carlo calculations of ground-state properties of manganese's oxides.

  13. Toward extending photosynthetic biosignatures: quantum dynamics calculation of light harvesting complexes

    NASA Astrophysics Data System (ADS)

    Komatsu, Yu; Umemura, Masayuki; Shoji, Mitsuo; Kayanuma, Megumi; Yabana, Kazuhiro; Shiraishi, Kenji

    For detecting life from reflectance spectra on extrasolar planets, several indicators called surface biosignatures have been proposed. One of them is the vegetation red edge (VRE) which derives from surface vegetation. VRE is observed in 700-750 nm on the Earth, but there is no guarantee that exovegetation show the red edge in this wavelength. Therefore it is necessary to check the validity of current standards of VRE as the signatures. In facts, M stars (cooler than Sun) will be the main targets in future missions, it is significantly important to know on the fundamental mechanisms in photosynthetic organism such as purple bacteria which absorb longer wavelength radiation. We investigated light absorptions and excitation energy transfers (EETs) in light harvesting complexes in purple bacteria (LH2s) by using quantum dynamics simulations. In LH2, effective EET is accomplished by corporative electronic excitation of the pigments. In our theoretical model, a dipole-dipole approximation was used for the electronic interactions between pigment excitations. Quantum dynamics simulations were performed according to Liouville equation to examine the EET process. The calculated oscillator strength and the transfer time between LH2 were good agreement with the experimental values. As the system size increases, the absorption bands shifted longer and the transfer velocities became larger. When two pigments in a LHC were exchanged to another pigments with lower excitation energy, faster and intensive light collection were observed.

  14. Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms

    SciTech Connect

    Song, Lei; Avoird, Ad van der; Karman, Tijs; Groenenboom, Gerrit C.; Balakrishnan, N.

    2015-05-28

    We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 − 30 to v′ = 0, j′ are calculated using the close coupling method for collision energies between 0.1 and 15 000 cm{sup −1} based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v′ = 0, j′ are reported for the first time at this level of theory. Also calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H–CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H–CO collisions in astrophysical models.

  15. Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms

    NASA Astrophysics Data System (ADS)

    Song, Lei; Balakrishnan, N.; van der Avoird, Ad; Karman, Tijs; Groenenboom, Gerrit C.

    2015-05-01

    We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 - 30 to v' = 0, j' are calculated using the close coupling method for collision energies between 0.1 and 15 000 cm-1 based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v' = 0, j' are reported for the first time at this level of theory. Also calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H-CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H-CO collisions in astrophysical models.

  16. Quantum scattering calculations for ro-vibrational de-excitation of CO by hydrogen atoms.

    PubMed

    Song, Lei; Balakrishnan, N; van der Avoird, Ad; Karman, Tijs; Groenenboom, Gerrit C

    2015-05-28

    We present quantum-mechanical scattering calculations for ro-vibrational relaxation of carbon monoxide (CO) in collision with hydrogen atoms. Collisional cross sections of CO ro-vibrational transitions from v = 1, j = 0 - 30 to v' = 0, j' are calculated using the close coupling method for collision energies between 0.1 and 15,000 cm(-1) based on the three-dimensional potential energy surface of Song et al. [J. Phys. Chem. A 117, 7571 (2013)]. Cross sections of transitions from v = 1, j ≥ 3 to v' = 0, j' are reported for the first time at this level of theory. Also calculations by the more approximate coupled states and infinite order sudden (IOS) methods are performed in order to test the applicability of these methods to H-CO ro-vibrational inelastic scattering. Vibrational de-excitation rate coefficients of CO (v = 1) are presented for the temperature range from 100 K to 3000 K and are compared with the available experimental and theoretical data. All of these results and additional rate coefficients reported in a forthcoming paper are important for including the effects of H-CO collisions in astrophysical models. PMID:26026443

  17. A formula for calculating theoretical photoelectron fluxes resulting from the He/+/ 304 A solar spectral line

    NASA Technical Reports Server (NTRS)

    Richards, P. G.; Torr, D. G.

    1981-01-01

    A simplified method for the evaluation of theoretical photoelectron fluxes in the upper atmosphere resulting from the solar radiation at 304 A is presented. The calculation is based on considerations of primary and cascade (secondary) photoelectron production in the two-stream model, where photoelectron transport is described by two electron streams, one moving up and one moving down, and of loss rates due to collisions with neutral gases and thermal electrons. The calculation is illustrated for the case of photoelectrons at an energy of 24.5 eV, and it is noted that the 24.5-eV photoelectron flux may be used to monitor variations in the solar 304 A flux. Theoretical calculations based on various ionization and excitation cross sections of Banks et al. (1974) are shown to be in generally good agreement with AE-E measurements taken between 200 and 235 km, however the use of more recent, larger cross sections leads to photoelectron values a factor of two smaller than observations but in agreement with previous calculations. It is concluded that a final resolution of the photoelectron problem may depend on a reevaluation of the inelastic electron collision cross sections.

  18. Evolution of Black Carbon Optical Properties during Atmospheric Aging: Comparison Between Theoretical Calculations and Laboratory Experiments

    NASA Astrophysics Data System (ADS)

    He, C.; Liou, K. N.; Takano, Y.; Li, Q.; Yang, P.; Zhang, R.

    2014-12-01

    The optical properties of black carbon (BC) are significantly affected by its aging process in the atmosphere. We have built a conceptual model defining three BC aging stages, including freshly emitted BC aggregates, coating by soluble material and hygroscopic growth. We apply an improved geometric-optics surface-wave approach (Liou et al., 2011; Takano et al., 2013) to calculate the absorption and scattering properties of BC at each stage and compare the theoretical results with those obtained from laboratory experiments (Zhang et al., 2008; Khalizov et al., 2009). Preliminary results show a general agreement between calculated and measured BC absorption cross sections (bias < 10%) and scattering cross sections (bias < 30%) for BC aerosols with mobility diameters of 155, 245 and 320 nm at Stages 1 and 2, where BC is coated by sulfuric acid and its water solution, respectively. We find that the calculated scattering and absorption cross sections for fresh BC aggregates (Stage 0) with different sizes are invariably larger than experimental results partly because of the uncertainty in theoretical calculations for BC with size parameters less than 1. It appears that the uncertainty in the experiment could also contribute to the discrepancy, considering that the measuring instrument missed some scattering in certain angles (0-7° and 170-180°). Finally, we will apply the conceptual model and the single-scattering results to assess the effects of BC aging processes on direct radiative forcing using observed BC vertical profiles.

  19. Evaluation of steam sterilization processes: comparing calculations using temperature data and biointegrator reduction data and calculation of theoretical temperature difference.

    PubMed

    Lundahl, Gunnel

    2007-01-01

    When calculating of the physical F121.1 degrees c-value by the equation F121.1 degrees C = t x 10(T-121.1/z the temperature (T), in combination with the z-value, influences the F121.1 degrees c-value exponentially. Because the z-value for spores of Geobacillus stearothermophilus often varies between 6 and 9, the biological F-value (F(Bio) will not always correspond to the F0-value based on temperature records from the sterilization process calculated with a z-value of 10, even if the calibration of both of them are correct. Consequently an error in calibration of thermocouples and difference in z-values influences the F121.1 degrees c-values logarithmically. The paper describes how results from measurements with different z-values can be compared. The first part describes the mathematics of a calculation program, which makes it easily possible to compare F0-values based on temperature records with the F(BIO)-value based on analysis of bioindicators such as glycerin-water-suspension sensors. For biological measurements, a suitable bioindicator with a high D121-value can be used (such a bioindicator can be manufactured as described in the article "A Method of Increasing Test Range and Accuracy of Bioindicators-Geobacillus stearothermophilus Spores"). By the mathematics and calculations described in this macro program it is possible to calculate for every position the theoretical temperature difference (deltaT(th)) needed to explain the difference in results between the thermocouple and the biointegrator. Since the temperature difference is a linear function and constant all over the process this value is an indication of the magnitude of an error. A graph and table from these calculations gives a picture of the run. The second part deals with product characteristics, the sterilization processes, loading patterns. Appropriate safety margins have to be chosen in the development phase of a sterilization process to achieve acceptable safety limits. Case studies are discussed and experiences are shared. PMID:17390699

  20. Theoretical calculation of positron affinities of solute clusters in aluminum alloys

    NASA Astrophysics Data System (ADS)

    Mizuno, Masataka; Araki, Hideki; Shirai, Yasuharu

    2016-01-01

    We have performed theoretical calculations of positron states for solute clusters in aluminum alloys to estimate the positron affinity of solute clusters. Positron states of solute clusters in aluminum alloys were calculated under the electronic structures obtained by first- principles molecular orbital calculations using Al158-X13 clusters. We defined the positron affinity of the solute clusters by the difference in the lowest potential sensed by positrons between the solute clusters and Al bulk. With increasing atomic number of 3d metals, the annihilation fraction of the solute clusters rapidly increases at Mn and shows a maximum at Ni. A similar trend is observed for 4d metals. The localization of positron at the solute clusters mainly arises from charge transfer from Al matrix to solute clusters. The positron affinity defined in this work well represents the localization of positron at the solute clusters in aluminum alloys.

  1. The calculation of theoretical chromospheric models and the interpretation of solar spectra from rockets and spacecraft

    NASA Technical Reports Server (NTRS)

    Avrett, E. H.

    1984-01-01

    Models and spectra of sunspots were studied, because they are important to energy balance and variability discussions. Sunspot observations in the ultraviolet region 140 to 168 nn was obtained by the NRL High Resolution Telescope and Spectrograph. Extensive photometric observations of sunspot umbrae and prenumbrae in 10 chanels covering the wavelength region 387 to 3800 nm were made. Cool star opacities and model atmospheres were computed. The Sun is the first testcase, both to check the opacity calculations against the observed solar spectrum, and to check the purely theoretical model calculation against the observed solar energy distribution. Line lists were finally completed for all the molecules that are important in computing statistical opacities for energy balance and for radiative rate calculations in the Sun (except perhaps for sunspots). Because many of these bands are incompletely analyzed in the laboratory, the energy levels are not well enough known to predict wavelengths accurately for spectrum synthesis and for detailed comparison with the observations.

  2. Synthesis, crystal structure, vibrational spectra and theoretical calculation of 1-carboxymethyl-3-methylimidazolium chloride.

    PubMed

    Xuan, Xiaopeng; Wang, Na; Xue, Zaikun

    2012-10-01

    In this paper, the structure of 1-carboxymethyl-3-methylimidazolium chloride was studied by X-ray diffraction, density functional theory, and FT-IR and Raman spectroscopic techniques for the first time. Title compound crystallizes in the orthorhombic space group Pca2(1) with the cell dimensions a=13.445 (6) , b=6.382 (3) , c=9.727 (5) and V=834.6 (7) (3). All the geometrical parameters have been calculated using by B3LYP with 6-311G++(d,p) basis set. Optimized geometries have been compared with the experimental data, and the hydrogen bond and short contact interactions were discussed. The vibrational frequencies, infrared intensities and Raman scattering activities of the title compound were calculated at the same level. The observed bands were assigned based on the theoretical calculations. The scaled vibrational frequencies seem to coincide with the experimental data with acceptable deviations. PMID:22728234

  3. Raman and infrared spectra and theoretical calculations of dipicolinic acid, dinicotinic acid, and their dianions

    NASA Astrophysics Data System (ADS)

    McCann, Kathleen; Laane, Jaan

    2008-11-01

    The Raman and infrared spectra of dipicolinic acid (DPA) and dinicotinic acid (DNic) and their salts (CaDPA, Na 2DPA, and CaDNic) have been recorded and the spectra have been assigned. Ab initio and DFT calculations were carried out to predict the structures and vibrational spectra and were compared to the experimental results. Because of extensive intermolecular hydrogen bonding in the crystals of these molecules, the calculated structures and spectra for the individual molecules agree only moderately well with the experimental values. Theoretical calculations were also carried out for DPA dimers and DPA·2H 2O to better understand the intermolecular interactions. The spectra do show that DPA and its calcium salt, which are present in anthrax spores, can be distinguished from the very similar DNic and CaDNic.

  4. A theoretical model for quantum nanostructures electronic wave functions, magnetic field effects

    NASA Astrophysics Data System (ADS)

    Even, J.; Cornet, C.; Loualiche, S.

    2005-09-01

    Analytical solutions of electronic wave functions in symmetric quantum ring (QR), quantum wire (QWR) and quantum dots (QD) structures are given using a parabolic coordinates system. The solutions for low-energy states are combinations of Bessel functions. The density of states of perfect 1D QR and QWR are shown to be equivalent. The continuous evolution from a 0D QD to a perfect 1D QR can be precisely described. The sharp variation of electronic properties, related to the build up of a potential energy barrier at the early stage of the QR formation, is studied analytically. Paramagnetic and diamagnetic couplings to a magnetic field are computed for QR and QD. It is shown theoretically that magnetic field induces an oscillation of the magnetization in QR.

  5. Single vs. Cumulative Grain Size Distribution: Effects on Theoretical Reflectance Calculations

    NASA Astrophysics Data System (ADS)

    King, T. V. V.; Calvin, W. M.

    1995-09-01

    We are developing a new approach to quantitative spectral characterization of remotely sensed objects. The work is an iterative and integrated theoretical and laboratory investigation. We are relating the spectral signature of the two types of carbonaceous chondrites (CV and CM) with their chemistry, mineralogy, and grain size distribution. In the future, the laboratory and theoretical portions of the study will be related to remote observations of asteroid surfaces. Radiative theory is being used to model the laboratory reflectance spectra of members of each of the two classes of carbonaceous chondrites (the theoretical mixtures will be generated using the known chemistry, mineralogy, optical constants and grain size distributions which have been previously determined) and verify the goodness of fit of the theoretical models to the laboratory spectra of meteorites. In using theoretical modeling assumptions about the physical and chemical properties of materials must be made. For the wavelength range we intend to consider (0.2-5 micrometers), we have previously obtained reasonable results using optical constants derived from reflectance spectra. That is, using a powdered sample in a narrow grain size range we invert a Hapke-based theoretical reflectance calculation to obtain an absorption coefficient. The primary disadvantage to this method is that it requires an assumption regarding the behavior of the index of refraction. However, as the index typically does not vary strongly in this wavelength interval, this is a reasonable assumption. Assumptions about the grain size of the materials being modelled are also important considerations when using Hapke-based theoretical modeling techniques. Commonly a single grain size range is deemed appropriate for a specific calculation and from that range an average grain size is estimated for the material. However, as most materials, including planetary regoliths and meteorites, are not composed of single mineralogies or single particle grain sizes we have investigated the disadvantages of making assumptions about a single grain size to represent the entire grain size distribution. For this preliminary study we selected pyroxene separates that were ground into narrow size intervals and for which an average grain size for each interval had been determined by Scanning Electron Microscope. Using a Hapke-based theoretical model we calculated the absorption coefficient. Then using a cumulative power-law distribution we calculated an absorption coefficient of the mixture. The average grain size of the cumulative distribution was determined to be 51.8 micrometers. This compound absorption coefficient was then used to compute a reflectance spectra of the pyroxene with a grain size of 52 micrometers. This spectrum was compared with the theoretical spectrum of the pyroxene in which the size distribution was a single size interval with an average grain size of 52 micrometers. Differences in the strengths of the resulting 2 micrometers absorption feature were nearly 7%, although no change was observed in the 1 micrometer absorption feature. Thus, suggesting that using a single grain size value to determine the absorption coefficient of a poly-grain size material needs to be reevaluated. Deriving the absorption coefficient based on a cumulative power-law distribution rather than a single average grain size is necessary, especially in multi-component mixtures where each mineral component, whether it is in the matrix or appears as an inclusion or chondrule, will likely have a unique grain size distribution. When modelling surfaces or materials with several mineralogic materials present, the failure to consider a cumulative size distribution will effect the estimates of mineral abundances.

  6. Theoretical performance of solar cell based on mini-bands quantum dots

    SciTech Connect

    Aly, Abou El-Maaty M. E-mail: ashraf.nasr@gmail.com; Nasr, A. E-mail: ashraf.nasr@gmail.com

    2014-03-21

    The tremendous amount of research in solar energy is directed toward intermediate band solar cell for its advantages compared with the conventional solar cell. The latter has lower efficiency because the photons have lower energy than the bandgap energy and cannot excite mobile carriers from the valence band to the conduction band. On the other hand, if mini intermediate band is introduced between the valence and conduction bands, then the smaller energy photons can be used to promote charge carriers transfer to the conduction band and thereby the total current increases while maintaining a large open circuit voltage. In this article, the influence of the new band on the power conversion efficiency for structure of quantum dots intermediate band solar cell is theoretically investigated and studied. The time-independent Schrödinger equation is used to determine the optimum width and location of the intermediate band. Accordingly, achievement of a maximum efficiency by changing the width of quantum dots and barrier distances is studied. Theoretical determination of the power conversion efficiency under the two different ranges of QD width is presented. From the obtained results, the maximum power conversion efficiency is about 70.42%. It is carried out for simple cubic quantum dot crystal under fully concentrated light. It is strongly dependent on the width of quantum dots and barrier distances.

  7. Theoretical Analysis About Quantum Noise Squeezing of Optical Fields From an Intracavity Frequency-Doubled Laser

    NASA Technical Reports Server (NTRS)

    Zhang, Kuanshou; Xie, Changde; Peng, Kunchi

    1996-01-01

    The dependence of the quantum fluctuation of the output fundamental and second-harmonic waves upon cavity configuration has been numerically calculated for the intracavity frequency-doubled laser. The results might provide a direct reference for the design of squeezing system through the second-harmonic-generation.

  8. Molecular structures of benzoic acid and 2-hydroxybenzoic acid, obtained by gas-phase electron diffraction and theoretical calculations.

    PubMed

    Aarset, Kirsten; Page, Elizabeth M; Rice, David A

    2006-07-20

    The structures of benzoic acid (C6H5COOH) and 2-hydroxybenzoic acid (C6H4OHCOOH) have been determined in the gas phase by electron diffraction using results from quantum chemical calculations to inform restraints used on the structural parameters. Theoretical methods (HF and MP2/6-311+G(d,p)) predict two conformers for benzoic acid, one which is 25.0 kJ mol(-1) (MP2) lower in energy than the other. In the low-energy form, the carboxyl group is coplanar with the phenyl ring and the O-H group eclipses the C=O bond. Theoretical calculations (HF and MP2/6-311+G(d,p)) carried out for 2-hydroxybenzoic acid gave evidence for seven stable conformers but one low-energy form (11.7 kJ mol(-1) lower in energy (MP2)) which again has the carboxyl group coplanar with the phenyl ring, the O-H of the carboxyl group eclipsing the C=O bond and the C=O of the carboxyl group oriented toward the O-H group of the phenyl ring. The effects of internal hydrogen bonding in 2-hydroxybenzoic acid can be clearly observed by comparison of pertinent structural parameters between the two compounds. These differences for 2-hydroxybenzoic acid include a shorter exocyclic C-C bond, a lengthening of the ring C-C bond between the substituents, and a shortening of the carboxylic single C-O bond. PMID:16836466

  9. Calculation of control coefficients of metabolic pathways. A flux-oriented graph-theoretic approach.

    PubMed Central

    Sen, A K

    1991-01-01

    Within the premises of the flux-oriented theory of Crabtree & Newsholme [(1987) Biochem. J. 247, 113-120], I have used a graph-theoretic approach for calculating the Control Coefficients of metabolic pathways. It is shown that a directed graph representing the control structure of a metabolic pathway can be constructed in a heuristic manner directly from the reaction diagram of the pathway, without the necessity of writing down the governing equations for the Control Coefficients. The Control Coefficients are derived from an analysis of the topology of the directed graph. The graph-theoretic approach also provides a visual framework for analysing the functional relationships of the individual enzymes. The control structures of the following pathways are examined here: (a) a simple unbranched pathway with four enzymes, (b) a simple branched pathway with three enzymes, and (c) a branched pathway with both carbon and energy (ATP) fluxes. PMID:1930155

  10. Theoretical calculation of the melting curve of Cu-Zr binary alloys

    DOE PAGESBeta

    Gunawardana, K. G.S.H.; Wilson, S. R.; Mendelev, M. I.; Song, Xueyu

    2014-11-14

    Helmholtz free energies of the dominant binary crystalline solids found in the Cu-Zr system at high temperatures close to the melting curve are calculated. This theoretical approach combines fundamental measure density functional theory (applied to the hard-sphere reference system) and a perturbative approach to include the attractive interactions. The studied crystalline solids are Cu(fcc), Cu51Zr14(β), CuZr(B2), CuZr2(C11b), Zr(hcp), and Zr(bcc). The calculated Helmholtz free energies of crystalline solids are in good agreement with results from molecular-dynamics (MD) simulations. Using the same perturbation approach, the liquid phase free energies are calculated as a function of composition and temperature, from which themore » melting curve of the entire composition range of this system can be obtained. Phase diagrams are determined in this way for two leading embedded atom method potentials, and the results are compared with experimental data. Furthermore, theoretical melting temperatures are compared both with experimental values and with values obtained directly from MD simulations at several compositions.« less

  11. Theoretical study of the electronic structure with dipole moment calculations of barium monofluoride

    NASA Astrophysics Data System (ADS)

    Tohme, Samir N.; Korek, Mahmoud

    2015-12-01

    The potential energy curves have been investigated for the 41 lowest doublet and quartet electronic states in the 2s+1Λ± representation below 55,000 cm-1 of the molecule BaF via CASSCF and MRCI (single and double excitations with Davidson correction) calculations. Twenty-five electronic states have been studied here theoretically for the first time. The crossing and avoided crossing of 20 doublet electronic states have been studied in the region 30,000-50,000 cm-1. The harmonic frequency ωe, the internuclear distance Re, the rotational constant Be, the electronic energy with respect to the ground state Te, and the permanent and transition dipole moments have been calculated in addition to static dipole polarizability of the ground state. By using the canonical functions approach, the eigenvalue Ev, the rotational constant Bv, and the abscissas of the turning points Rmin and Rmax have been calculated for the electronic states up to the vibrational level v=98. The comparison of these values with the theoretical results available in the literature shows a very good agreement.

  12. Theoretical calculation of the melting curve of Cu-Zr binary alloys

    SciTech Connect

    Gunawardana, K. G.S.H.; Wilson, S. R.; Mendelev, M. I.; Song, Xueyu

    2014-11-14

    Helmholtz free energies of the dominant binary crystalline solids found in the Cu-Zr system at high temperatures close to the melting curve are calculated. This theoretical approach combines fundamental measure density functional theory (applied to the hard-sphere reference system) and a perturbative approach to include the attractive interactions. The studied crystalline solids are Cu(fcc), Cu51Zr14(β), CuZr(B2), CuZr2(C11b), Zr(hcp), and Zr(bcc). The calculated Helmholtz free energies of crystalline solids are in good agreement with results from molecular-dynamics (MD) simulations. Using the same perturbation approach, the liquid phase free energies are calculated as a function of composition and temperature, from which the melting curve of the entire composition range of this system can be obtained. Phase diagrams are determined in this way for two leading embedded atom method potentials, and the results are compared with experimental data. Furthermore, theoretical melting temperatures are compared both with experimental values and with values obtained directly from MD simulations at several compositions.

  13. A simple theoretical approach to calculate the electrical conductivity of nonideal copper plasma

    SciTech Connect

    Zaghloul, Mofreh R.

    2008-04-15

    A simple theoretical approach to calculate the electrical conductivity of partially ionized nonideal copper plasma is introduced. The densities of plasma species are calculated, to machine accuracy, including electronic excitation and allowing for high ionization states up to the atomic number of the element. Depression of ionization energies is taken into account using an interpolation formula that is valid over a wide range of densities. The formula yields the results of the Debye-Hueckel and the ion-sphere models at the limiting boundaries of low and high densities, respectively. The nonideal Coulomb logarithm is represented by an analytic wide-range formula supplemented by a specially tailored cutoff parameter. Effects of excluding excited and high ionization states on the calculation of ionization equilibrium and electrical conductivity of copper are investigated and assessed. Computational results of the electrical conductivity are compared with results from other theoretical models and available experimental measurements and showed reasonable agreement. A discussion about the choice of the ion-sphere radius is included and concerns about thermodynamic inconsistency when using the modified nonideal Saha equations are discussed and cleared.

  14. Quantum entanglement of identical particles by standard information-theoretic notions.

    PubMed

    Lo Franco, Rosario; Compagno, Giuseppe

    2016-01-01

    Quantum entanglement of identical particles is essential in quantum information theory. Yet, its correct determination remains an open issue hindering the general understanding and exploitation of many-particle systems. Operator-based methods have been developed that attempt to overcome the issue. Here we introduce a state-based method which, as second quantization, does not label identical particles and presents conceptual and technical advances compared to the previous ones. It establishes the quantitative role played by arbitrary wave function overlaps, local measurements and particle nature (bosons or fermions) in assessing entanglement by notions commonly used in quantum information theory for distinguishable particles, like partial trace. Our approach furthermore shows that bringing identical particles into the same spatial location functions as an entangling gate, providing fundamental theoretical support to recent experimental observations with ultracold atoms. These results pave the way to set and interpret experiments for utilizing quantum correlations in realistic scenarios where overlap of particles can count, as in Bose-Einstein condensates, quantum dots and biological molecular aggregates. PMID:26857475

  15. Quantum entanglement of identical particles by standard information-theoretic notions

    NASA Astrophysics Data System (ADS)

    Lo Franco, Rosario; Compagno, Giuseppe

    2016-02-01

    Quantum entanglement of identical particles is essential in quantum information theory. Yet, its correct determination remains an open issue hindering the general understanding and exploitation of many-particle systems. Operator-based methods have been developed that attempt to overcome the issue. Here we introduce a state-based method which, as second quantization, does not label identical particles and presents conceptual and technical advances compared to the previous ones. It establishes the quantitative role played by arbitrary wave function overlaps, local measurements and particle nature (bosons or fermions) in assessing entanglement by notions commonly used in quantum information theory for distinguishable particles, like partial trace. Our approach furthermore shows that bringing identical particles into the same spatial location functions as an entangling gate, providing fundamental theoretical support to recent experimental observations with ultracold atoms. These results pave the way to set and interpret experiments for utilizing quantum correlations in realistic scenarios where overlap of particles can count, as in Bose-Einstein condensates, quantum dots and biological molecular aggregates.

  16. Quantum entanglement of identical particles by standard information-theoretic notions

    PubMed Central

    Lo Franco, Rosario; Compagno, Giuseppe

    2016-01-01

    Quantum entanglement of identical particles is essential in quantum information theory. Yet, its correct determination remains an open issue hindering the general understanding and exploitation of many-particle systems. Operator-based methods have been developed that attempt to overcome the issue. Here we introduce a state-based method which, as second quantization, does not label identical particles and presents conceptual and technical advances compared to the previous ones. It establishes the quantitative role played by arbitrary wave function overlaps, local measurements and particle nature (bosons or fermions) in assessing entanglement by notions commonly used in quantum information theory for distinguishable particles, like partial trace. Our approach furthermore shows that bringing identical particles into the same spatial location functions as an entangling gate, providing fundamental theoretical support to recent experimental observations with ultracold atoms. These results pave the way to set and interpret experiments for utilizing quantum correlations in realistic scenarios where overlap of particles can count, as in Bose-Einstein condensates, quantum dots and biological molecular aggregates. PMID:26857475

  17. Experimental investigation and theoretical calculation for 3He induced nuclear reactions on vanadium

    NASA Astrophysics Data System (ADS)

    Ali, B. M.; Al-Abyad, M.; Seddik, U.; El-Kameesy, S. U.; Ditrói, F.; Takács, S.; Tárkányi, F.

    2016-04-01

    Using stacked-foil activation technique and gamma-ray spectrometry, excitation functions for 3He induced nuclear reactions on natV were measured. Cross-sections for natV(3He, xn)52m,gMn and natV(3He, pxn)51Cr nuclear reactions were measured up to 27 MeV utilizing the MGC-20E cyclotron of ATOMKI. The measurements establish for the first time consistent excitation curves. Comparisons with results for values derived from different theoretical codes were included. Integral yield were calculated.

  18. Fast LiH Destruction in Reaction with H: Quantum Calculations and Astrophysical Consequences

    NASA Astrophysics Data System (ADS)

    Bovino, S.; Wernli, M.; Gianturco, F. A.

    2009-07-01

    We present a quantum-mechanical study of the exothermic 7LiH reaction with H. Accurate reactive probabilities and rate coefficients are obtained by solving the Schrödinger equation for the motion of the three nuclei on a single Born-Oppenheimer potential energy surface and using a coupled-channel hyperspherical coordinate method. Our new rates indeed confirm earlier, qualitative predictions and some previous theoretical calculations, as discussed in the main text. In the astrophysical domain, we find that the depletion process largely dominates for redshift (z) between 400 and 100, a range significant for early universe models. This new result from first-principle calculations leads us to definitively surmise that LiH should be already destroyed when the survival processes become important. Because of this very rapid depletion reaction, the fractional abundance of LiH is found to be drastically reduced, so that it should be very difficult to manage to observe it as an imprinted species in the cosmic background radiation. The present findings appear to settle the question of LiH observability in the early universe. We further report several state-to-state computed reaction rates in the same range of temperatures of interest for the present problem.

  19. Theoretical calculations of vibrational frequencies and rotational constants of the N 2O isotopomers

    NASA Astrophysics Data System (ADS)

    Zúñiga, José; Bastida, Adolfo; Requena, Alberto

    2003-01-01

    Theoretical values of vibrational frequencies and rotational constants for all the isotopomers of nitrous oxide are reported. The calculations are carried out variationally using an empirical Morse-cosine potential energy surface previously determined for N 2O, and a set of optimal internal vibrational coordinates. The spectroscopic constants obtained are compared to those extracted from spectroscopic measurements for the 14N216O, 14N15N16O, 15N14N16O, 15N216O, 14N217O, and 14N218O isotopomers. The agreement between calculated and observed values for these isotopomers is shown to be excellent, especially for the rotational constants. As a result, an unidentified band recently recorded is properly assigned. The spectroscopic constants computed for the rest of the isotopomers, for which observed information is much scarcer, have therefore a predictive character. The vibrational zero point energies for all the N 2O isotopomers are also given.

  20. Calculation of membrane bending rigidity using field-theoretic umbrella sampling.

    PubMed

    Smirnova, Y G; Müller, M

    2015-12-28

    The free-energy change of membrane shape transformations can be small, e.g., as in the case of membrane bending. Therefore, the calculation of the free-energy difference between different membrane morphologies is a challenge. Here, we discuss a computational method - field-theoretic umbrella sampling - to compute the local chemical potential of a non-equilibrium configuration and illustrate how one can apply it to study free-energy changes of membrane transformations using simulations. Specifically, the chemical potential profile of the bent membrane and the bending rigidity of membrane are calculated for a soft, coarse-grained amphiphile model and the MARTINI model of a dioleoylphosphatidylcholine (DOPC) membrane. PMID:26723640

  1. Calculation of membrane bending rigidity using field-theoretic umbrella sampling

    NASA Astrophysics Data System (ADS)

    Smirnova, Y. G.; Müller, M.

    2015-12-01

    The free-energy change of membrane shape transformations can be small, e.g., as in the case of membrane bending. Therefore, the calculation of the free-energy difference between different membrane morphologies is a challenge. Here, we discuss a computational method — field-theoretic umbrella sampling — to compute the local chemical potential of a non-equilibrium configuration and illustrate how one can apply it to study free-energy changes of membrane transformations using simulations. Specifically, the chemical potential profile of the bent membrane and the bending rigidity of membrane are calculated for a soft, coarse-grained amphiphile model and the MARTINI model of a dioleoylphosphatidylcholine (DOPC) membrane.

  2. Theoretical calculation of the low-lying electronic states of the molecule BN

    NASA Astrophysics Data System (ADS)

    Mahmoud, Salman; Bechelany, Mikhael; Miele, Philippe; Korek, Mahmoud

    2015-01-01

    The potential energy curves have been investigated for the 42 singlet, triplet, and quintet lowest electronic states in the (±) 2s+1 Λ representation below 95,000 cm-1 of the molecule BN via CASSCF and MRCI (singly and doubly excitation with Davidson correction) calculations. Eighteen electronic states have been investigated in the present work for the first time. The harmonic frequency ωe, the internuclear distance Re, the rotational constants Be, the electronic energy with respect to the ground state Te, and the static dipole moment have been calculated. A very good agreement has been noticed by comparing the present results with those reported in the literature, theoretically as well as experimentally.

  3. Quantum chemical calculation of the equilibrium structures of small metal atom clusters

    NASA Technical Reports Server (NTRS)

    Kahn, L. R.

    1982-01-01

    Metal atom clusters are studied based on the application of ab initio quantum mechanical approaches. Because these large 'molecular' systems pose special practical computational problems in the application of the quantum mechanical methods, there is a special need to find simplifying techniques that do not compromise the reliability of the calculations. Research is therefore directed towards various aspects of the implementation of the effective core potential technique for the removal of the metal atom core electrons from the calculations.

  4. Theoretical calculation of nitrogen isotope equilibrium exchange fractionation factors for various NOy molecules

    NASA Astrophysics Data System (ADS)

    Walters, Wendell W.; Michalski, Greg

    2015-09-01

    The nitrogen stable isotope ratio (15N/14N) of nitrogen oxides (NOx = NO + NO2) and its oxidation products (NOy = NOx + PAN (peroxyacetyl nitrate = C2H3NO5) + HNO3 + NO3 + HONO + N2O5 + ⋯ + particulate nitrates) has been suggested as a tool for partitioning NOx sources; however, the impact of nitrogen (N) equilibrium isotopic fractionation on 15N/14N ratios during the conversion of NOx to NOy must also be considered, but few fractionation factors for these processes have been determined. To address this limitation, computational quantum chemistry calculations of harmonic frequencies, reduced partition function ratios (15β), and N equilibrium isotope exchange fractionation factors (αA/B) were performed for various gaseous and aqueous NOy molecules in the rigid rotor and harmonic oscillator approximations using the B3LYP and EDF2 density functional methods for the mono-substitution of 15N. The calculated harmonic frequencies, 15β, and αA/B are in good agreement with available experimental measurements, suggesting the potential to use computational methods to calculate αA/B values for N isotope exchange processes that are difficult to measure experimentally. Additionally, the effects of solvation (water) on 15β and αA/B were evaluated using the IEF-PCM model, and resulted in lower 15β and αA/B values likely due to the stabilization of the NOy molecules from dispersion interactions with water. Overall, our calculated 15β and αA/B values are accurate in the rigid rotor and harmonic oscillator approximations and will allow for the estimation of αA/B involving various NOy molecules. These calculated αA/B values may help to explain the trends observed in the N stable isotope ratio of NOy molecules in the atmosphere.

  5. Vibrational spectra and density functional theoretical calculations on the anti-neurodegenerative drug: Orphenadrine hydrochloride

    NASA Astrophysics Data System (ADS)

    Edwin, Bismi; Hubert Joe, I.

    2012-11-01

    Vibrational spectral analysis and quantum chemical computations based on density functional theory have been performed on the anti-neuro-degenerative drug Orphenadrine hydrochloride. The geometry, intermolecular hydrogen bond, and harmonic vibrational frequencies of the title molecule have been investigated with the help of B3LYP method. The calculated molecular geometry has been compared with the experimental data. The various intramolecular interactions have been exposed by natural bond orbital analysis. The distribution of Mulliken atomic charges and bending of natural hybrid orbitals also reflect the presence of intramolecular hydrogen bonding. The analysis of the electron density of HOMO and LUMO gives an idea of the delocalization and low value of energy gap indicates electron transport in the molecule and thereby bioactivity. Effective docking of the drug molecule with NMDA receptor subunit 3A also enhances its bioactive nature.

  6. A Calculation of Cosmological Scale from Quantum Coherence

    SciTech Connect

    Lindesay, J

    2004-07-23

    We use general arguments to examine the energy scales for which a quantum coherent description of gravitating quantum energy units is necessary. The cosmological dark energy density is expected to decouple from the Friedman-Lemaitre energy density when the Friedman-Robertson-Walker scale expansion becomes sub-luminal at R = c, at which time the usual microscopic interactions of relativistic quantum mechanics (QED, QCD, etc) open new degrees of freedom. We assume that these microscopic interactions cannot signal with superluminal exchanges, only superluminal quantum correlations. The expected gravitational vacuum energy density at that scale would be expected to freeze out due to the loss of gravitational coherence. We define the vacuum energy which generates this cosmological constant to be that of a zero temperature Bose condensate at this gravitational de-coherence scale. We presume a universality throughout the universe in the available degrees of freedom determined by fundamental constants during its evolution. Examining the reverse evolution of the universe from the present, long before reaching Planck scale dynamics one expects major modifications from the de-coherent thermal equations of state, suggesting that the pre-coherent phase has global coherence properties. Since the arguments presented involve primarily counting of degrees of freedom, we expect the statistical equilibrium states of causally disconnected regions of space to be independently identical. Thus, there is no horizon problem associated with the lack of causal influences between spatially separated regions in this approach. The scale of the amplitude of fluctuations produced during de-coherence of cosmological vacuum energy are found to evolve to values consistent with those observed in cosmic microwave background radiation and galactic clustering.

  7. Investigation on the Gas-Phase Decomposition of Trichlorfon by GC-MS and Theoretical Calculation

    PubMed Central

    Jiang, Kezhi; Zhang, Ningwen; Zhang, Hu; Wang, Jianmei; Qian, Mingrong

    2015-01-01

    The gas phase pyrolysis of trichlorfon was investigated by the on-line gas chromatography – mass spectrometry (GC-MS) pyrolysis and theoretical calculations. Two reaction channels were proposed in the pyrolytic reaction, by analyzing the detected pyrolytic products in the total ion chromatography, including 2,2,2-trichloroacetaldehyde, dimethyl phosphite, and dichlorvos. Theoretical calculations showed that there is an intramolecular hydrogen bond between the hydroxyl group and the phosphate O atom in trichlorfon, through which the hydroxyl H atom can be easily transferred to phosphate O atom to trigger two pyrolytic channels. In path-a, migration of H atom results in direct decomposition of trichlorfon to give 2,2,2-trichloroacetaldehyde and dimethyl phosphite in one step. In path-b, migration of H atom in trichlorfon is combined with formation of the O-P bond to give an intermediate, followed by HCl elimination to afford dichlorvos. Path-a is kinetically more favorable than path-b, which is consistent with the GC-MS results. PMID:25856549

  8. Theoretical calculation (DFT), Raman and surface-enhanced Raman scattering (SERS) study of ponceau 4R

    NASA Astrophysics Data System (ADS)

    Xie, Yunfei; Li, Yan; Sun, Yingying; Wang, Heya; Qian, He; Yao, Weirong

    2012-10-01

    Ponceau 4R is used as a coloring agent in many different products, such as food, drinks, medicines, cosmetics and tobacco. However, ponceau 4R also shows carcinogenic, teratogenic and mutagenic behavior in high doses. In this work, standard Raman, theoretical Raman and surface-enhanced Raman scattering (SERS) spectra have been used to investigate ponceau 4R. More specifically, density functional theory (DFT) calculations have been used to calculate the optimized Raman spectrum of ponceau 4R at the B3LYP/6-31G(d) level. This has provided a better understanding of the optimized geometry and vibrational frequencies of this dye. In addition, the experimental spectrum of ponceau 4R has been compared with the theoretical spectrum; good agreement was obtained. Finally, it has shown that using SERS the detection limit of the ponceau 4R solution can be as low as 5 μg/mL. This has been achieved by SERS measurements of ponceau 4R on a substrate of gold nanoparticles. The SERS peaks at 1030, 1236, 1356 and 1502 cm-1 were chosen as index for semi-quantitative analysis, showing that the SERS technique provided a useful ultrasensitive method for the detection of ponceau 4R.

  9. Synthesis, characterization, optical properties and theoretical calculations of 6-fluoro coumarin

    NASA Astrophysics Data System (ADS)

    Bai, Yihui; Du, Jinyan; Weng, Xuexiang

    6-Fluoro coumarin is synthesized and characterized by 1H NMR and 13C NMR. The optical properties of the title compound are investigated by UV-vis absorption and fluorescence emission spectra, the results show the title compound can absorb UV-vis light at 319, 269 and 215 nm, moreover it exhibits blue-purple fluorescence emission at 416 nm. Theoretical studies on molecular structure, infrared spectra (IR), nuclear magnetic resonance (1H NMR, 13C NMR) chemical shifts, UV-vis absorption and fluorescence emission of the synthesized compound have been worked out. Most chemical calculations were performed by density functional theory (DFT) method at the B3LYP/6-311G(d,p) level (NMR at B3LYP/Aug-CC-Pvdz level) using Gaussian 09 program. The compared results reveal that the scaled theoretical vibrational frequencies are in good accordance with the observed spectra; computational chemical shifts are consistent with the experimental values in most parts, except for some minor deviations; the UV-vis absorption calculated matches the experimental one very well, and the fluorescence emission spectrum is in good agreement with the experimental one when the solute-solvent hydrogen-bonding interaction is considered. These good coincidences prove that the computational methods selected can be used to predict these properties of other similar materials where it is difficult to arrive at experimental results.

  10. Uncertainties Associated with Theoretically Calculated N2-Broadened Half-Widths of H2O Lines

    NASA Technical Reports Server (NTRS)

    Ma, Q.; Tipping, R. H.; Gamache, R. R.

    2010-01-01

    With different choices of the cut-offs used in theoretical calculations, we have carried out extensive numerical calculations of the N2-broadend Lorentzian half-widths of the H2O lines using the modified Robert-Bonamy formalism. Based on these results, we are able to thoroughly check for convergence. We find that, with the low-order cut-offs commonly used in the literature, one is able to obtain converged values only for lines with large half-widths. Conversely, for lines with small half-widths, much higher cut-offs are necessary to guarantee convergence. We also analyse the uncertainties associated with calculated half-widths, and these are correlated as above. In general, the smaller the half-widths, the poorer the convergence and the larger the uncertainty associated with them. For convenience, one can divide all H2O lines into three categories, large, intermediate, and small, according to their half-width values. One can use this division to judge whether the calculated half-widths are converged or not, based on the cut-offs used, and also to estimate how large their uncertainties are. We conclude that with the current Robert- Bonamy formalism, for lines in category lone can achieve the accuracy requirement set by HITRAN, whereas for lines in category 3, it 'is impossible to meet this goal.

  11. Analytic and numerical calculations of quantum synchrotron spectra from relativistic electron distributions

    NASA Technical Reports Server (NTRS)

    Brainerd, J. J.; Petrosian, V.

    1987-01-01

    Calculations are performed numerically and analytically of synchrotron spectra for thermal and power-law electron distributions using the single-particle synchrotron power spectrum derived from quantum electrodynamics. It is found that the photon energy at which quantum effects appear is proportional to temperature and independent of field strength for thermal spectra; quantum effects introduce an exponential roll-off away from the classical spectra. For power law spectra, the photon energy at which quantum effects appear is inversely proportional to the magnetic field strength; quantum effects produce a steeper power law than is found classically. The results are compared with spectra derived from the classical power spectrum with an energy cutoff ensuring conservation of energy. It is found that an energy cutoff is generally an inadequate approximation of quantum effects for low photon energies and for thermal spectra, but gives reasonable results for high-energy emission from power-law electron distributions.

  12. Quantum-field-theoretical approach to phase-space techniques: Generalizing the positive-P representation

    SciTech Connect

    Plimak, L.I.; Fleischhauer, M.; Olsen, M.K.; Collett, M.J.

    2003-01-01

    We present an introduction to phase-space techniques (PST) based on a quantum-field-theoretical (QFT) approach. In addition to bridging the gap between PST and QFT, our approach results in a number of generalizations of the PST. First, for problems where the usual PST do not result in a genuine Fokker-Planck equation (even after phase-space doubling) and hence fail to produce a stochastic differential equation (SDE), we show how the system in question may be approximated via stochastic difference equations (S{delta}E). Second, we show that introducing sources into the SDE's (or S{delta}E's) generalizes them to a full quantum nonlinear stochastic response problem (thus generalizing Kubo's linear reaction theory to a quantum nonlinear stochastic response theory). Third, we establish general relations linking quantum response properties of the system in question to averages of operator products ordered in a way different from time normal. This extends PST to a much wider assemblage of operator products than are usually considered in phase-space approaches. In all cases, our approach yields a very simple and straightforward way of deriving stochastic equations in phase space.

  13. Thermochemical properties and contribution groups for ketene dimers and related structures from theoretical calculations.

    PubMed

    Morales, Giovanni; Martínez, Ramiro

    2009-07-30

    This research's main goals were to analyze ketene dimers' relative stability and expand group additivity value (GAV) methodology for estimating the thermochemical properties of high-weight ketene polymers (up to tetramers). The CBS-Q multilevel procedure and statistical thermodynamics were used for calculating the thermochemical properties of 20 cyclic structures, such as diketenes, cyclobutane-1,3-diones, cyclobut-2-enones and pyran-4-ones, as well as 57 acyclic base compounds organized into five groups. According to theoretical heat of formation predictions, diketene was found to be thermodynamically favored over cyclobutane-1,3-dione and its enol-tautomeric form (3-hydroxycyclobut-2-enone). This result did not agree with old combustion experiments. 3-Hydroxycyclobut-2-enone was found to be the least stable dimer and its reported experimental detection in solution may have been due to solvent effects. Substituted diketenes had lower stability than substituted cyclobutane-1,3-diones with an increased number of methyl substituents, suggesting that cyclobutane-1,3-dione type dimers are the major products because of thermodynamic control of alkylketene dimerization. Missing GAVs for the ketene dimers and related structures were calculated through linear regression on the 57 acyclic base compounds. Corrections for non next neighbor interactions (such as gauche, eclipses, and internal hydrogen bond) were needed for obtaining a highly accurate and precise regression model. To the best of our knowledge, the hydrogen bond correction for GAV methodology is the first reported in the literature; this correction was correlated to MP2/6-31Gdagger and HF/6-31Gdagger derived geometries to facilitate its application. GAVs assessed by the linear regression model were able to reproduce acyclic compounds' theoretical thermochemical properties and experimental heat of formation for acetylacetone. Ring formation and substituent position corrections were calculated by consecutively replacing the GAVs regarding the 20 cyclic structures' thermochemical properties. PMID:19572711

  14. Regioselective enzymatic acylations of polyhydroxylated eudesmanes: semisynthesis, theoretical calculations, and biotransformation of cyclic sulfites.

    PubMed

    García-Granados, A; Melguizo, E; Parra, A; Simeó, Y; Viseras, B; Dobado, J A; Molina, J; Arias, J M

    2000-12-01

    Different lipase enzymes have been tested in order to perform regioselective acetylations on the eudesmane tetrol from vulgarin. High yields (95%) of 1,12-diacetoxy derivative (4) were achieved in 1 h with Candida antarctica lipase (CAL). However, only the 12-acetyl derivative (6) was obtained in similar yield with Mucor miehei (MML) or Candida cylindracea (CCL) lipases. The enzymatic protection at C-1 and C-12 has been used to form eudesmane cyclic-sulfites between C-6 and C-4 atoms. The R/S-sulfur configuration has been assigned by means of the experimental and theoretical (13)C and (1)H NMR chemical shifts. The theoretical shifts were calculated using the GIAO method, with a MM+ geometry optimization followed by a single-point calculation at the B3LYP/6-31G(*) level (B3LYP/6-31G(*)//MM+). Moreover, B3LYP/6-31G(*) geometry optimizations were carried out to test the B3LYP/6-31G(*)//MM+ results, for the deacetylated sulfites (12 and 15). In addition to the delta(C) and delta(H) shifts, the (3)J(HH) coupling constants were also calculated and compared with the experimental values when available. Finally, different reactivities have been checked in both sulfites by biotransformation with Rhizopus nigricans. While the R-sulfite gave 2 alpha- and 11 beta-hydroxylated metabolites, the S-sulfite yielded only regioselective deacetylations. Furthermore, both sulfites showed different reactivities in redox processes. PMID:11101376

  15. Quantum Monte Carlo calculation of reduced density matrices

    NASA Astrophysics Data System (ADS)

    Wagner, Lucas

    2012-02-01

    Quantum Monte Carlo(QMC) methods offer an efficient way to approximate the interacting ground state and some excited states of realistic model Hamiltonians based on the fundamental Coulomb interaction between electrons and nuclei. Many highly accurate results have been obtained using this method; however, it is often a challenge to extract the important correlations that the QMC wave function contains. I will describe some new results using the reduced density matrices(RDM's) to understand the electron correlation in the many-body wave function. The RDM's have both informative usage for describing correlation and pragmatic uses in further improving the variational wave function.

  16. Quantum chemical calculations for polymers and organic compounds

    NASA Technical Reports Server (NTRS)

    Lopez, J.; Yang, C.

    1982-01-01

    The relativistic effects of the orbiting electrons on a model compound were calculated. The computational method used was based on 'Modified Neglect of Differential Overlap' (MNDO). The compound tetracyanoplatinate was used since empirical measurement and calculations along "classical" lines had yielded many known properties. The purpose was to show that for large molecules relativity effects could not be ignored and that these effects could be calculated and yield data in closer agreement to empirical measurements. Both the energy band structure and molecular orbitals are depicted.

  17. Conformational and stereoeletronic investigations of muscarinic agonists of acetylcholine by NMR and theoretical calculations

    NASA Astrophysics Data System (ADS)

    da Silva, Julio Cesar A.; Ducati, Lucas C.; Rittner, Roberto

    2012-05-01

    NMR solvent effects and theoretical calculations showed muscarinic agonists present a large stability for their near synclinal conformations, indicating the presence of significant stabilization factors. Analysis of the results clearly indicated that this stability is not determined by the dihedral around the substituted C-C ethane bond, as stated by some authors, but a consequence of the geometry adopted in order to maximize N+/O interactions in this type of molecules. It can be assumed that acetylcholine and its muscarinic agonists exhibit their biologic activity when the positively charged nitrogen and the oxygen atoms are in the same side of the molecule within an interatomic distance ranging from 3.0 to 6.0 Å.

  18. Electron-Ion Recombination of Fe12 + Forming Fe11 +: Laboratory Measurements and Theoretical Calculations

    NASA Astrophysics Data System (ADS)

    Hahn, M.; Badnell, N. R.; Grieser, M.; Krantz, C.; Lestinsky, M.; Müller, A.; Novotný, O.; Repnow, R.; Schippers, S.; Wolf, A.; Savin, D. W.

    2014-06-01

    We have measured dielectronic recombination (DR) for Fe12 + forming Fe11 + using the heavy ion storage ring TSR located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. Using our results, we have calculated a plasma rate coefficient from these data that can be used for modeling astrophysical and laboratory plasmas. For the low temperatures characteristic of photoionized plasmas, the experimentally derived rate coefficient is orders of magnitude larger than the previously recommended atomic data. The existing atomic data were also about 40% smaller than our measurements at temperatures relevant for collisionally ionized plasmas. Recent state-of-the-art theory has difficulty reproducing the detailed energy dependence of the DR spectrum. However, for the Maxwellian plasma rate coefficient, recent theoretical results agree with our measurements to within about 30% for both photoionized and collisionally ionized plasmas.

  19. Quantum mechanical method of fragment's angular and energy distribution calculation for binary and ternary fission

    SciTech Connect

    Kadmensky, S. G. Titova, L. V.; Pen'kov, N. V.

    2006-08-15

    In the framework of quantum-mechanical fission theory, the method of calculation for partial fission width amplitudes and asymptotic behavior of the fissile nucleus wave function with strong channel coupling taken into account has been suggested. The method allows one to solve the calculation problem of angular and energy distribution countation for binary and ternary fission.

  20. On the Theoretical Calculation of the Stability Line of an Axial-flow Compressor Stage

    NASA Astrophysics Data System (ADS)

    Benavides, Efrn M.

    2011-12-01

    Recently, an analytical model to calculate the stability of an axial-flow compressor rotor has been presented in the scientific literature. The range of validity of that theoretical characterization was supported by several lemmas and theorems. One of the main results was the definition of a dimensionless coefficient for determining the location of the stability line in the rotor map. In this work the mathematical structure of that solution is studied. As a result of this detailed study, a new stability theorem and a new stability coefficient are obtained. This stability coefficient is an improvement of the previous one since it is physically and mathematically well defined in all the operational points of the compressor map. As a consequence, the new model is able to capture the stall inception for rotors and stators as well as the full characteristic curve (pressure rise versus mass flow rate) including rotating stall and possibly reverse flow. It is proved, as a consequence of the restriction imposed by the Stability Theorem, that each local component (rotor or stator) has its own instability point and its own post-stall characteristic curve. This theoretical criterion for predicting the averaged characteristic curve is in good accord with the experimental data. The stability coefficient is also verified for a compressor stage. Finally, the model is shown to provide an adequate quantitative and qualitative description of the averaged stall line giving a physical explanation of the mechanism involved in the instable region of the compressor map.

  1. Isodesmic reaction for accurate theoretical pKa calculations of amino acids and peptides.

    PubMed

    Sastre, S; Casasnovas, R; Muñoz, F; Frau, J

    2016-04-20

    Theoretical and quantitative prediction of pKa values at low computational cost is a current challenge in computational chemistry. We report that the isodesmic reaction scheme provides semi-quantitative predictions (i.e. mean absolute errors of 0.5-1.0 pKa unit) for the pKa1 (α-carboxyl), pKa2 (α-amino) and pKa3 (sidechain groups) of a broad set of amino acids and peptides. This method fills the gaps of thermodynamic cycles for the computational pKa calculation of molecules that are unstable in the gas phase or undergo proton transfer reactions or large conformational changes from solution to the gas phase. We also report the key criteria to choose a reference species to make accurate predictions. This method is computationally inexpensive and makes use of standard density functional theory (DFT) and continuum solvent models. It is also conceptually simple and easy to use for researchers not specialized in theoretical chemistry methods. PMID:27052591

  2. Theoretical study and rate constant calculation of the CH2O+CH3 reaction

    NASA Astrophysics Data System (ADS)

    Liu, Jing-yao; Li, Ze-sheng; Wu, Jia-yan; Wei, Zhi-gang; Zhang, Gang; Sun, Chia-chung

    2003-10-01

    The potential energy surface of the CH2O+CH3 reaction is explored at the MP2/6-311++G(d,p), MP4SDQ/6-311G(d,p), and QCISD(T)/6-311+G(3df,2p) (single point) levels of theory. Theoretical calculations suggest that the major product channel (R1) is the hydrogen abstraction leading to the product P1 CHO+CH4 (R1), while the addition process leading to P2H+CH3CHO (R2) appears to be negligibly small. The calculated enthalpies and dissociation activation energies for CH3CH2O and CH3OCH2 radicals involved in the reaction are in line with the experimental values. Dual-level dynamics calculation is carried out for the direct hydrogen abstraction channel. The energy profile of (R1) is refined with the interpolated single-point energies (ISPE) method at the QCISD(T)//MP2 level. The rate constants, which are evaluated by canonical variational transition-state theory (CVT) including small-curvature tunneling (SCT) correction, are in good agreement with the available experimental data. It is shown that tunneling effect plays a significant role in the rate constant calculation; and as a result, the CVT/SCT rate constants exhibit typical non-Arrhenius behavior over a wide temperature range 300-2000 K. The three parameter expression is k=6.35×10-26 T4.4 exp(-2450/T) cm3 molecule-1 s-1.

  3. Geometry effects on quasi-particle inelastic scattering rate in a coupled-quantum-layers system at finite temperature: A theoretical study

    NASA Astrophysics Data System (ADS)

    Salavati-fard, T.; Rafee, V.

    2016-01-01

    Geometry effects on intra-layer inelastic scattering rate of interacting electrons in a coupled-quantum-wells structure, at finite temperature, is theoretically investigated. The random phase approximation is employed to calculate the dynamically screened electron-electron interactions at different temperatures, electron energies and densities. This study is limited to the electrons which are close to the Fermi level so that only quasi-particles contribute to the scattering rate. It is shown that while scattering rate increases slightly with increasing well separation, this effect weakens quickly and broadening tends to a certain limit which is the electron broadening in a single quantum layer. Moreover, the thickness effect in a coupled-quantum-wells structure shows a strong decreasing trend with increasing well width. While the electrons in the same layer make a substantial contribution to screening and as a result to inelastic scattering rate, the electrons in the adjacent layer play an important role, as well.

  4. Many-body calculation for charge transport through triangular quantum dot molecules

    NASA Astrophysics Data System (ADS)

    Chen, Chih-Chieh; Chang, Yia-Chung; Kuo, David M. T.

    2015-03-01

    We study the many-body effect of electron tunneling through the coupled quantum dots systems in the Coulomb blockade regime. Using the equation of motion method for the non-equilibrium Green's function, we calculate the charge current and conductance of junctions consisting of metallic electrodes and a few quantum dots. Many-particle correlation functions are explicitly solved numerically. Quantum phenomena like quantum interference, Coulomb blockade and spin blockade for the triangular quantum dot molecules are discussed. Our work suggests a new method for the modeling of the mesoscopic transport. This work was supported in part by the Ministry of Science and Technology, Taiwan under Contract Nos. NSC 101-2112-M-001-024-MY3 and NSC 103-2112-M-008-009-MY3.

  5. Photoabsorption measurements and theoretical calculations of the electronic state spectroscopy of propionic, butyric, and valeric acids.

    PubMed

    Vicente, A; Antunes, R; Almeida, D; Franco, I J A; Hoffmann, S V; Mason, N J; Eden, S; Duflot, D; Canneaux, S; Delwiche, J; Hubin-Franskin, M J; Limão-Vieira, P

    2009-07-21

    Absolute photoabsorption cross sections of propionic (C2H5COOH), butyric (C3H7COOH), and valeric (C4H9COOH) acids have been measured from the dissociative pi* <-- n(o) transition (beginning around 5.0 eV) up to 10.7 eV. This constitutes the first study of the neutral electronic states of propionic and butyric acids at energies above the pi* <-- n(o) band, while no previous spectroscopic data is available for valeric acid in the present range. The present assignments are supported by the first theoretical calculations of electronic transition energies and oscillator strengths for these organic acids. In addition, the excitation energies of the vibrational modes of propionic acid in its neutral electronic ground state and the vertical ionisation energies of all three molecules have been calculated for the first time. The He(I) photoelectron spectroscopy of propionic acid has been measured from 10 to 16 eV, revealing new fine structure in the first ionic band. PMID:19842491

  6. Conformational preferences for some 5-substituted 2-acetylthiophenes through infrared spectroscopy and theoretical calculations.

    PubMed

    Rittner, Roberto; Ducati, Lucas C; Tormena, Cláudio F; Fiorin, Barbara C; Braga, Carolyne B

    2011-09-01

    The s-cis-trans isomerisms of some derivatives of thiophene (2-acetyl, AT; 2-acetyl-5-bromo, ABT and 2-acetyl-5-chloro, ACT) were analyzed, using data from deconvolution of their carbonyl absorption bands in two solvents (CCl4 and CHCl3). These infrared data showed that the O,S-cis conformer largely predominates in the studied solvents and that the same occurs in the gas phase, as observed from theoretical calculations. The latter results were obtained using B3LYP/6-311++G(3df,3p) and MP2/6-311++G(3df,3p) levels of theory, with zero-point energy correction. Moreover, the use of the IEFPCM (Integral Equation Formalism Polarizable Continuum Model) to take into account the solvent effects, using the same levels of theory, confirmed the results observed from infrared data. Low temperature 13C NMR spectra in CS2/CD2Cl2 (-90 °C) and in acetone-d6 (-80°C) did not show pairs of signals for each carbon, due to the known low energy barrier (∼8 kcal mol(-1)) for the cis-trans interconversion. Data from NBO calculations show that the nO(2)→σS-C5* and nO(2)→σC2-C3* interactions occur only in the O,S-cis isomer and can explain its conformational preference. PMID:21620762

  7. Quantum robots and quantum computers

    SciTech Connect

    Benioff, P.

    1998-07-01

    Validation of a presumably universal theory, such as quantum mechanics, requires a quantum mechanical description of systems that carry out theoretical calculations and systems that carry out experiments. The description of quantum computers is under active development. No description of systems to carry out experiments has been given. A small step in this direction is taken here by giving a description of quantum robots as mobile systems with on board quantum computers that interact with different environments. Some properties of these systems are discussed. A specific model based on the literature descriptions of quantum Turing machines is presented.

  8. Machine learning of parameters for accurate semiempirical quantum chemical calculations

    SciTech Connect

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempirical OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.

  9. Machine learning of parameters for accurate semiempirical quantum chemical calculations

    DOE PAGESBeta

    Dral, Pavlo O.; von Lilienfeld, O. Anatole; Thiel, Walter

    2015-04-14

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempiricalmore » OM2 method using a set of 6095 constitutional isomers C7H10O2, for which accurate ab initio atomization enthalpies are available. The ML-OM2 results show improved average accuracy and a much reduced error range compared with those of standard OM2 results, with mean absolute errors in atomization enthalpies dropping from 6.3 to 1.7 kcal/mol. They are also found to be superior to the results from specific OM2 reparameterizations (rOM2) for the same set of isomers. The ML-SQC approach thus holds promise for fast and reasonably accurate high-throughput screening of materials and molecules.« less

  10. Stabilisation of a laser by the calculated quantum transition frequency

    SciTech Connect

    Bagaev, S N; Lugovoy, A A; Dmitriev, A K

    2008-01-31

    A method is proposed to stabilise the frequency of a He-Ne laser with an intracavity nonlinear absorption cell by the calculated frequency of the 7{yields}6 transition of F{sub 2}{sup (2)}P(7){nu}{sub 3} in methane. The long-term frequency stability and reproducibility are measured for a He-Ne/CH{sub 4} laser with a telescopic cavity. (control of laser radiation parameters)

  11. Theoretical calculating the thermodynamic properties of solid sorbents for CO{sub 2} capture applications

    SciTech Connect

    Duan, Yuhua

    2012-11-02

    Since current technologies for capturing CO{sub 2} to fight global climate change are still too energy intensive, there is a critical need for development of new materials that can capture CO{sub 2} reversibly with acceptable energy costs. Accordingly, solid sorbents have been proposed to be used for CO{sub 2} capture applications through a reversible chemical transformation. By combining thermodynamic database mining with first principles density functional theory and phonon lattice dynamics calculations, a theoretical screening methodology to identify the most promising CO{sub 2} sorbent candidates from the vast array of possible solid materials has been proposed and validated. The calculated thermodynamic properties of different classes of solid materials versus temperature and pressure changes were further used to evaluate the equilibrium properties for the CO{sub 2} adsorption/desorption cycles. According to the requirements imposed by the pre- and post- combustion technologies and based on our calculated thermodynamic properties for the CO{sub 2} capture reactions by the solids of interest, we were able to screen only those solid materials for which lower capture energy costs are expected at the desired pressure and temperature conditions. Only those selected CO{sub 2} sorbent candidates were further considered for experimental validations. The ab initio thermodynamic technique has the advantage of identifying thermodynamic properties of CO{sub 2} capture reactions without any experimental input beyond crystallographic structural information of the solid phases involved. Such methodology not only can be used to search for good candidates from existing database of solid materials, but also can provide some guidelines for synthesis new materials. In this presentation, we first introduce our screening methodology and the results on a testing set of solids with known thermodynamic properties to validate our methodology. Then, by applying our computational method to several different kinds of solid systems, we demonstrate that our methodology can predict the useful information to help developing CO{sub 2} capture Technologies.

  12. Spectroscopic analysis of cinnamic acid using quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Vinod, K. S.; Periandy, S.; Govindarajan, M.

    2015-02-01

    In this present study, FT-IR, FT-Raman, 13C NMR and 1H NMR spectra for cinnamic acid have been recorded for the vibrational and spectroscopic analysis. The observed fundamental frequencies (IR and Raman) were assigned according to their distinctiveness region. The computed frequencies and optimized parameters have been calculated by using HF and DFT (B3LYP) methods and the corresponding results are tabulated. On the basis of the comparison between computed and experimental results assignments of the fundamental vibrational modes are examined. A study on the electronic and optical properties; absorption wavelengths, excitation energy, dipole moment and frontier molecular orbital energies, were performed by HF and DFT methods. The alternation of the vibration pattern of the pedestal molecule related to the substitutions was analyzed. The 13C and 1H NMR spectra have been recorded and the chemical shifts have been calculated using the gauge independent atomic orbital (GIAO) method. The Mulliken charges, UV spectral analysis and HOMO-LUMO analysis of have been calculated and reported. The molecular electrostatic potential (MEP) was constructed.

  13. The theoretical apparatus of semantic realism: A new language for classical and quantum physics

    NASA Astrophysics Data System (ADS)

    Garola, Claudio; Solombrino, Luigi

    1996-09-01

    The standard interpretation of quantum physics (QP) and some recent generalizations of this theory rest on the adoption of a rerificationist theory of truth and meaning, while most proposals for modifying and interpreting QP in a “realistic” way attribute an ontological status to theoretical physical entities (ontological realism). Both terms of this dichotomy are criticizable, and many quantum paradoxes can be attributed to it. We discuss a new viewpoint in this paper (semantic realism, or briefly SR), which applies both to classical physics (CP) and to QP. and is characterized by the attempt of giving up verificationism without adopting ontological realism. As a first step, we construct a formalized observative language L endowed with a correspondence truth theory. Then, we state a set of axioms by means of L which hold both in CP and in QP. and construct a further language Lv which can express both testable and theoretical properties of a given physical system. The concepts of meaning and testability do not collapse in L and Le hence we can distinguish between semantic and pragmatic compatibility of physical properties and define the concepts of testability and conjoint testability of statements of L and Le. In this context a new metatheoretical principle (MGP) is stated, which limits the validity of empirical physical laws. By applying SR (in particular. MGP) to QP, one can interpret quantum logic as a theory of testability in QP, show that QP is semantically incomplete, and invalidate the widespread claim that contextuality is unavoidable in QP. Furthermore. SR introduces some changes in the conventional interpretation of ideal measurements and Heisenberg’s uncertainty principle.

  14. A theoretical analysis of the optical absorption properties in one-dimensional InAs/GaAs quantum dot superlattices

    SciTech Connect

    Kotani, Teruhisa; Birner, Stefan; Lugli, Paolo; Hamaguchi, Chihiro

    2014-04-14

    We present theoretical investigations of miniband structures and optical properties of InAs/GaAs one-dimensional quantum dot superlattices (1D-QDSLs). The calculation is based on the multi-band k·p theory, including the conduction and valence band mixing effects, the strain effect, and the piezoelectric effect; all three effects have periodic boundary conditions. We find that both the electronic and optical properties of the 1D-QDSLs show unique states which are different from those of well known single quantum dots (QDs) or quantum wires. We predict that the optical absorption spectra of the 1D-QDSLs strongly depend on the inter-dot spacing because of the inter-dot carrier coupling and changing strain states, which strongly influence the conduction and valence band potentials. The inter-miniband transitions form the absorption bands. Those absorption bands can be tuned from almost continuous (closely stacked QD case) to spike-like shape (almost isolated QD case) by changing the inter-dot spacing. The polarization of the lowest absorption peak for the 1D-QDSLs changes from being parallel to the stacking direction to being perpendicular to the stacking direction as the inter-dot spacing increases. In the case of closely stacked QDs, in-plane anisotropy, especially [110] and [11{sup ¯}0] directions also depend on the inter-dot spacing. Our findings and predictions will provide an additional degree of freedom for the design of QD-based optoelectronic devices.

  15. Feeding biomechanics and theoretical calculations of bite force in bull sharks (Carcharhinus leucas) during ontogeny.

    PubMed

    Habegger, Maria L; Motta, Philip J; Huber, Daniel R; Dean, Mason N

    2012-12-01

    Evaluations of bite force, either measured directly or calculated theoretically, have been used to investigate the maximum feeding performance of a wide variety of vertebrates. However, bite force studies of fishes have focused primarily on small species due to the intractable nature of large apex predators. More massive muscles can generate higher forces and many of these fishes attain immense sizes; it is unclear how much of their biting performance is driven purely by dramatic ontogenetic increases in body size versus size-specific selection for enhanced feeding performance. In this study, we investigated biting performance and feeding biomechanics of immature and mature individuals from an ontogenetic series of an apex predator, the bull shark, Carcharhinus leucas (73-285cm total length). Theoretical bite force ranged from 36 to 2128N at the most anterior bite point, and 170 to 5914N at the most posterior bite point over the ontogenetic series. Scaling patterns differed among the two age groups investigated; immature bull shark bite force scaled with positive allometry, whereas adult bite force scaled isometrically. When the bite force of C. leucas was compared to those of 12 other cartilaginous fishes, bull sharks presented the highest mass-specific bite force, greater than that of the white shark or the great hammerhead shark. A phylogenetic independent contrast analysis of anatomical and dietary variables as determinants of bite force in these 13 species indicated that the evolution of large adult bite forces in cartilaginous fishes is linked predominantly to the evolution of large body size. Multiple regressions based on mass-specific standardized contrasts suggest that the evolution of high bite forces in Chondrichthyes is further correlated with hypertrophication of the jaw adductors, increased leverage for anterior biting, and widening of the head. Lastly, we discuss the ecological significance of positive allometry in bite force as a possible "performance gain" early in the life history of C. leucas. PMID:23040789

  16. Quantum and quasiclassical calculations on the OH+CO --> CO2+H reaction

    NASA Astrophysics Data System (ADS)

    Clary, David C.; Schatz, George C.

    1993-09-01

    Scattering calculations on the OH+CO?CO2+H reaction are reported using both quantum and quasiclassical methods. The rotating bond approximation is used in the quantum calculations. This method explicitly treats the OH vibration and CO rotation in the reactants and the bending vibration and a local CO stretch in the CO2 product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to ab initio data is used. The quantum reaction probabilities are dominated by sharp resonances corresponding to vibrationally excited states of the HOCO complex formed in the reaction. The quantum and quasiclassical lifetimes of these resonances compare quite well with measurements made by Wittig et al. Calculations of differential cross sections, rate coefficients, and CO2 vibrational product distributions are also compared with experimental data. The comparisons of quantum and quasiclassical calculations for models that treat explicitly different numbers of degrees of freedom provide detailed insight into the dynamics of the OH+CO reaction.

  17. Nonadiabatic quantum dynamics calculations for the N + NH --> N(2) + H reaction.

    PubMed

    Yang, Huan; Hankel, M; Varandas, Antonio; Han, Keli

    2010-09-01

    Nonadiabatic quantum dynamics calculations on the two coupled potential energy surfaces (PESs) (1(2)A' and 2(2)A') and also adiabatic quantum calculations on the lowest adiabatic PES are reported for the title reaction. Reaction probabilities for total angular momenta, J, varying from 0 to 160, are calculated to obtain the integral cross section (ICS) for collision energies ranging from 0.05 to 1.0 eV. Calculations using both the close coupling and the Centrifugal Sudden (CS) approximation are carried out to evaluate the role of Coriolis coupling effects for this reaction. The results of the nonadiabatic calculations show that the nonadiabatic effects in the title reaction for the initial state of NH (v = 0, j = 0) could be neglected, at least in the collision energy range considered in this study. PMID:20607172

  18. Energetic factors determining the binding of type I inhibitors to c-Met kinase: experimental studies and quantum mechanical calculations

    PubMed Central

    Yu, Zhe; Ma, Yu-chi; Ai, Jing; Chen, Dan-qi; Zhao, Dong-mei; Wang, Xin; Chen, Yue-lei; Geng, Mei-yu; Xiong, Bing; Cheng, Mao-sheng; Shen, Jing-kang

    2013-01-01

    Aim: To decipher the molecular interactions between c-Met and its type I inhibitors and to facilitate the design of novel c-Met inhibitors. Methods: Based on the prototype model inhibitor 1, four ligands with subtle differences in the fused aromatic rings were synthesized. Quantum chemistry was employed to calculate the binding free energy for each ligand. Symmetry-adapted perturbation theory (SAPT) was used to decompose the binding energy into several fundamental forces to elucidate the determinant factors. Results: Binding free energies calculated from quantum chemistry were correlated well with experimental data. SAPT calculations showed that the predominant driving force for binding was derived from a sandwich ?? interaction with Tyr-1230. Arg-1208 was the differentiating factor, interacting with the 6-position of the fused aromatic ring system through the backbone carbonyl with a force pattern similar to hydrogen bonding. Therefore, a hydrogen atom must be attached at the 6-position, and changing the carbon atom to nitrogen caused unfavorable electrostatic interactions. Conclusion: The theoretical studies have elucidated the determinant factors involved in the binding of type I inhibitors to c-Met. PMID:24056705

  19. Theoretical calculations of nonlinear refraction and absorption coefficients of doped graphene

    NASA Astrophysics Data System (ADS)

    Margulis, Vl A.; Muryumin, E. E.; Gaiduk, E. A.

    2014-12-01

    In this study, we present the first theoretical predictions concerning the nonlinear refractive and absorptive properties of the doped graphene in which the Fermi energy {{E}F} of charge carriers (noninteracting massless Dirac fermions) is controlled by an external gate voltage. We base our study on the original perturbation theory technique developed by Genkin and Mednis (1968 Sov. Phys. JETP 27 609) for calculating the nonlinear-optical (NLO) response coefficients of bulk crystalline semiconductors with partially filled bands. Using a simple tight-binding model for the π-electron energy bands of graphene, we obtain analytic expressions for the nonlinear refractive index {{n}2}(ω ) and the nonlinear absorption coefficient {{α }2}(ω ) of the doped graphene at photon energies above twice the value of the Fermi energy (\\hbar ω \\gt 2{{E}F}). We show that in this spectral region, both the nonlinear refraction ant the nonlinear absorption are determined predominantly by the combined processes which simultaneously involve intraband and interband motion of π-electrons. Our calculations indicate that extremely large negative values of n2 (of the order of -{{10}-6} cm2 W-1) can be achieved in the graphene at a relatively low doping level (of about 1012 cm-2) provided that the excitation frequency slightly exceeds the threshold frequency corresponding to the onset of interband transitions. With a further increase of the radiation frequency, the {{n}2}(ω ) becomes positive and begins to decrease in its absolute magnitude. The peculiar frequency dispersion of n2 and a negative sign of the {{α }2} (absorption bleaching), as predicted by our theory, suggest that the doped graphene is a prospective NLO material to be used in practical optical switching applications.

  20. Postseismic viscoelastic surface deformation and stress. Part 1: Theoretical considerations, displacement and strain calculations

    NASA Technical Reports Server (NTRS)

    Cohen, S. C.

    1979-01-01

    A model of viscoelastic deformations associated with earthquakes is presented. A strike-slip fault is represented by a rectangular dislocation in a viscoelastic layer (lithosphere) lying over a viscoelastic half-space (asthenosphere). Deformations occur on three time scales. The initial response is governed by the instantaneous elastic properties of the earth. A slower response is associated with viscoelastic relaxation of the lithosphere and a yet slower response is due to viscoelastic relaxation of the asthenosphere. The major conceptual contribution is the inclusion of lithospheric viscoelastic properties into a dislocation model of earthquake related deformations and stresses. Numerical calculations using typical fault parameters reveal that the postseismic displacements and strains are small compared to the coseismic ones near the fault, but become significant further away. Moreover, the directional sense of the deformations attributable to the elastic response, the lithospheric viscoelastic softening, and the asthenospheric viscoelastic flow may differ and depend on location and model details. The results and theoretical arguments suggest that the stress changes accompanying lithospheric relaxation may also be in a different sense than and be larger than the strain changes.

  1. Path integral calculation of free energies: Quantum effects on the melting temperature of neon

    NASA Astrophysics Data System (ADS)

    Ramírez, R.; Herrero, C. P.; Antonelli, A.; Hernández, E. R.

    2008-08-01

    The path integral formulation has been combined with several methods to determine free energies of quantum many-body systems, such as adiabatic switching and reversible scaling. These techniques are alternatives to the standard thermodynamic integration method. A quantum Einstein crystal is used as a model to demonstrate the accuracy and reliability of these free energy methods in quantum simulations. Our main interest focuses on the calculation of the melting temperature of Ne at ambient pressure, taking into account quantum effects in the atomic dynamics. The free energy of the solid was calculated by considering a quantum Einstein crystal as reference state, while for the liquid, the reference state was defined by the classical limit of the fluid. Our findings indicate that, while quantum effects in the melting temperature of this system are small, they still amount to about 6% of the melting temperature, and are therefore not negligible. The particle density as well as the melting enthalpy and entropy of the solid and liquid phases at coexistence is compared to results obtained in the classical limit and also to available experimental data.

  2. Quantum-Chemical Calculation of Carbododecahedron Formation in Carbon Plasma.

    PubMed

    Poklonski, Nikolai A; Ratkevich, Sergey V; Vyrko, Sergey A

    2015-08-27

    The ground state of the molecule consisting of 10 carbon atoms in C10(rg) "ring" conformation and the energy of its metastable C10(st) "star" conformation are reported. The reaction coordinate for the isomeric transition C10(st) → C10(rg) was calculated using density functional theory (DFT) with UB3LYP/6-31G(d,p). It was established that a 5-fold symmetry axis is conserved in this isomeric transition. The total energy of the ring isomer is by 10.33 eV (9.16 eV as zero-point energy corrected) lower than that of the star isomer. The energy barrier for the transition from the metastable star state to the ring state is 2.87 eV (3.57 eV as zero-point energy corrected). An analysis of possible chemical reactions in carbon plasma involving C10(st) and C10(rg) and leading to the formation of C20 fullerenes was performed. It was revealed that the presence of the C10(st) conformation in the reaction medium is a necessary condition for C20 fullerene formation. It was shown that the presence of hydrogen atoms in carbon plasma and UV radiation accelerate the C10(st) → C10(rg) transition and thus suppress the C20 fullerene formation. PMID:26267290

  3. Pseudopotential-based electron quantum transport: Theoretical formulation and application to nanometer-scale silicon nanowire transistors

    NASA Astrophysics Data System (ADS)

    Fang, Jingtian; Vandenberghe, William G.; Fu, Bo; Fischetti, Massimo V.

    2016-01-01

    We present a formalism to treat quantum electronic transport at the nanometer scale based on empirical pseudopotentials. This formalism offers explicit atomistic wavefunctions and an accurate band structure, enabling a detailed study of the characteristics of devices with a nanometer-scale channel and body. Assuming externally applied potentials that change slowly along the electron-transport direction, we invoke the envelope-wavefunction approximation to apply the open boundary conditions and to develop the transport equations. We construct the full-band open boundary conditions (self-energies of device contacts) from the complex band structure of the contacts. We solve the transport equations and present the expressions required to calculate the device characteristics, such as device current and charge density. We apply this formalism to study ballistic transport in a gate-all-around (GAA) silicon nanowire field-effect transistor with a body-size of 0.39 nm, a gate length of 6.52 nm, and an effective oxide thickness of 0.43 nm. Simulation results show that this device exhibits a subthreshold slope (SS) of ˜66 mV/decade and a drain-induced barrier-lowering of ˜2.5 mV/V. Our theoretical calculations predict that low-dimensionality channels in a 3D GAA architecture are able to meet the performance requirements of future devices in terms of SS swing and electrostatic control.

  4. Theoretical studies of optical gain tuning by hydrostatic pressure in GaInNAs/GaAs quantum wells

    SciTech Connect

    Gladysiewicz, M.; Wartak, M. S.; Kudrawiec, R.

    2014-01-21

    In order to describe theoretically the tuning of the optical gain by hydrostatic pressure in GaInNAs/GaAs quantum wells (QWs), the optical gain calculations within kp approach were developed and applied for N-containing and N-free QWs. The electronic band structure and the optical gain for GaInNAs/GaAs QW were calculated within the 10-band kp model which takes into account the interaction of electron levels in the QW with the nitrogen resonant level in GaInNAs. It has been shown that this interaction increases with the hydrostatic pressure and as a result the optical gain for GaInNAs/GaAs QW decreases by about 40% and 80% for transverse electric and transverse magnetic modes, respectively, for the hydrostatic pressure change from 0 to 40 kilobars. Such an effect is not observed for N-free QWs where the dispersion of electron and hole energies remains unchanged with the hydrostatic pressure. This is due to the fact that the conduction and valence band potentials in GaInAs/GaAs QW scale linearly with the hydrostatic pressure.

  5. Molecular structure and nicotinic activity of arecoline. A gas electron diffraction study combined with theoretical calculations

    NASA Astrophysics Data System (ADS)

    Takeshima, Tsuguhide; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro

    2005-01-01

    The molecular structure of arecoline (methyl 1,2,5,6-tetrahydro-1-methylnicotinate, ? has been determined by gas electron diffraction. Diffraction patterns were taken at about 370 K. Structural constraints for the data analysis were obtained from MP2/6-31G** calculations. Vibrational mean amplitudes and shrinkage corrections were calculated from the force constants obtained from the gas-phase vibrational frequencies and the B3LYP/6-31G** calculations. The electron diffraction data were well reproduced by assuming the mixture of four conformers. The determined structural parameters ( rg (Å) and ∠ (°)) for the main conformer with 3 σ in parentheses are as follows: < rg(N-C ring)>=1.456(4); rg(N-C methyl)=1.451 (d.p.); rg(C dbnd6 C)=1.339(9); < rg(C-C)>=1.512(3); rg(O-C methyl)=1.434(5); rg(C(O)-O)=1.355 (d.p.); rg(C dbnd6 O)=1.209(4); the out-of-plane angle of the methyl group=50.3(23); ∠C ringN ringC ring=112.8(30); ∠N ringC ringC ring(H 2)=110.5(16); <∠C ringC ringC ring>=118.4(5); ∠C dbnd6 CC(O)=116.8(7); ∠CC dbnd6 O=127.6(9); ∠CC-O=109.8(8), where the angle brackets denote averaged values and d.p. denotes dependent parameters. Fixing the abundances of the minor conformers, Ax-s- cis and Ax-s- trans, at the theoretical values (13% in total), those of the Eq-s- cis and Eq-s- trans conformers were determined to be 46(16) and 41(16)%, respectively. Here Ax and Eq denote the axial and equatorial directions of the N-CH 3 bond and s- cis and s- trans show the orientation of the methoxycarbonyl group expressed by the configuration of the C dbnd6 O and C dbnd6 C bonds. The N⋯O carbonyl distances of the Eq-s- cis and Ax-s- cis conformers are 4.832(13) and 4.874(16) Å, respectively. They are close to the N⋯N distance of the most abundant conformer of nicotine, 4.885(6) Å, suggesting that the Eq-s- cis and Ax-s- cis conformers have nicotinic activity.

  6. Quantum calculations for the photodetachment cross sections of H- located between two walls

    NASA Astrophysics Data System (ADS)

    Zhao, H. J.; Ma, Z. J.; Du, M. L.

    2015-06-01

    We re-investigate the photodetachment cross sections of H- in a quantum well consisting of two parallel hard walls using a quantum approach. The formulas for the cross sections are explicitly derived and compared with those derived by using closed-orbit theory (G.C. Yang, et al., Physica B 404 (2009) 1576 [15]). The present quantum results confirm the staircase pattern of the cross sections obtained earlier when the polarization of photons is parallel to the normal direction of the walls. However, we find that when the polarization is perpendicular to the normal direction of the walls, oscillations in the cross sections in the present quantum calculations are still present in contrast to the predictions of closed-orbit theory. The differences in the two results are large enough to be observable.

  7. Quantum Humor: The Playful Side of Physics at Bohr's Institute for Theoretical Physics

    NASA Astrophysics Data System (ADS)

    Halpern, Paul

    2012-09-01

    From the 1930s to the 1950s, a period of pivotal developments in quantum, nuclear, and particle physics, physicists at Niels Bohr's Institute for Theoretical Physics in Copenhagen took time off from their research to write humorous articles, letters, and other works. Best known is the Blegdamsvej Faust, performed in April 1932 at the close of one of the Institute's annual conferences. I also focus on the Journal of Jocular Physics, a humorous tribute to Bohr published on the occasions of his 50th, 60th, and 70th birthdays in 1935, 1945, and 1955. Contributors included Léon Rosenfeld, Victor Weisskopf, George Gamow, Oskar Klein, and Hendrik Casimir. I examine their contributions along with letters and other writings to show that they offer a window into some issues in physics at the time, such as the interpretation of complementarity and the nature of the neutrino, as well as the politics of the period.

  8. Investigation of the ICT state of DPA-DSB using spectroscopic experiments and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    He, Xing; Wang, Yang; Liu, Weilong; Yang, Zhenling; Du, Xin; Liu, Yuqiang; Yang, Yanqiang

    2011-01-01

    The excited states of a symmetric D- π-D structure two-photon excited fluorescence material 1,4-di (4'- N, N-diphenylaminostyryl) benzene (DPA-DSB) have been investigated by spectroscopic experiments and quantum chemical calculations. The solvent polarity dependent fluorescence properties indicate that upon photoexcitation, a radiative intramolecular charge-transfer (ICT) state is formed resulting from the ICT process. The molecular structure does not have large change during the ICT process, which is confirmed by the quantum chemical calculations performed by G AUSSIAN 03 software. The planar structure of the fluorescent ICT state results in the high fluorescence quantum yield which is important in the two-photon excited fluorescence application.

  9. Information-theoretic security proof for quantum-key-distribution protocols

    SciTech Connect

    Renner, Renato; Gisin, Nicolas; Kraus, Barbara

    2005-07-15

    We present a technique for proving the security of quantum-key-distribution (QKD) protocols. It is based on direct information-theoretic arguments and thus also applies if no equivalent entanglement purification scheme can be found. Using this technique, we investigate a general class of QKD protocols with one-way classical post-processing. We show that, in order to analyze the full security of these protocols, it suffices to consider collective attacks. Indeed, we give new lower and upper bounds on the secret-key rate which only involve entropies of two-qubit density operators and which are thus easy to compute. As an illustration of our results, we analyze the Bennett-Brassard 1984, the six-state, and the Bennett 1992 protocols with one-way error correction and privacy amplification. Surprisingly, the performance of these protocols is increased if one of the parties adds noise to the measurement data before the error correction. In particular, this additional noise makes the protocols more robust against noise in the quantum channel.

  10. InAsSb /InP quantum dots for midwave infrared emitters: A theoretical study

    NASA Astrophysics Data System (ADS)

    Cornet, C.; Doré, F.; Ballestar, A.; Even, J.; Bertru, N.; Le Corre, A.; Loualiche, S.

    2005-12-01

    A theoretical study of the electronic properties of InAsSb quantum dots (QDs) deposited on InP substrate is presented. Unstrained bulk materials present a direct gap between 0.1and 0.35eV suitable for mid-infrared emitters (2-5μm). However, strain and quantum-confinement effects may limit the extension of the emission spectrum of these nanostructures towards the higher wavelengths. Various associations of materials in the barrier are considered. Among the possible associations, InAs0.5Sb0.5/GaAs0.5Sb0.5 QDs may provide a low-energy emission with a material system similar to the well-known InAs /GaAs system. Other materials associations such as InAsSb /InGaAsP/InP are also studied. Band lineups, optical transitions, optical losses, and effective masses are computed and discussed.

  11. An information-theoretic link between spacetime symmetries and quantum linearity

    NASA Astrophysics Data System (ADS)

    Parwani, Rajesh R.

    2005-02-01

    A nonlinear generalisation of Schrodinger's equation is obtained using information-theoretic arguments. The nonlinearities are controlled by an intrinsic length scale and involve derivatives to all orders thus making the equation mildly nonlocal. The nonlinear equation is homogeneous, separable, conserves probability, but is not invariant under spacetime symmetries. Spacetime symmetries are recovered when a dimensionless parameter is tuned to vanish, whereby linearity is simultaneously established and the length scale becomes hidden. It is thus suggested that if, in the search for a more basic foundation for Nature's Laws, an inference principle is given precedence over symmetry requirements, then the symmetries of spacetime and the linearity of quantum theory might both be emergent properties that are intrinsically linked. Supporting arguments are provided for this point of view and some testable phenomenological consequences are highlighted. The generalised Klien-Gordon and Dirac equations are also studied, leading to the suggestion that nonlinear quantum dynamics with intrinsically broken spacetime symmetries might be relevant to understanding the problem of neutrino mass (lessness) and oscillations: among other observations, this approach hints at the existence of a hidden discrete family symmetry in the Standard Model of particle physics.

  12. Semiclassical and quantum field theoretic bounds for traversable Lorentzian stringy wormholes

    SciTech Connect

    Nandi, Kamal Kanti; Zhang Yuanzhong; Kumar, K.B. Vijaya

    2004-09-15

    A lower bound on the size of a Lorentzian wormhole can be obtained by semiclassically introducing the Planck cutoff on the magnitude of tidal forces (Horowitz-Ross constraint). Also, an upper bound is provided by the quantum field theoretic constraint in the form of the Ford-Roman Quantum Inequality for massless minimally coupled scalar fields. To date, however, exact static solutions belonging to this scalar field theory have not been worked out to verify these bounds. To fill this gap, we examine the wormhole features of two examples from the Einstein frame description of the vacuum low energy string theory in four dimensions which is the same as the minimally coupled scalar field theory. Analyses in this paper support the conclusion of Ford and Roman that wormholes in this theory can have sizes that are indeed only a few order of magnitudes larger than the Planck scale. It is shown that the two types of bounds are also compatible. In the process, we point out a 'wormhole' analog of naked black holes.

  13. Low frequency internal vibrations of norbornane and its derivatives studied by IINS and quantum chemistry calculations

    SciTech Connect

    Holderna-Natkaniec, K.; Natkaniec, I.; Khavryutchenko, V. D.

    1999-06-15

    The observed and calculated INS vibrational densities of states for globular molecules of norbornane, norborneole and borneole are compared in the frequency range up to 600 cm{sup -1}. Inelastic incoherent neutron scattering (IINS) spectra were measured at ca. 20 K on the high resolution NERA spectrometer at the IBR-2 pulsed reactor. The IINS intensities were calculated by semi-empirical quantum chemistry method and the assignments of the low-frequency internal modes were proposed.

  14. Young’s modulus calculations for cellulose Iß by MM3 and quantum mechanics

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Quantum mechanics (QM) and molecular mechanics (MM) calculations were performed to elucidate Young’s moduli for a series of cellulose Iß models. Computations using the second generation empirical force field MM3 with a disaccharide cellulose model, 1,4'-O-dimethyl-ß-cellobioside (DMCB), and an analo...

  15. Methacrolein in the IR Atmospheric Window: Mm-Wave and FTIR Spectroscopies Complemented by Quantum Calculations

    NASA Astrophysics Data System (ADS)

    Zakharenko, Olena; Aviles Moreno, Juan-Ramon; Imane, Haykal; Motiyenko, R. A.; Huet, T. R.; Pirali, Olivier

    2014-06-01

    Methacrolein, CH_2=C(CH_3)CHO or MAC, is an important atmospheric molecule because it is a major product of the isoprene-OH reaction. Meanwhile the spectroscopic information on MAC is very scarse. On the theoretical side, we have performed quantum calculations at different levels of theory (DFT and ab initio) to model the structure of the two conformers, the large amplitude motion associated with the methyl top, and the anharmonic vibrational structure. On the experimental side, we have at first characterized the millimeter-wave spectrum of MAC in the 150-465 GHz range using the Lille frequency multiplication chain spectrometer. In particular the ground state has been analyzed up to J, K_a = 37, 17 and the first excited states are currently investigated. Secondly, FTIR spectra have been recorded on the AILES beamline of SOLEIL using a long path cell, between 30 and 3500 wn at medium resolution (0.5 wn). A few bands of atmospheric interest have also been recorded at higher resolution (0.001 wn). We will report the details of the vibrational analysis, as well as the molecular parameters derived from the analysis of the high resolution spectrum of the c-type band located around 930 wn. Support from the French Laboratoire d'Excellence CaPPA (Chemical and Physical Properties of the Atmosphere) through contract ANR-10-LABX-0005 of the Programme d'Investissements d'Avenir is acknowledged. The experiment on the AILES beam-line of the synchrotron SOLEIL was performed under project number 20130192. M. Suzuki and K. Kozima, J. Molec. Spectrosc. 38 (1971) 314 J. R. Durig, J. Qiu, B. Dehoff and T. S. Little, Spectrochimica Acta 42A (1986) 89

  16. Fragment quantum chemical approach to geometry optimization and vibrational spectrum calculation of proteins.

    PubMed

    Liu, Jinfeng; Zhang, John Z H; He, Xiao

    2016-01-21

    Geometry optimization and vibrational spectra (infrared and Raman spectra) calculations of proteins are carried out by a quantum chemical approach using the EE-GMFCC (electrostatically embedded generalized molecular fractionation with conjugate caps) method (J. Phys. Chem. A, 2013, 117, 7149). The first and second derivatives of the EE-GMFCC energy are derived and employed in geometry optimization and vibrational frequency calculations for several test systems, including a polypeptide ((GLY)6), an ?-helix (AKA), a ?-sheet (Trpzip2) and ubiquitin (76 residues with 1231 atoms). Comparison of the present results with those obtained from full system QM (quantum mechanical) calculations shows that the EE-GMFCC approach can give accurate molecular geometries, vibrational frequencies and vibrational intensities. The EE-GMFCC method is also employed to simulate the amide I vibration of proteins, which has been widely used for the analysis of peptide and protein structures, and the results are in good agreement with the experimental observations. PMID:26686896

  17. The potential, limitations, and challenges of divide and conquer quantum electronic structure calculations on energetic materials.

    SciTech Connect

    Tucker, Jon R.; Magyar, Rudolph J.

    2012-02-01

    High explosives are an important class of energetic materials used in many weapons applications. Even with modern computers, the simulation of the dynamic chemical reactions and energy release is exceedingly challenging. While the scale of the detonation process may be macroscopic, the dynamic bond breaking responsible for the explosive release of energy is fundamentally quantum mechanical. Thus, any method that does not adequately describe bonding is destined to lack predictive capability on some level. Performing quantum mechanics calculations on systems with more than dozens of atoms is a gargantuan task, and severe approximation schemes must be employed in practical calculations. We have developed and tested a divide and conquer (DnC) scheme to obtain total energies, forces, and harmonic frequencies within semi-empirical quantum mechanics. The method is intended as an approximate but faster solution to the full problem and is possible due to the sparsity of the density matrix in many applications. The resulting total energy calculation scales linearly as the number of subsystems, and the method provides a path-forward to quantum mechanical simulations of millions of atoms.

  18. Systematic study of finite-size effects in quantum Monte Carlo calculations of real metallic systems.

    PubMed

    Azadi, Sam; Foulkes, W M C

    2015-09-14

    We present a systematic and comprehensive study of finite-size effects in diffusion quantum Monte Carlo calculations of metals. Several previously introduced schemes for correcting finite-size errors are compared for accuracy and efficiency, and practical improvements are introduced. In particular, we test a simple but efficient method of finite-size correction based on an accurate combination of twist averaging and density functional theory. Our diffusion quantum Monte Carlo results for lithium and aluminum, as examples of metallic systems, demonstrate excellent agreement between all of the approaches considered. PMID:26374000

  19. Ab initio no core calculations of light nuclei and preludes to Hamiltonian quantum field theory

    SciTech Connect

    Vary, J.P.; Maris, P.; Shirokov, A.M.; Honkanen, H.; li, J.; Brodsky, S.J.; Harindranath, A.; Teramond, G.F.de; /Costa Rica U.

    2009-08-03

    Recent advances in ab initio quantum many-body methods and growth in computer power now enable highly precise calculations of nuclear structure. The precision has attained a level sufficient to make clear statements on the nature of 3-body forces in nuclear physics. Total binding energies, spin-dependent structure effects, and electroweak properties of light nuclei play major roles in pinpointing properties of the underlying strong interaction. Eventually,we anticipate a theory bridge with immense predictive power from QCD through nuclear forces to nuclear structure and nuclear reactions. Light front Hamiltonian quantum field theory offers an attractive pathway and we outline key elements.

  20. Ab initio no core calculations of light nuclei and preludes to Hamiltonian quantum field theory

    SciTech Connect

    Vary, J. P.; Maris, P.; Honkanen, H.; Li, J.; Shirokov, A. M.; Brodsky, S. J.; Harindranath, A.

    2009-12-17

    Recent advances in ab initio quantum many-body methods and growth in computer power now enable highly precise calculations of nuclear structure. The precision has attained a level sufficient to make clear statements on the nature of 3-body forces in nuclear physics. Total binding energies, spin-dependent structure effects, and electroweak properties of light nuclei play major roles in pinpointing properties of the underlying strong interaction. Eventually, we anticipate a theory bridge with immense predictive power from QCD through nuclear forces to nuclear structure and nuclear reactions. Light front Hamiltonian quantum field theory offers an attractive pathway and we outline key elements.

  1. Systematic study of finite-size effects in quantum Monte Carlo calculations of real metallic systems

    SciTech Connect

    Azadi, Sam Foulkes, W. M. C.

    2015-09-14

    We present a systematic and comprehensive study of finite-size effects in diffusion quantum Monte Carlo calculations of metals. Several previously introduced schemes for correcting finite-size errors are compared for accuracy and efficiency, and practical improvements are introduced. In particular, we test a simple but efficient method of finite-size correction based on an accurate combination of twist averaging and density functional theory. Our diffusion quantum Monte Carlo results for lithium and aluminum, as examples of metallic systems, demonstrate excellent agreement between all of the approaches considered.

  2. Single-step propagators for calculation of time evolution in quantum systems with arbitrary interactions

    NASA Astrophysics Data System (ADS)

    Gonoskov, Ivan; Marklund, Mattias

    2016-05-01

    We propose and develop a general method of numerical calculation of the wave function time evolution in a quantum system which is described by Hamiltonian of an arbitrary dimensionality and with arbitrary interactions. For this, we obtain a general n-order single-step propagator in closed-form, which could be used for the numerical solving of the problem with any prescribed accuracy. We demonstrate the applicability of the proposed approach by considering a quantum problem with non-separable time-dependent Hamiltonian: the propagation of an electron in focused electromagnetic field with vortex electric field component.

  3. A Theoretical Mechanism of Szilard Engine Function in Nucleic Acids and the Implications for Quantum Coherence in Biological Systems

    SciTech Connect

    Matthew Mihelic, F.

    2010-12-22

    Nucleic acids theoretically possess a Szilard engine function that can convert the energy associated with the Shannon entropy of molecules for which they have coded recognition, into the useful work of geometric reconfiguration of the nucleic acid molecule. This function is logically reversible because its mechanism is literally and physically constructed out of the information necessary to reduce the Shannon entropy of such molecules, which means that this information exists on both sides of the theoretical engine, and because information is retained in the geometric degrees of freedom of the nucleic acid molecule, a quantum gate is formed through which multi-state nucleic acid qubits can interact. Entangled biophotons emitted as a consequence of symmetry breaking nucleic acid Szilard engine (NASE) function can be used to coordinate relative positioning of different nucleic acid locations, both within and between cells, thus providing the potential for quantum coherence of an entire biological system. Theoretical implications of understanding biological systems as such 'quantum adaptive systems' include the potential for multi-agent based quantum computing, and a better understanding of systemic pathologies such as cancer, as being related to a loss of systemic quantum coherence.

  4. Theoretical Study of All-Electrical Quantum Wire Valley Filters in Bilayer Graphene

    NASA Astrophysics Data System (ADS)

    Wu, Yu-Shu; Lue, Ning-Yuan; Chen, Yen-Chun; Jiang, Jia-Huei; Chou, Mei-Yin

    Graphene electrons carry valley pseudospin, due to the double valley degeneracy in graphene band structure. In gapped graphene, the pseudospin is coupled to an in-plane electric field, through the mechanism of valley-orbit interaction (VOI), Based on the VOI, a family of electrically-controlled valleytronic devices have been proposed. Here, we report the theoretical study of a recently proposed valley filter consisting of a Q1D channel in bilayer graphene defined and controlled by electrical gates. We discuss two types of calculations - those of energy subband structure in the channel and electron transmission through a valley valve consisting of two proposed filters. For the former, we have developed a tight binding formulation in the continuum limit. For the latter, we employ the recursive Green's function method. Results from the calculations will be presented. Financial support by MoST, Taiwan, ROC is acknowledged.

  5. The Effect of Molecular Conformation on the Accuracy of Theoretical (1)H and (13)C Chemical Shifts Calculated by Ab Initio Methods for Metabolic Mixture Analysis.

    PubMed

    Chikayama, Eisuke; Shimbo, Yudai; Komatsu, Keiko; Kikuchi, Jun

    2016-04-14

    NMR spectroscopy is a powerful method for analyzing metabolic mixtures. The information obtained from an NMR spectrum is in the form of physical parameters, such as chemical shifts, and construction of databases for many metabolites will be useful for data interpretation. To increase the accuracy of theoretical chemical shifts for development of a database for a variety of metabolites, the effects of sets of conformations (structural ensembles) and the levels of theory on computations of theoretical chemical shifts were systematically investigated for a set of 29 small molecules in the present study. For each of the 29 compounds, 101 structures were generated by classical molecular dynamics at 298.15 K, and then theoretical chemical shifts for 164 (1)H and 123 (13)C atoms were calculated by ab initio quantum chemical methods. Six levels of theory were used by pairing Hartree-Fock, B3LYP (density functional theory), or second order Møller-Plesset perturbation with 6-31G or aug-cc-pVDZ basis set. The six average fluctuations in the (1)H chemical shift were ±0.63, ± 0.59, ± 0.70, ± 0.62, ± 0.75, and ±0.66 ppm for the structural ensembles, and the six average errors were ±0.34, ± 0.27, ± 0.32, ± 0.25, ± 0.32, and ±0.25 ppm. The results showed that chemical shift fluctuations with changes in the conformation because of molecular motion were larger than the differences between computed and experimental chemical shifts for all six levels of theory. In conclusion, selection of an appropriate structural ensemble should be performed before theoretical chemical shift calculations for development of an accurate database for a variety of metabolites. PMID:26963288

  6. Theoretical oxidation state analysis of Ru-(bpy){sub 3}: Influence of water solvation and Hubbard correction in first-principles calculations

    SciTech Connect

    Reeves, Kyle G.; Kanai, Yosuke

    2014-07-14

    Oxidation state is a powerful concept that is widely used in chemistry and materials physics, although the concept itself is arguably ill-defined quantum mechanically. In this work, we present impartial comparison of four, well-recognized theoretical approaches based on Lowdin atomic orbital projection, Bader decomposition, maximally localized Wannier function, and occupation matrix diagonalization, for assessing how well transition metal oxidation states can be characterized. Here, we study a representative molecular complex, tris(bipyridine)ruthenium. We also consider the influence of water solvation through first-principles molecular dynamics as well as the improved electronic structure description for strongly correlated d-electrons by including Hubbard correction in density functional theory calculations.

  7. Molecular structure of cotinine studied by gas electron diffraction combined with theoretical calculations

    NASA Astrophysics Data System (ADS)

    Takeshima, Tsuguhide; Takeuchi, Hiroshi; Egawa, Toru; Konaka, Shigehiro

    2007-09-01

    The molecular structure of cotinine (( S)-1-methyl-5-(3-pyridinyl)-2-pyrrolidinone), the major metabolite of nicotine, has been determined at about 182 °C by gas electron diffraction combined with MP2 and DFT calculations. The diffraction data are consistent with the existence of the (ax, sc), (ax, ap), (eq, sp) and (eq, ap) conformers, where ax and eq indicate the configuration of the pyrrolidinone ring by means of the position (axial and equatorial) of the pyridine ring, and sc, sp and ap distinguish the isomers arising from the internal rotation around the bond connecting the two rings. The (CH 3)NCCC(N) dihedral angles, ϕ, of the (ax, sc) and (eq, sp) conformers were determined independently to be 158(12)° and 129(13)°, respectively, where the numbers in parentheses are three times the standard errors, 3 σ. According to the MP2 calculations, the corresponding dihedral angles for the (ax, ap) and (eq, ap) conformers were assumed to differ by 180° from their syn counterparts. The ratios x(ax, sc)/ x(ax, ap) and x(eq, sp)/ x(eq, ap) were taken from the theoretically estimated free energy differences, Δ G, where x is the abundance of the conformer. The resultant abundances of (ax, sc), (ax, ap), (eq, sp) and (eq, ap) conformers are 34(6)%, 21% (d.p.), 28% (d.p.), and 17% (d.p.), respectively, where d.p. represents dependent parameters. The determined structural parameters ( rg (Å) and ∠ α (°)) of the most abundant conformer, (ax, sc), are as follows: r(N sbnd C) pyrrol = 1.463(5); r(N sbnd C methyl) = 1.457(←); r(N sbnd C( dbnd O)) = 1.384(12); r(C dbnd O) = 1.219(5); < r(C sbnd C) pyrrol> = 1.541(3); r(C pyrrolsbnd C pyrid) = 1.521(←); < r(C sbnd C) pyrid> = 1.396(2); < r(C sbnd N) pyrid> = 1.343(←); ∠(CNC) pyrrol = 113.9(11); ∠CCC pyrrol(-C pyrid) = 103.6(←); ∠NCO = 124.1(13); ∠NC pyrrolC pyrid = 113.1(12); ∠C pyrrolC pyrrolC pyrid = 113.3(←); ∠(CNC) pyrid = 117.1(2); <∠(NCC) pyrid> = 124.4(←); ∠C methylNC( dbnd O) = ∠C methylNC(-C pyrid) = 122.8(d.p.); ∠NC( dbnd O)C = 107.1(d.p.); ∠NC pyrrol(-C pyrid)C pyrrol = 103.0(d.p.) and ∠CCC( dbnd O) = 105.2(d.p.), where ← in the parentheses means that the parameter is bound to the preceding one and < > denote average values. The puckering angle, α, of the pyrrolidinone ring is 26(3)°. The N⋯N distances of the (ax, sc) and (eq, sp) conformers, which are 4.844(5) and 4.740(5) Å, respectively, are close to that of the most stable conformer of nicotine, 4.885(6) Å and the corresponding one of arecoline, 4.832(13) Å. It is concluded that the weak nicotinic activity of cotinine cannot be ascribed to such a small difference in the N⋯N distances.

  8. A theoretical study of electronic and optical properties of SiC nanowires and their quantum confinement effects.

    PubMed

    Laref, A; Alshammari, Nuyer; Laref, S; Luo, S J

    2014-04-14

    We have performed a theoretical study of silicon carbide nanowires (SiCNWs) within the framework of first-principles calculations by incorporating the size effect and hydrogen terminated surface. Specifically, the variation of the energy gap and optical absorption spectra for hydrogen passivated SiCNWs and pristine wires are examined with respect to the wire diameter. All the [001]-orientated SiCNWs derived from the parent zinc-blende (3C) exhibit semiconducting behavior. Our study demonstrates that the saturated 3C-SiCNWs grown along the [001] direction with larger wire sizes are energetically more favorable than the wires with a smaller diameter. Additionally, the energy gaps are reduced with the increment of wire size because of the quantum-confinement effects. The unsaturated SiCNWs possess smaller band gaps than those of saturated ones when the Si- and C-dangling bonds are passivated by hydrogen atoms. Interestingly, the surface terminated by hydrogen atoms substantially alters the onset of absorption as well as the spectrum behavior at upper energies. Moreover, some pronounced fine structures in the absorption peak are conspicuous at the lower energy region of hydrogen saturated SiCNWs as the wire size increases. We find that the distributions of the highest occupied molecular orbitals and the lowest unoccupied molecular orbitals are uniform along the wire axis, which reveals that the SiCNWs are exceptional candidates in producing nano-optoelectronic devices. PMID:24535574

  9. Scaled Quantum Mechanical scale factors for vibrational calculations using alternate polarized and augmented basis sets with the B3LYP density functional calculation model

    NASA Astrophysics Data System (ADS)

    Legler, C. R.; Brown, N. R.; Dunbar, R. A.; Harness, M. D.; Nguyen, K.; Oyewole, O.; Collier, W. B.

    2015-06-01

    The Scaled Quantum Mechanical (SQM) method of scaling calculated force constants to predict theoretically calculated vibrational frequencies is expanded to include a broad array of polarized and augmented basis sets based on the split valence 6-31G and 6-311G basis sets with the B3LYP density functional. Pulay's original choice of a single polarized 6-31G(d) basis coupled with a B3LYP functional remains the most computationally economical choice for scaled frequency calculations. But it can be improved upon with additional polarization functions and added diffuse functions for complex molecular systems. The new scale factors for the B3LYP density functional and the 6-31G, 6-31G(d), 6-31G(d,p), 6-31G+(d,p), 6-31G++(d,p), 6-311G, 6-311G(d), 6-311G(d,p), 6-311G+(d,p), 6-311G++(d,p), 6-311G(2d,p), 6-311G++(2d,p), 6-311G++(df,p) basis sets are shown. The double d polarized models did not perform as well and the source of the decreased accuracy was investigated. An alternate system of generating internal coordinates that uses the out-of plane wagging coordinate whenever it is possible; makes vibrational assignments via potential energy distributions more meaningful. Automated software to produce SQM scaled vibrational calculations from different molecular orbital packages is presented.

  10. Amorphous Solid Simulation and Trial Fabrication of the Organic Field-Effect Transistor of Tetrathienonaphthalenes Prepared by Using Microflow Photochemical Reactions: A Theoretical Calculation-Inspired Investigation.

    PubMed

    Yamamoto, Atsushi; Matsui, Yasunori; Asada, Toshio; Kumeda, Motoki; Takagi, Kenichiro; Suenaga, Yu; Nagae, Kunihiko; Ohta, Eisuke; Sato, Hiroyasu; Koseki, Shiro; Naito, Hiroyoshi; Ikeda, Hiroshi

    2016-04-15

    The p-type organic semiconductor (OSC) material tetrathieno[2,3-a:3',2'-c:2″,3″-f:3‴,2‴-h]naphthalene (2TTN) and its alkyl-substituted derivatives Cn-2TTNs (n = 6, 8, and 10) have been developed based on the results of theoretical calculation-inspired investigation. A hole mobility for amorphous Cn-2TTNs (10(-2)-10(-3) cm(2) V(-1) s(-1)) was accurately predicted by using a novel statistical method in which the geometric mean of the mobilities for many individual small molecular flocks in an amorphous solid was obtained by using molecular mechanical molecular dynamics simulations and quantum chemical calculations. The simulation also suggests that upon increasing the length of alkyl chains in Cn-2TTNs the mobilities become smaller as a consequence of a decrease in transfer integral values. Cn-2TTNs are synthesized in a microflow reactor through photoreactions of the corresponding precursors. Cn-2TTNs are then utilized in the fabrication of organic field-effect transistors (OFETs). Although spin-coated thin films of Cn-2TTNs are crystalline, the hole mobilities (10(-2)-10(-3) cm(2) V(-1) s(-1)) of trial OFETs decrease upon elongation of the alkyl chains. This finding parallels the results of theoretical simulation. The simulation method for amorphous solids developed in this effort should become a useful tool in studies aimed at designing new OSC materials. PMID:27010327

  11. Quantum dynamics calculations using symmetrized, orthogonal Weyl-Heisenberg wavelets with a phase space truncation scheme. III. Representations and calculations.

    PubMed

    Poirier, Bill; Salam, A

    2004-07-22

    In a previous paper [J. Theo. Comput. Chem. 2, 65 (2003)], one of the authors (B.P.) presented a method for solving the multidimensional Schrodinger equation, using modified Wilson-Daubechies wavelets, and a simple phase space truncation scheme. Unprecedented numerical efficiency was achieved, enabling a ten-dimensional calculation of nearly 600 eigenvalues to be performed using direct matrix diagonalization techniques. In a second paper [J. Chem. Phys. 121, 1690 (2004)], and in this paper, we extend and elaborate upon the previous work in several important ways. The second paper focuses on construction and optimization of the wavelength functions, from theoretical and numerical viewpoints, and also examines their localization. This paper deals with their use in representations and eigenproblem calculations, which are extended to 15-dimensional systems. Even higher dimensionalities are possible using more sophisticated linear algebra techniques. This approach is ideally suited to rovibrational spectroscopy applications, but can be used in any context where differential equations are involved. PMID:15260721

  12. Quantum Matching Theory (with new complexity-theoretic, combinatorial and topical insights on the nature of the quantum entanglement)

    SciTech Connect

    Gurvits, L.

    2002-01-01

    Classical matching theory can be defined in terms of matrices with nonnegative entries. The notion of Positive operator, central in Quantum Theory, is a natural generalization of matrices with non-negative entries. Based on this point of view, we introduce a definition of perfect Quantum (operator) matching. We show that the new notion inherits many 'classical' properties, but not all of them. This new notion goes somewhere beyound matroids. For separable bipartite quantum states this new notion coinsides with the full rank property of the intersection of two corresponding geometric matroids. In the classical situation, permanents are naturally associated with perfects matchings. We introduce an analog of permanents for positive operators, called Quantum Permanent and show how this generalization of the permanent is related to the Quantum Entanglement. Besides many other things, Quantum Permanents provide new rational inequalities necessary for the separability of bipartite quantum states. Using Quantum Permanents, we give deterministic poly-time algorithm to solve Hidden Matroids Intersection Problem and indicate some 'classical' complexity difficulties associated with the Quantum Entanglement. Finally, we prove that the weak membership problem for the convex set of separable bipartite density matrices is NP-HARD.

  13. Artificial Bee Colony Optimization of Capping Potentials for Hybrid Quantum Mechanical/Molecular Mechanical Calculations.

    PubMed

    Schiffmann, Christoph; Sebastiani, Daniel

    2011-05-10

    We present an algorithmic extension of a numerical optimization scheme for analytic capping potentials for use in mixed quantum-classical (quantum mechanical/molecular mechanical, QM/MM) ab initio calculations. Our goal is to minimize bond-cleavage-induced perturbations in the electronic structure, measured by means of a suitable penalty functional. The optimization algorithm-a variant of the artificial bee colony (ABC) algorithm, which relies on swarm intelligence-couples deterministic (downhill gradient) and stochastic elements to avoid local minimum trapping. The ABC algorithm outperforms the conventional downhill gradient approach, if the penalty hypersurface exhibits wiggles that prevent a straight minimization pathway. We characterize the optimized capping potentials by computing NMR chemical shifts. This approach will increase the accuracy of QM/MM calculations of complex biomolecules. PMID:26610125

  14. Bosonic helium droplets with cationic impurities: onset of electrostriction and snowball effects from quantum calculations.

    PubMed

    Coccia, E; Bodo, E; Marinetti, F; Gianturco, F A; Yildrim, E; Yurtsever, M; Yurtsever, E

    2007-03-28

    Variational Monte Carlo and diffusion Monte Carlo calculations have been carried out for cations such as Li(+), Na(+), and K(+) as dopants of small helium clusters over a range of cluster sizes up to about 12 solvent atoms. The interaction has been modeled through a sum-of-potential picture that disregards higher order effects beyond atom-atom and atom-ion contributions. The latter were obtained from highly correlated ab initio calculations over a broad range of interatomic distances. This study focuses on two of the most striking features of the microsolvation in a quantum solvent of a cationic dopant: electrostriction and snowball effects. They are discussed here in detail and in relation with the nanoscopic properties of the interaction forces at play within a fully quantum picture of the cluster features. PMID:17411135

  15. Bosonic helium droplets with cationic impurities: Onset of electrostriction and snowball effects from quantum calculations

    SciTech Connect

    Coccia, E.; Bodo, E.; Marinetti, F.; Gianturco, F. A.; Yildrim, E.; Yurtsever, M.; Yurtsever, E.

    2007-03-28

    Variational Monte Carlo and diffusion Monte Carlo calculations have been carried out for cations such as Li{sup +}, Na{sup +}, and K{sup +} as dopants of small helium clusters over a range of cluster sizes up to about 12 solvent atoms. The interaction has been modeled through a sum-of-potential picture that disregards higher order effects beyond atom-atom and atom-ion contributions. The latter were obtained from highly correlated ab initio calculations over a broad range of interatomic distances. This study focuses on two of the most striking features of the microsolvation in a quantum solvent of a cationic dopant: electrostriction and snowball effects. They are discussed here in detail and in relation with the nanoscopic properties of the interaction forces at play within a fully quantum picture of the cluster features.

  16. Variational calculation on ground-state energy of bound polarons in parabolic quantum wires

    NASA Astrophysics Data System (ADS)

    Wang, Zhuang-bing; Wu, Fu-li; Chen, Qing-hu; Jiao, Zheng-kuan

    2001-05-01

    Within the framework of Feynman path-integral variational theory, we calculate the ground-state energy of a polaron in parabolic quantum wires in the presence of a Coulomb potential. It is shown that the polaronic correction to the ground-state energy is more sensitive to the electron-phonon coupling constant than the Coulomb binding parameter and it increases monotonically with decreasing effective wire radius. Moreover, compared to the results obtained by Feynman Haken variational path-integral theory, we obtain better results within the Feynman path-integral variational approach (FV approach). Applying our calculation to several polar semiconductor quantum wires, we find that the polaronic correction can be considerably large.

  17. Quantum microscopic vs. classical macroscopic calculations on the phenomenon of electrostatic influence

    NASA Astrophysics Data System (ADS)

    Blaive, B.; Julg, A.; Pellegatti, A.

    2005-09-01

    In order to compare microscopic and macroscopic approaches to the phenomenon of electrostatic influence, we have studied the atomic charges of an electric conductor, obtained either from macroscopic classical electrostatics, or microscopic quantum ab initio calculations. A torus was chosen as conducting material, built from valence monoelectronic atoms and influenced by an external point charge. The classical electric charges are obtained by integrating the macroscopic density over “atomic" sectors. This density is determined from a numerical integration of linearized electrostatic equations. The quantum charges are defined from Natural Orbitals in MP2/6-31G* calculations on clusters of different sizes. The overall agreement is good, with reasonable discrepancies due (i) to the continuity of the macroscopic model, which ignores the oscillations on atomic distances; and (ii) to the linearity constraint in the macroscopic equations.

  18. A discussion of theoretical ionization equilibrium calculations based on solar flare X-ray spectra

    NASA Technical Reports Server (NTRS)

    Feldman, U.; Doschek, G. A.; Cowan, R. D.

    1981-01-01

    Several sets of ionization equilibrium calculations exist for use in interpreting X-ray and EUV spectra of astrophysical plasmas. In particular, the calculations of Jordan (1969, 1970), Jacobs et al. (1977, 1978) and Summers (1974) are well known. The temperatures of maximum fractional abundance calculated by Summers for the more highly ionized and heavier elements such as iron are about a factor of two higher than the temperatures calculated by Jordan and Jacobs et al. By the use of recently obtained X-ray spectra of solar flares, it is shown that the temperatures calculated by Summers (1974) for iron are incorrect. The temperatures calculated by Jordan or Jacobs et al. should be used until further improvements become available.

  19. Theoretical Calculations on Sediment Transport on Titan, and the Possible Production of Streamlined Forms

    NASA Technical Reports Server (NTRS)

    Burr, D. M.; Emery, J. P.; Lorenz, R. D.

    2005-01-01

    The Cassini Imaging Science System (ISS) has been returning images of Titan, along with other Saturnian satellites. Images taken through the 938 nm methane window see down to Titan's surface. One of the purposes of the Cassini mission is to investigate possible fluid cycling on Titan. Lemniscate features shown recently and radar evidence of surface flow prompted us to consider theoretically the creation by methane fluid flow of streamlined forms on Titan. This follows work by other groups in theoretical consideration of fluid motion on Titan's surface.

  20. Perturbation approach for the calculation of the magnetoexciton ground state in an asymmetric quantum well

    NASA Astrophysics Data System (ADS)

    Henriques, A. B.; Valadares, E. C.

    The magnetoexciton ground state in an n-type one-side doped quantum well for a magnetic field applied parallel to the growth axis is calculated numerically in the Hartree self-consistent approximation. Results compare favorably with magneto-optical experimental data for a well width of 150Å and carrier density n s = 8.2 × 10 11 cm -2 in a magnetic field up to 15T.

  1. Experimental and Theoretical Electron Density Analysis of Copper Pyrazine Nitrate Quasi-Low-Dimensional Quantum Magnets.

    PubMed

    Dos Santos, Leonardo H R; Lanza, Arianna; Barton, Alyssa M; Brambleby, Jamie; Blackmore, William J A; Goddard, Paul A; Xiao, Fan; Williams, Robert C; Lancaster, Tom; Pratt, Francis L; Blundell, Stephen J; Singleton, John; Manson, Jamie L; Macchi, Piero

    2016-02-24

    The accurate electron density distribution and magnetic properties of two metal-organic polymeric magnets, the quasi-one-dimensional (1D) Cu(pyz)(NO3)2 and the quasi-two-dimensional (2D) [Cu(pyz)2(NO3)]NO3·H2O, have been investigated by high-resolution single-crystal X-ray diffraction and density functional theory calculations on the whole periodic systems and on selected fragments. Topological analyses, based on quantum theory of atoms in molecules, enabled the characterization of possible magnetic exchange pathways and the establishment of relationships between the electron (charge and spin) densities and the exchange-coupling constants. In both compounds, the experimentally observed antiferromagnetic coupling can be quantitatively explained by the Cu-Cu superexchange pathway mediated by the pyrazine bridging ligands, via a σ-type interaction. From topological analyses of experimental charge-density data, we show for the first time that the pyrazine tilt angle does not play a role in determining the strength of the magnetic interaction. Taken in combination with molecular orbital analysis and spin density calculations, we find a synergistic relationship between spin delocalization and spin polarization mechanisms and that both determine the bulk magnetic behavior of these Cu(II)-pyz coordination polymers. PMID:26811927

  2. Quantum calculations of the carrier mobility: Methodology, Matthiessen's rule, and comparison with semi-classical approaches

    NASA Astrophysics Data System (ADS)

    Niquet, Yann-Michel; Nguyen, Viet-Hung; Triozon, Franois; Duchemin, Ivan; Nier, Olivier; Rideau, Denis

    2014-02-01

    We discuss carrier mobilities in the quantum Non-Equilibrium Green's Functions (NEGF) framework. We introduce a method for the extraction of the mobility that is free from contact resistance contamination and with minimal needs for ensemble averages. We focus on silicon thin films as an illustration, although the method can be applied to various materials such as semiconductor nanowires or carbon nanostructures. We then introduce a new paradigm for the definition of the partial mobility ?M associated with a given elastic scattering mechanism "M," taking phonons (PH) as a reference (?M-1=?PH+M-1-?PH-1). We argue that this definition makes better sense in a quantum transport framework as it is free from long range interference effects that can appear in purely ballistic calculations. As a matter of fact, these mobilities satisfy Matthiessen's rule for three mechanisms [e.g., surface roughness (SR), remote Coulomb scattering (RCS) and phonons] much better than the usual, single mechanism calculations. We also discuss the problems raised by the long range spatial correlations in the RCS disorder. Finally, we compare semi-classical Kubo-Greenwood (KG) and quantum NEGF calculations. We show that KG and NEGF are in reasonable agreement for phonon and RCS, yet not for SR. We discuss the reasons for these discrepancies.

  3. Calculation of Host-Guest Binding Affinities Using a Quantum-Mechanical Energy Model

    PubMed Central

    Muddana, Hari S.; Gilson, Michael K.

    2012-01-01

    The prediction of protein-ligand binding affinities is of central interest in computer-aided drug discovery, but it is still difficult to achieve a high degree of accuracy. Recent studies suggesting that available force fields may be a key source of error motivate the present study, which reports the first mining minima (M2) binding affinity calculations based on a quantum mechanical energy model, rather than an empirical force field. We apply a semi-empirical quantum-mechanical energy function, PM6-DH+, coupled with the COSMO solvation model, to 29 host-guest systems with a wide range of measured binding affinities. After correction for a systematic error, which appears to derive from the treatment of polar solvation, the computed absolute binding affinities agree well with experimental measurements, with a mean error 1.6 kcal/mol and a correlation coefficient of 0.91. These calculations also delineate the contributions of various energy components, including solute energy, configurational entropy, and solvation free energy, to the binding free energies of these host-guest complexes. Comparison with our previous calculations, which used empirical force fields, point to significant differences in both the energetic and entropic components of the binding free energy. The present study demonstrates successful combination of a quantum mechanical Hamiltonian with the M2 affinity method. PMID:22737045

  4. Quantum calculations of the carrier mobility: Methodology, Matthiessen's rule, and comparison with semi-classical approaches

    SciTech Connect

    Niquet, Yann-Michel Nguyen, Viet-Hung; Duchemin, Ivan; Nier, Olivier; Rideau, Denis

    2014-02-07

    We discuss carrier mobilities in the quantum Non-Equilibrium Green's Functions (NEGF) framework. We introduce a method for the extraction of the mobility that is free from contact resistance contamination and with minimal needs for ensemble averages. We focus on silicon thin films as an illustration, although the method can be applied to various materials such as semiconductor nanowires or carbon nanostructures. We then introduce a new paradigm for the definition of the partial mobility μ{sub M} associated with a given elastic scattering mechanism “M,” taking phonons (PH) as a reference (μ{sub M}{sup −1}=μ{sub PH+M}{sup −1}−μ{sub PH}{sup −1}). We argue that this definition makes better sense in a quantum transport framework as it is free from long range interference effects that can appear in purely ballistic calculations. As a matter of fact, these mobilities satisfy Matthiessen's rule for three mechanisms [e.g., surface roughness (SR), remote Coulomb scattering (RCS) and phonons] much better than the usual, single mechanism calculations. We also discuss the problems raised by the long range spatial correlations in the RCS disorder. Finally, we compare semi-classical Kubo-Greenwood (KG) and quantum NEGF calculations. We show that KG and NEGF are in reasonable agreement for phonon and RCS, yet not for SR. We discuss the reasons for these discrepancies.

  5. Quantum phase space theory for the calculation of v{center_dot}j vector correlations

    SciTech Connect

    Hall, G.E.

    1995-07-01

    The quantum state-counting phase space theory commonly used to describe barrierless dissociation is recast in a helicity basis to calculate photofragment v{center_dot}j correlations. Counting pairs of fragment states with specific angular momentum projection numbers on the relative velocity provides a simple connection between angular momentum conservation and the v{center_dot}j correlation, which is not so evident in the conventional basis for phase space state counts. The upper bound on the orbital angular momentum, l, imposed by the centrifugal barrier cannot be included simply in the helicity basis, where l is not a good quantum number. Two approaches for a quantum calculation of the v{center_dot}j correlation are described to address this point. An application to the photodissociation of NCCN is consistent with recent classical phase space calculations of Cline and Klippenstein. The observed vector correlation exceeds the phase space theory prediction. The authors take this as evidence of incomplete mixing of the K states of the linear parent molecule at the transition state, corresponding to an evolution of the body-fixed projection number K into the total helicity of the fragment pair state. The average over a thermal distribution of parent angular momentum in the special case of a linear molecule does not significantly reduce the v{center_dot}j correlation below that computed for total J = 0.

  6. Dynamical basis sets for algebraic variational calculations in quantum-mechanical scattering theory

    NASA Technical Reports Server (NTRS)

    Sun, Yan; Kouri, Donald J.; Truhlar, Donald G.; Schwenke, David W.

    1990-01-01

    New basis sets are proposed for linear algebraic variational calculations of transition amplitudes in quantum-mechanical scattering problems. These basis sets are hybrids of those that yield the Kohn variational principle (KVP) and those that yield the generalized Newton variational principle (GNVP) when substituted in Schlessinger's stationary expression for the T operator. Trial calculations show that efficiencies almost as great as that of the GNVP and much greater than the KVP can be obtained, even for basis sets with the majority of the members independent of energy.

  7. Assignment of absolute stereostructures through quantum mechanics electronic and vibrational circular dichroism calculations.

    PubMed

    Dai, Peng; Jiang, Nan; Tan, Ren-Xiang

    2016-01-01

    Elucidation of absolute configuration of chiral molecules including structurally complex natural products remains a challenging problem in organic chemistry. A reliable method for assigning the absolute stereostructure is to combine the experimental circular dichroism (CD) techniques such as electronic and vibrational CD (ECD and VCD), with quantum mechanics (QM) ECD and VCD calculations. The traditional QM methods as well as their continuing developments make them more applicable with accuracy. Taking some chiral natural products with diverse conformations as examples, this review describes the basic concepts and new developments of QM approaches for ECD and VCD calculations in solution and solid states. PMID:26880597

  8. Reptation Quantum Monte Carlo Calculation of Charge Transfer in The Na-Cl Dimer

    NASA Astrophysics Data System (ADS)

    Yao, Yi; Kanai, Yosuke

    2015-03-01

    Reptation Quantum Monte Carlo (QMC) calculations are performed to describe the charge transfer behavior in a NaCl dimer. Influence of fixed node approximation on the charge transfer was examined by obtaining electron density via reputation QMC. We employ Slater-Jastrow wavefunction as the trial wavefunction, and the fermion nodes are obtained from single particle orbitals of Hartree-Fock and Density Functional Theory (DFT) with several exchange-correlation approximations. We will discuss our QMC results together with DFT calculations to give insights into observed dependence of the charge transfer behavior on the fixed-node approximation.

  9. Auxiliary-field quantum Monte Carlo calculations for systems with long-range repulsive interactions

    SciTech Connect

    Silvestrelli, P.L.; Baroni, S.; Car, R. Scuola Internazionale Superiore di Studi Avanzati , via Beirut 2/4, I-34014 Trieste Institut Romand de Recherche Numerique en Physique des Materiaux , PHB Ecublens, CH-1015 Lausanne )

    1993-08-23

    We report on the first successful attempt to apply the auxiliary-field quantum Monte Carlo technique to the calculation of ground-state properties of systems of many electrons interacting via a Coulomb potential. We have been able to substantially reduce the huge statistical fluctuations arising from the repulsive, long-range character of the interactions, which had so far hindered the application of this method to [ital realistic] Hamiltonians for atoms, molecules, and solids. Our technique is demonstrated with calculations of ground-state properties of the simplest molecular and solid-state systems, i.e., the H[sub 2] molecule and the homogeneous electron gas.

  10. Self-consistent calculation of dephasing in quantum cascade structures within a density matrix method

    NASA Astrophysics Data System (ADS)

    Freeman, Will

    2016-05-01

    Dephasing in terahertz quantum cascade structures is studied within a density matrix formalism. We self-consistently calculate the pure dephasing time from the intrasubband interactions within the upper and lower lasing states. Interface roughness and ionized impurity scattering interactions are included in the calculation. Dephasing times are shown to be consistent with measured spontaneous emission spectra, and the lattice temperature dependence of the device output power is consistent with experiment. The importance of including multiple optical transitions when a lower miniband continuum is present and the resulting multi-longitudinal modes within the waveguide resonant cavity are also shown.

  11. Using experimental studies and theoretical calculations to analyze the molecular mechanism of coumarin, p-hydroxybenzoic acid, and cinnamic acid

    NASA Astrophysics Data System (ADS)

    Hsieh, Tiane-Jye; Su, Chia-Ching; Chen, Chung-Yi; Liou, Chyong-Huey; Lu, Li-Hwa

    2005-05-01

    Three natural products, Coumarin ( 1), p-hydroxybenzoic acid ( 2), trans-cinnamic acid ( 3) were isolated from the natural plant of indigenous cinnamon and the structures including relative stereochemistry were elucidated on the basis of spectroscopic data and theoretical calculations. Their sterochemical structures were determined by NMR spectroscopy, mass spectroscopy, and X-ray crystallography. The p-hydroxybenzoic acid complex with water is reported to show the existence of two hydrogen bonds. The two hydrogen bonds are formed in the water molecule of two hydrogen-accepting oxygen of carbonyl group of the p-hydroxybenzoic acid. The intermolecular interaction two hydrogen bond of the model system of the water- p-hydroxybenzoic acid was investigated. An experimental study and a theoretical analysis using the B3LYP/6-31G* method in the GAUSSIAN-03 package program were conducted on the three natural products. The theoretical results are supplemented by experimental data. Optimal geometric structures of three compounds were also determined. The calculated molecular mechanics compared quite well with those obtained from the experimental data. The ionization potentials, highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy, energy gaps, heat of formation, atomization energies, and vibration frequencies of the compounds were also calculated. The results of the calculations show that three natural products are stable molecules with high reactive and various other physical properties. The study also provided an explicit understanding of the sterochemical structure and thermodynamic properties of the three natural products.

  12. Quantum preequilibrium multistep direct calculations for nucleon scattering on deformed nuclei: a microscopic approach

    SciTech Connect

    Dupuis, Marc; Kawano, Toshihiko; Bonneau, Ludovic

    2008-04-17

    An introduction of the different quantum mechanics models is given for the calculation of pre-equilibrium multistep direct process for nucleon induced reaction. A practical application is presented for {sup 238}U neutron induced reaction at medium energy (10-20 MeV). The double differential cross-sections are calculated with no adjustable parameter and reproduced the data very well. The cross-sections are expressed as a sum of DWBA transition amplitudes computed with a microscopic two-body interaction. The exited states of the target are expressed as particle-hole excitations built from single particle states obtained with the HF+BCS calculation with a Skyrme force. We also perform a sensitivity study our calculations with respect to the ingredients of the model, namely the two-body interaction which generates the transitions and the target states description.

  13. Structure and properties of electronic and hole centers in CsBr from theoretical calculations

    SciTech Connect

    Halliday, Matthew T.; Hess, Wayne P.; Shluger, Alexander L.

    2015-06-24

    The electronic structure, geometry, diffusion barriers and optical properties of fundamental defects of CsBr are calculated using hybrid functional DFT and TD- DFT methods. The B3LYP functional with a modified exchange contribution has been used in an embedded cluster scheme to model the structure and spectroscopic properties of self-trapped triplet exciton, interstitial Br atoms and ions, self-trapped holes and Br vacancies. The calculated migration barriers and positions of maxima of optical absorption bands are in good agreement with experiment, justifying the obtained defect geometries. The o*-center triplet exciton luminescence energy is also accurately calculated.

  14. SU-E-T-191: First Principle Calculation of Quantum Yield in Photodynamic Therapy

    SciTech Connect

    Abolfath, R; Guo, F; Chen, Z; Nath, R

    2014-06-01

    Purpose: We present a first-principle method to calculate the spin transfer efficiency in oxygen induced by any photon fields especially in MeV energy range. The optical pumping is mediated through photosensitizers, e.g., porphyrin and/or ensemble of quantum dots. Methods: Under normal conditions, oxygen molecules are in the relatively non-reactive triplet state. In the presence of certain photosensitizer compounds such as porphyrins, electromagnetic radiation of specific wavelengths can excite oxygen to highly reactive singlet state. With selective uptake of photosensitizers by certain malignant cells, photon irradiation of phosensitized tumors can lead to selective killing of cancer cells. This is the basis of photodynamic therapy (PDT). Despite several attempts, PDT has not been clinically successful except in limited superficial cancers. Many parameters such as photon energy, conjugation with quantum dots etc. can be potentially combined with PDT in order to extend the role of PDT in cancer management. The key quantity for this optimization is the spin transfer efficiency in oxygen by any photon field. The first principle calculation model presented here, is an attempt to fill this need. We employ stochastic density matrix description of the quantum jumps and the rate equation methods in quantum optics based on Markov/Poisson processes and calculate time evolution of the population of the optically pumped singlet oxygen. Results: The results demonstrate the feasibility of our model in showing the dependence of the optical yield in generating spin-singlet oxygen on the experimental conditions. The adjustable variables can be tuned to maximize the population of the singlet oxygen hence the efficacy of the photodynamic therapy. Conclusion: The present model can be employed to fit and analyze the experimental data and possibly to assist researchers in optimizing the experimental conditions in photodynamic therapy.

  15. Ocean color spectrum calculations. [theoretical models relating oceanographic parameters to upwelling radiances

    NASA Technical Reports Server (NTRS)

    Mccluney, W. R.

    1974-01-01

    The development is considered of procedures for measuring a number of subsurface oceanographic parameters using remotely sensed ocean color data. It is proposed that the first step in this effort should be the development of adequate theoretical models relating the desired oceanographic parameters to the upwelling radiances to be observed. A portion of a contributory theoretical model is shown to be described by a modified single scattering approach based upon a simple treatment of multiple scattering. The resulting quasi-single scattering model can be used to predict the upwelling distribution of spectral radiance emerging from the sea. The shape of the radiance spectrum predicted by this model for clear ocean water shows encouraging agreement with measurments made at the edge of the Sargasso Sea off Cape Hatteras.

  16. Theoretical calculations of emission of wolframite and scheelite-type tungstate crystals

    SciTech Connect

    Nikolaenko, T.; Hizhnyi, Y.; Nedilko, S.

    2009-01-21

    Tungstate crystals AWO{sub 4} (A = Zn,Cd,Pb) are well-known scintillation materials for various applications in science and technology. In recent years the optical properties of these crystals were intensively studied experimentally and theoretically. However, the origin of luminescence in lead, cadmium and zinc tungstates is still the subject of discussion. According to generally accepted view, the centers of luminescence in AWO{sub 4} crystals are in some or other way related to the tungstate anionic groups. We developed a cluster approach in theoretical investigation of the electronic structure of AWO{sub 4} tungstate crystals based on the configuration interaction (CI) computation in which the lattice vibrations were taken into account.

  17. BOOK REVIEW: Mathematica for Theoretical Physics: Electrodynamics, Quantum Mechanics, General Relativity and Fractals

    NASA Astrophysics Data System (ADS)

    Heusler, Stefan

    2006-12-01

    The main focus of the second, enlarged edition of the book Mathematica for Theoretical Physics is on computational examples using the computer program Mathematica in various areas in physics. It is a notebook rather than a textbook. Indeed, the book is just a printout of the Mathematica notebooks included on the CD. The second edition is divided into two volumes, the first covering classical mechanics and nonlinear dynamics, the second dealing with examples in electrodynamics, quantum mechanics, general relativity and fractal geometry. The second volume is not suited for newcomers because basic and simple physical ideas which lead to complex formulas are not explained in detail. Instead, the computer technology makes it possible to write down and manipulate formulas of practically any length. For researchers with experience in computing, the book contains a lot of interesting and non-trivial examples. Most of the examples discussed are standard textbook problems, but the power of Mathematica opens the path to more sophisticated solutions. For example, the exact solution for the perihelion shift of Mercury within general relativity is worked out in detail using elliptic functions. The virial equation of state for molecules' interaction with Lennard-Jones-like potentials is discussed, including both classical and quantum corrections to the second virial coefficient. Interestingly, closed solutions become available using sophisticated computing methods within Mathematica. In my opinion, the textbook should not show formulas in detail which cover three or more pages—these technical data should just be contained on the CD. Instead, the textbook should focus on more detailed explanation of the physical concepts behind the technicalities. The discussion of the virial equation would benefit much from replacing 15 pages of Mathematica output with 15 pages of further explanation and motivation. In this combination, the power of computing merged with physical intuition would be of benefit even for newcomers. In summary, this book shows in a convincing manner how classical problems in physics can be attacked with modern computing technology. The second volume is interesting for experienced users of Mathematica. For students, the textbook can be very useful in combination with a seminar.

  18. Infrared and Raman spectra and theoretical calculations for benzocyclobutane in its electronic ground state

    NASA Astrophysics Data System (ADS)

    Ocola, Esther J.; Shin, Hee Won; Laane, Jaan

    2015-02-01

    The infrared and Raman spectra of vapor-phase and liquid-phase benzocyclobutane (BCB) have been recorded and assigned. The structure of the molecule was calculated using the MP2/cc-pVTZ basis set and the vibrational frequencies and spectral intensities were calculated using the B3LYP/cc-pVTZ level of theory. The agreement between experimental and calculated spectra is excellent. In order to allow comparisons with related molecules, ab initio and DFT calculations were also carried out for indan (IND), tetralin (TET), 1,4-benzodioxan (14BZD), 1,3-benzodioxan (13BZD) and 1,4-dihydronaphthalene (14DHN). The ring-puckering, ring-twisting, and ring-flapping vibrations were of particular interest as these reflect the rigidity of the bicyclic ring system. The infrared spectra of BCB show very nice examples of vapor-phase band types and combination bands.

  19. Infrared and Raman spectra and theoretical calculations for benzocyclobutane in its electronic ground state.

    PubMed

    Ocola, Esther J; Shin, Hee Won; Laane, Jaan

    2015-02-01

    The infrared and Raman spectra of vapor-phase and liquid-phase benzocyclobutane (BCB) have been recorded and assigned. The structure of the molecule was calculated using the MP2/cc-pVTZ basis set and the vibrational frequencies and spectral intensities were calculated using the B3LYP/cc-pVTZ level of theory. The agreement between experimental and calculated spectra is excellent. In order to allow comparisons with related molecules, ab initio and DFT calculations were also carried out for indan (IND), tetralin (TET), 1,4-benzodioxan (14BZD), 1,3-benzodioxan (13BZD) and 1,4-dihydronaphthalene (14DHN). The ring-puckering, ring-twisting, and ring-flapping vibrations were of particular interest as these reflect the rigidity of the bicyclic ring system. The infrared spectra of BCB show very nice examples of vapor-phase band types and combination bands. PMID:24507997

  20. Theoretical calculations of pressure broadening coefficients for H2O perturbed by hydrogen or helium gas

    NASA Technical Reports Server (NTRS)

    Gamache, Robert R.; Pollack, James B.

    1995-01-01

    Halfwidths were calculated for H2O with H2 as a broadening gas and were estimated for He as the broadening species. The calculations used the model of Robert and Bonamy with parabolic trajectories and all relevant terms in the interaction potential. The calculations investigated the dependence of the halfwidth on the order of the atom-atom expansion, the rotational states, and the temperature in the range 200 to 400K. Finally, calculations were performed for many transitions of interest in the 5 micrometer window region of the spectrum. The resulting data will be supplied to Dr. R. Freedman for extracting accurate water mixing ratios from the analysis of the thermal channels for the Net Flux experiment on the Galileo probe.

  1. Recombination of W19 + ions with electrons: Absolute rate coefficients from a storage-ring experiment and from theoretical calculations

    NASA Astrophysics Data System (ADS)

    Badnell, N. R.; Spruck, K.; Krantz, C.; Novotný, O.; Becker, A.; Bernhardt, D.; Grieser, M.; Hahn, M.; Repnow, R.; Savin, D. W.; Wolf, A.; Müller, A.; Schippers, S.

    2016-05-01

    Experimentally measured and theoretically calculated rate coefficients for the recombination of W19 +([Kr ] 4 d10 4 f9 ) ions with free electrons (forming W18 +) are presented. At low electron-ion collision energies, the merged-beam rate coefficient is dominated by strong, mutually overlapping, recombination resonances as already found previously for the neighboring charge-state ions W18 + and W20 +. In the temperature range where W19 + is expected to form in a collisionally ionized plasma, the experimentally derived recombination rate coefficient deviates by up to a factor of about 20 from the theoretical rate coefficient obtained from the Atomic Data and Analysis Structure database. The present calculations, which employ a Breit-Wigner redistributive partitioning of autoionizing widths for dielectronic recombination via multi-electron resonances, reproduce the experimental findings over the entire temperature range.

  2. Theoretical considerations of monitor unit calculations for intensity modulated beam treatment planning.

    PubMed

    Boyer, A; Xing, L; Ma, C M; Curran, B; Hill, R; Kania, A; Bleier, A

    1999-02-01

    A treatment planning system to compute intensity modulated radiotherapy (IMRT) treatments using inverse planning was investigated. The system was designed to optimize the intensity patterns required to treat a specified target volume with specified normal structure constraints. A beam model that uses the convolution of pencil beams was used to compute the dose distributions. A multileaf collimator leaf-setting sequence intended to produce the intensity pattern was computed along with the monitor units required to deliver each of a number of fixed-gantry modulated fields. Computer calculations are commonly verified using an independent manual procedure. It is difficult to calculate treatment delivery monitor units for this variant of IMRT using manual methods. Since manual calculations are not feasible, it is important both to understand and to verify the calculation of treatment monitor units by the planning system algorithm. A formal analysis was made of the dose calculation model and the monitor unit calculation embedded in the algorithm. Experimental verification of the dose delivered by plans computed with the methodology demonstrated an agreement of better than 4% between the dose model and measurements. PMID:10076972

  3. Collective excitations in quantum Hall liquid crystals: Single-mode approximation calculations

    SciTech Connect

    Lapilli, Cintia M.; Wexler, Carlos

    2006-02-15

    A variety of recent experiments probing the low-temperature transport properties of quantum Hall systems have suggested an interpretation in terms of liquid crystalline mesophases dubbed quantum Hall liquid crystals. The single mode approximation (SMA) has been a useful tool for the determination of the excitation spectra of various systems such as phonons in {sup 4}He and in the fractional quantum Hall effect. In this paper we calculate (via the SMA) the spectrum of collective excitations in a quantum Hall liquid crystal by considering nematic, tetratic, and hexatic generalizations of Laughlin's trial wave function having twofold, fourfold, and sixfold broken rotational symmetry, respectively. In the limit of zero wave vector q the dispersion of these modes is singular, with a gap that is dependent on the direction along which q=0 is approached for nematic and tetratic liquid crystalline states, but remains regular in the hexatic state, as permitted by the fourth order wave-vector dependence of the (projected) oscillator strength and static structure factor.

  4. Microscopic Model Calculations for the Magnetization Process of Layered Triangular-Lattice Quantum Antiferromagnets

    NASA Astrophysics Data System (ADS)

    Yamamoto, Daisuke; Marmorini, Giacomo; Danshita, Ippei

    2015-01-01

    Magnetization processes of spin-1 /2 layered triangular-lattice antiferromagnets (TLAFs) under a magnetic field H are studied by means of a numerical cluster mean-field method with a scaling scheme. We find that small antiferromagnetic couplings between the layers give rise to several types of extra quantum phase transitions among different high-field coplanar phases. Especially, a field-induced first-order transition is found to occur at H ≈0.7 Hs, where Hs is the saturation field, as another common quantum effect of ideal TLAFs in addition to the well-established one-third plateau. Our microscopic model calculation with appropriate parameters shows excellent agreement with experiments on Ba3CoSb2O9 [T. Susuki et al., Phys. Rev. Lett. 110, 267201 (2013)]. Given this fact, we suggest that the Co2 + -based compounds may allow for quantum simulations of intriguing properties of this simple frustrated model, such as quantum criticality and supersolid states.

  5. Orbital reconstruction through interlayer cation charge imbalance: insights from wave-function-based quantum chemistry calculations

    NASA Astrophysics Data System (ADS)

    Hozoi, Liviu

    A promising route to engineering the electronic properties of quantum materials and devices rests on the idea of orbital reconstruction in multilayered oxide heterostructures. In this context, we identify and discuss in detail one simple, appealing mechanism for tailoring the sequence of d-electron energy levels: interplanar cation charge imbalance (ICCI) along successive metal-oxygen layers. Through interplay with distortions of the ligand cages, it provides a knob for tunning the order of electronic levels in even intrinsically stacked oxides. We analyze in this regard electron spin resonance data for the 214 Sr-iridate oxide compound. While canonical ligand-field theory predicts z-axis g factors smaller than 2 for positive tetragonal distortions as present in Sr214, the experiment indicates values larger than 2. This implies that the iridium d levels are inverted with respect to their normal ordering. State-of-the-art quantum chemistry calculations confirm the level switching in Sr214, whereas we find them to be instead normally ordered in the sister compound Ba214. Given the nonpolar character of the metal-oxygen layers, our findings highlight the tetravalent transition-metal 214 oxides as ideal platforms to explore d-orbital engineering in the context of oxide electronics. The crucial role of internal anisotropic fields related to the environment beyond nearest-neighbor ligands is further highlighted by ab initio quantum chemistry calculations on 3D pyrochlore osmates and iridates.

  6. The calculation of theoretical chromospheric models and the interpretation of the solar spectrum

    NASA Technical Reports Server (NTRS)

    Avrett, Eugene H.

    1994-01-01

    Since the early 1970s we have been developing the extensive computer programs needed to construct models of the solar atmosphere and to calculate detailed spectra for use in the interpretation of solar observations. This research involves two major related efforts: work by Avrett and Loeser on the Pandora computer program for non-LTE modeling of the solar atmosphere including a wide range of physical processes, and work by Kurucz on the detailed synthesis of the solar spectrum based on opacity data for over 58 million atomic and molecular lines. Our goals are to determine models of the various features observed on the sun (sunspots, different components of quiet and active regions, and flares) by means of physically realistic models, and to calculate detailed spectra at all wavelengths that match observations of those features. These two goals are interrelated: discrepancies between calculated and observed spectra are used to determine improvements in the structure of the models, and in the detailed physical processes used in both the model calculations and the spectrum calculations. The atmospheric models obtained in this way provide not only the depth variation of various atmospheric parameters, but also a description of the internal physical processes that are responsible for nonradiative heating, and for solar activity in general.

  7. The Calculation of Theoretical Chromospheric Models and the Interpretation of the Solar Spectrum

    NASA Technical Reports Server (NTRS)

    Avrett, Eugene H.

    1998-01-01

    Since the early 1970s we have been developing the extensive computer programs needed to construct models of the solar atmosphere and to calculate detailed spectra for use in the interpretation of solar observations. This research involves two major related efforts: work by Avrett and Loeser on the Pandora computer program for non-LTE modeling of the solar atmosphere including a wide range of physical processes, and work by Rurucz on the detailed synthesis of the solar spectrum based on opacity data or over 58 million atomic and molecular lines. our goals are: to determine models of the various features observed on the Sun (sunspots, different components of quiet and active regions, and flares) by means of physically realistic models, and to calculate detailed spectra at all wavelengths that match observations of those features. These two goals are interrelated: discrepancies between calculated and observed spectra are used to determine improvements in the structure of the models, and in the detailed physical processes used in both the model calculations and the spectrum calculations. The atmospheric models obtained in this way provide not only the depth variation of various atmospheric parameters, but also a description of the internal physical processes that are responsible for non-radiative heating, and for solar activity in general.

  8. Automated Routines for Calculating Whole-Stream Metabolism: Theoretical Background and User's Guide

    USGS Publications Warehouse

    Bales, Jerad D.; Nardi, Mark R.

    2007-01-01

    In order to standardize methods and facilitate rapid calculation and archival of stream-metabolism variables, the Stream Metabolism Program was developed to calculate gross primary production, net ecosystem production, respiration, and selected other variables from continuous measurements of dissolved-oxygen concentration, water temperature, and other user-supplied information. Methods for calculating metabolism from continuous measurements of dissolved-oxygen concentration and water temperature are fairly well known, but a standard set of procedures and computation software for all aspects of the calculations were not available previously. The Stream Metabolism Program addresses this deficiency with a stand-alone executable computer program written in Visual Basic.NET?, which runs in the Microsoft Windows? environment. All equations and assumptions used in the development of the software are documented in this report. Detailed guidance on application of the software is presented, along with a summary of the data required to use the software. Data from either a single station or paired (upstream, downstream) stations can be used with the software to calculate metabolism variables.

  9. The calculation of theoretical chromospheric models and the interpretation of solar spectra from rockets and spacecraft

    NASA Technical Reports Server (NTRS)

    Avrett, Eugene H.

    1993-01-01

    Since the early 1970s we have been developing the extensive computer programs needed to construct models of the solar atmosphere and to calculate detailed spectra for use in the interpretation of solar observations. This research involves two major related efforts: work by Avrett and Loeser on the Pandora computer program for non-LTE modeling of the solar atmosphere including a wide range of physical processes, and work by Kurucz on the detailed synthesis of the solar spectrum based on opacity data for over 58 million atomic and molecular lines. Our goals are to determine models of the various features observed on the Sun (sunspots, different components of quiet and active regions, and flares) by means of physically realistic models, and to calculate detailed spectra at all wavelengths that match observations of those features. These two goals are interrelated: discrepancies between calculated and observed spectra are used to determine improvements in the structure of the models, and in the detailed physical processes used in both the model calculations and the spectrum calculations. The atmospheric models obtained in this way provide not only the depth variation of various atmospheric parameters, but also a description of the internal physical processes that are responsible for non-radiative heating, and for solar activity in general.

  10. Theoretical issues in quantum computing: Graph isomorphism, PageRank, and Hamiltonian determination

    NASA Astrophysics Data System (ADS)

    Rudinger, Kenneth Michael

    This thesis explores several theoretical questions pertaining to quantum computing. First we examine several questions regarding multi-particle quantum random walk-based algorithms for the graph isomorphism problem. We find that there exists a non-trivial difference between continuous-time walks of one and two non-interacting particles as compared to non-interacting walks of three or more particles, in that the latter are able to distinguish many strongly regular graphs (SRGs), a class of graphs with many graph pairs that are difficult to distinguish. We demonstrate analytically where this distinguishing power comes from, and we show numerically that three-particle and four-particle non-interacting continuous-time walks can distinguish many pairs of strongly regular graphs. We additionally show that this distinguishing power, while it grows with particle number, is bounded, so that no continuous-time non-interacting walk of fixed particle number can distinguish all strongly regular graphs. We then investigate the relationship between continuous-time and discrete-time walks, in the context of the graph isomorphism problem. While it has been previously demonstrated numerically that discrete-time walks of non-interacting particles can distinguish some SRGs, we demonstrate where this distinguishing power comes from. We also show that while no continuous-time non-interacting walk of fixed particle number can distinguish SRGs, it remains a possibility that such a discrete-time walk could, leaving open the possibility of a non-trivial difference between discrete-time and continuous-time walks. The last piece of our work on graph isomorphism examines limitations on certain kinds of continuous-time walk-based algorithms for distinguishing graphs. We show that a very general class of continuous-time walk algorithms, with a broad class of allowable interactions, cannot distinguish all graphs. We next consider a previously-proposed quantum adiabatic algorithm for computing the PageRank vector, a necessary step in one of Google's search algorithms. It had been previously believed that this algorithm might offer a non-trivial speedup in preparing the PageRank vector. We demonstrate, however, that when this algorithm is tested on graphs that sufficiently resemble the graph of the World Wide Web, there is no appreciable speedup. Lastly, we consider the problem of Hamiltonian determination. We show that in the high temperature limit, the classical signal processing technique of compressed sensing may be used to recover the Hamiltonian for a system of qubits, provided that the Hamiltonian does not possess too many interactions, i.e., it is "sparse". This new procedure allows for the determination of the Hamiltonian with a number of measurements that can be significantly smaller than required by standard techniques.

  11. A Comparison of Two Topos-Theoretic Approaches to Quantum Theory

    NASA Astrophysics Data System (ADS)

    Wolters, Sander A. M.

    2013-01-01

    The aim of this paper is to compare the two topos-theoretic approaches to quantum mechanics that may be found in the literature to date. The first approach, which we will call the contravariant approach, was originally proposed by Isham and Butterfield, and was later extended by Döring and Isham. The second approach, which we will call the covariant approach, was developed by Heunen, Landsman and Spitters. Motivated by coarse-graining and the Kochen-Specker theorem, the contravariant approach uses the topos of presheaves on a specific context category, defined as the poset of commutative von Neumann subalgebras of some given von Neumann algebra. In particular, the approach uses the spectral presheaf. The intuitionistic logic of this approach is given by the (complete) Heyting algebra of closed open subobjects of the spectral presheaf. We show that this Heyting algebra is, in a natural way, a locale in the ambient topos, and compare this locale with the internal Gelfand spectrum of the covariant approach. In the covariant approach, a non-commutative C*-algebra (in the topos Set) defines a commutative C*-algebra internal to the topos of covariant functors from the context category to the category of sets. We give an explicit description of the internal Gelfand spectrum of this commutative C*-algebra, from which it follows that the external spectrum is spatial. Using the daseinisation of self-adjoint operators from the contravariant approach, we give a new definition of the daseinisation arrow in the covariant approach and compare it with the original version. States and state-proposition pairing in both approaches are compared. We also investigate the physical interpretation of the covariant approach.

  12. Theoretical comparison of multiple quantum wells and thick-layer designs in InGaN/GaN solar cells

    SciTech Connect

    Cavassilas, Nicolas; Michelini, Fabienne; Bescond, Marc

    2014-08-11

    This theoretical work analyzes the photovoltaic effect in non-polar InGaN/GaN solar cells. Our electronic transport model considers quantum behaviors related to confinement, tunneling, electron-phonon, and electron-photon scatterings. Based on this model, we compare a multiple quantum wells cell with its thick-layer counterpart. We show that the structure of multiple quantum wells is a promising design providing better compromise between photon-absorption and electronic transport. This balance is necessary since these two phenomena are shown to be antagonist in nanostructure based solar cells. In these devices, we also show that phonon absorption increases the short-circuit current, while phonon emission reduces the open-circuit voltage.

  13. The dipole moment derivatives of nitrosyl cyanide— theoretical calculations and analysis

    NASA Astrophysics Data System (ADS)

    Ramos, Mozart N.; Neto, B. B.

    1986-01-01

    The results of an ab initio (9 s5 p/3 s2 p) molecular orbital calculation of the dipole moment derivatives and gas phase IR intensities of ONCN are reported for all the five in-plane IR active modes. The results are compared with the corresponding values previously obtained from an MNDO calculation. The directions of the dipole derivatives calculated by the two methods agree very well, whereas the intensities differ significantly. The MNDO results, which are in better agreement with the experimental spectrum, are analyzed for the charge—charge flux—overlap (CCFO) electronic contributions to the dipole derivatives. The resulting CCFO partition is used to study the electronic substituent effect on the CN stretching.

  14. Vibrational spectra, structure, and theoretical calculations of 2-fluoro- and 3-fluoropyridine.

    PubMed

    Boopalachandran, Praveenkumar; Laane, Jaan

    2011-09-01

    The infrared and Raman spectra of liquid and vapor-phase 2-fluoropyridine and 3-fluoropyridine have been recorded and assigned. Ab initio and DFT calculations were carried out to compute the molecular structures and to verify the vibrational assignments. The observed and calculated spectra agree extremely well. The ring bond distances of the fluoropyridines are very similar to those of pyridine except for a shortening of the C-N(F) bond in 2-fluoropyridine. The C-F bond stretching frequencies are similar to that in fluorobenzene reflecting the influence of the ring π bonding. PMID:21570895

  15. Analytical Calculation of Energy levels of mono- and bilayer Graphene Quantum Dots Used as Light Absorber in Solar Cells

    NASA Astrophysics Data System (ADS)

    Tamandani, Shahryar; Darvish, Ghafar; Faez, Rahim

    2016-01-01

    In this paper by solving Dirac equation, we present an analytical solution to calculate energy levels and wave functions of mono- and bilayer graphene quantum dots. By supposing circular quantum dots, we solve Dirac equation and obtain energy levels and band gap with relations in a new closed and practical form. The energy levels are correlated with a radial quantum number and radius of quantum dots. In addition to monolayer quantum dots, AA- and AB-stacked bilayer quantum dots are investigated and their energy levels and band gap are calculated as well. Also, we analyze the influence of the quantum dots size on their energy spectrum. It can be observed that the band gap decreases as quantum dots' radius increases. On the other hand, increase in the band gap is more in AB-stacked bilayer quantum dots. Using the obtained relations, the band gap is obtained in each state. Comparing the energy spectra obtained from the tight-binding approximation with those of our obtained relations shows that the behavior of the energies as function of the dot size is qualitatively similar, but in some cases, quantitative differences can be seen. As quantum dots radius increases, the analytical results approach to the tight-binding method results.

  16. Development of a non-equilibrium quantum transport calculation method based on constrained density functional

    NASA Astrophysics Data System (ADS)

    Kim, Han Seul; Kim, Yong-Hoon

    2015-03-01

    We report on the development of a novel first-principles method for the calculation of non-equilibrium quantum transport process. Within the scheme, non-equilibrium situation and quantum transport within the open-boundary condition are described by the region-dependent Δ self-consistent field method and matrix Green's function theory, respectively. We will discuss our solutions to the technical difficulties in describing bias-dependent electron transport at complicated nanointerfaces and present several application examples. Global Frontier Program (2013M3A6B1078881), Basic Science Research Grant (2012R1A1A2044793), EDISON Program (No. 2012M3C1A6035684), and 2013 Global Ph.D fellowship program of the National Research Foundation. KISTI Supercomputing Center (KSC-2014-C3-021).

  17. FragBuilder: an efficient Python library to setup quantum chemistry calculations on peptides models

    PubMed Central

    Hamelryck, Thomas; Jensen, Jan H.

    2014-01-01

    We present a powerful Python library to quickly and efficiently generate realistic peptide model structures. The library makes it possible to quickly set up quantum mechanical calculations on model peptide structures. It is possible to manually specify a specific conformation of the peptide. Additionally the library also offers sampling of backbone conformations and side chain rotamer conformations from continuous distributions. The generated peptides can then be geometry optimized by the MMFF94 molecular mechanics force field via convenient functions inside the library. Finally, it is possible to output the resulting structures directly to files in a variety of useful formats, such as XYZ or PDB formats, or directly as input files for a quantum chemistry program. FragBuilder is freely available at https://github.com/jensengroup/fragbuilder/ under the terms of the BSD open source license. PMID:24688855

  18. Stretched DNA Investigated Using Molecular-Dynamics and Quantum-Mechanical Calculations

    PubMed Central

    Řezáč, Jan; Hobza, Pavel; Harris, Sarah A.

    2010-01-01

    Abstract We combined atomistic molecular-dynamics simulations with quantum-mechanical calculations to investigate the sequence dependence of the stretching behavior of duplex DNA. Our combined quantum-mechanical/molecular-mechanical approach demonstrates that molecular-mechanical force fields are able to describe both the backbone and base-base interactions within the highly distorted nucleic acid structures produced by stretching the DNA from the 5′ ends, which include conformations containing disassociated basepairs, just as well as these force fields describe relaxed DNA conformations. The molecular-dynamics simulations indicate that the force-induced melting pathway is sequence-dependent and is influenced by the availability of noncanonical hydrogen-bond interactions that can assist the disassociation of the DNA basepairs. The biological implications of these results are discussed. PMID:20074515

  19. Calculating work in weakly driven quantum master equations: Backward and forward equations.

    PubMed

    Liu, Fei

    2016-01-01

    I present a technical report indicating that the two methods used for calculating characteristic functions for the work distribution in weakly driven quantum master equations are equivalent. One involves applying the notion of quantum jump trajectory [Phys. Rev. E 89, 042122 (2014)PLEEE81539-375510.1103/PhysRevE.89.042122], while the other is based on two energy measurements on the combined system and reservoir [Silaev et al., Phys. Rev. E 90, 022103 (2014)PLEEE81539-375510.1103/PhysRevE.90.022103]. These represent backward and forward methods, respectively, which adopt a very similar approach to that of the Kolmogorov backward and forward equations used in classical stochastic theory. The microscopic basis for the former method is also clarified. In addition, a previously unnoticed equality related to the heat is also revealed. PMID:26871044

  20. Low-Mode Conformational Search Method with Semiempirical Quantum Mechanical Calculations: Application to Enantioselective Organocatalysis.

    PubMed

    Kamachi, Takashi; Yoshizawa, Kazunari

    2016-02-22

    A conformational search program for finding low-energy conformations of large noncovalent complexes has been developed. A quantitatively reliable semiempirical quantum mechanical PM6-DH+ method, which is able to accurately describe noncovalent interactions at a low computational cost, was employed in contrast to conventional conformational search programs in which molecular mechanical methods are usually adopted. Our approach is based on the low-mode method whereby an initial structure is perturbed along one of its low-mode eigenvectors to generate new conformations. This method was applied to determine the most stable conformation of transition state for enantioselective alkylation by the Maruoka and cinchona alkaloid catalysts and Hantzsch ester hydrogenation of imines by chiral phosphoric acid. Besides successfully reproducing the previously reported most stable DFT conformations, the conformational search with the semiempirical quantum mechanical calculations newly discovered a more stable conformation at a low computational cost. PMID:26815336

  1. Quantum chemical calculation of the equilibrium structures of small metal atom clusters

    NASA Technical Reports Server (NTRS)

    Kahn, L. R.

    1981-01-01

    The application of ab initio quantum mechanical approaches in the study of metal atom clusters requires simplifying techniques that do not compromise the reliability of the calculations. Various aspects of the implementation of the effective core potential (ECP) technique for the removal of the metal atom core electrons from the calculation were examined. The ECP molecular integral formulae were modified to bring out the shell characteristics as a first step towards fulfilling the increasing need to speed up the computation of the ECP integrals. Work on the relationships among the derivatives of the molecular integrals that extends some of the techniques pioneered by Komornicki for the calculation of the gradients of the electronic energy was completed and a formulation of the ECP approach that quite naturally unifies the various state-of-the-art "shape- and Hamiltonian-consistent" techniques was discovered.

  2. The three-fold theoretical basis of the Gravity Probe B gyro precession calculation

    NASA Astrophysics Data System (ADS)

    Adler, Ronald J.

    2015-11-01

    The Gravity Probe B (GP-B) experiment is complete and the results are in agreement with the predictions of general relativity (GR) for both the geodetic precession, 6.6 arcsec yr-1 to about 0.3%, and the Lense-Thirring precession, 39 marcsec to about 19%. This note is concerned with the theoretical basis for the predictions. The predictions depend on three elements of gravity theory, firstly that macroscopic gravity is described by a metric theory such as GR, secondly that the Lense-Thirring metric provides an approximate description of the gravitational field of the spinning Earth, and thirdly that the spin axis of a gyroscope is parallel displaced in spacetime, which gives its equation of motion. We look at each of these three elements to show how each is solidly based on previous experiments and well-tested theory. The agreement of GP-B with theory strengthens our belief that all three elements are correct and increases our confidence in applying GR to astrophysical phenomena. Conversely, if GP-B had not verified the predictions a major theoretical quandary would have occurred.

  3. Theoretical comparison of advanced methods for calculating nitrous oxide fluxes using non-steady state chambers

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Several flux-calculation (FC) schemes are available for determining soil-to-atmosphere emissions of nitrous oxide (N2O) and other trace gases using data from non-steady-state flux chambers. Recently developed methods claim to provide more accuracy in estimating the true pre-deployment flux (f0) comp...

  4. Comparison between Theoretical Calculation and Experimental Results of Excitation Functions for Production of Relevant Biomedical Radionuclides

    SciTech Connect

    Menapace, E.; Birattari, C.; Bonardi, M.L.; Groppi, F.; Morzenti, S.; Zona, C.

    2005-05-24

    The radionuclide production for biomedical applications has been brought up in the years, as a special nuclear application, at INFN LASA Laboratory, particularly in co-operation with the JRC-Ispra of EC. Mainly scientific aspects concerning radiation detection and the relevant instruments, the measurements of excitation functions of the involved nuclear reactions, the requested radiochemistry studies and further applications have been investigated. On the side of the nuclear data evaluations, based on nuclear model calculations and critically selected experimental data, the appropriate competence has been developed at ENEA Division for Advanced Physics Technologies. A series of high specific activity accelerator-produced radionuclides in no-carrier-added (NCA) form, for uses in metabolic radiotherapy and for PET radiodiagnostics, are investigated. In this work, last revised measurements and model calculations are reviewed for excitation functions of natZn(d,X)64Cu, 66Ga reactions, referring to irradiation experiments at K=38 variable energy Cyclotron of JRC-Ispra. Concerning the reaction data for producing 186gRe and 211At/211gPo (including significant emission spectra) and 210At, most recent and critically selected experimental results are considered and discussed in comparison with model calculations paying special care to pre-equilibrium effects estimate and to the appropriate overall parameterization. Model calculations are presented for 226Ra(p,2n)225Ac reaction, according to the working program of the ongoing IAEA CRP on the matter.

  5. Vibrational analysis of 4-chloro-3-nitrobenzonitrile by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Sert, Yusuf; Çırak, Çağrı; Ucun, Fatih

    2013-04-01

    In the present study, the experimental and theoretical harmonic and anharmonic vibrational frequencies of 4-chloro-3-nitrobenzonitrile were investigated. The experimental FT-IR (400-4000 cm-1) and μ-Raman spectra (100-4000 cm-1) of the molecule in the solid phase were recorded. Theoretical vibrational frequencies and geometric parameters (bond lengths and bond angles) were calculated using ab initio Hartree Fock (HF), density functional B3LYP and M06-2X methods with 6-311++G(d,p) basis set by Gaussian 09 W program, for the first time. The assignments of the vibrational frequencies were performed by potential energy distribution (PED) analysis by using VEDA 4 program. The theoretical optimized geometric parameters and vibrational frequencies were compared with the corresponding experimental data, and they were seen to be in a good agreement with each other. Also, the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies were found.

  6. Quantum Computational Calculations of the Ionization Energies of Acidic and Basic Amino Acids: Aspartate, Glutamate, Arginine, Lysine, and Histidine

    NASA Astrophysics Data System (ADS)

    de Guzman, C. P.; Andrianarijaona, M.; Lee, Y. S.; Andrianarijaona, V.

    An extensive knowledge of the ionization energies of amino acids can provide vital information on protein sequencing, structure, and function. Acidic and basic amino acids are unique because they have three ionizable groups: the C-terminus, the N-terminus, and the side chain. The effects of multiple ionizable groups can be seen in how Aspartate's ionizable side chain heavily influences its preferred conformation (J Phys Chem A. 2011 April 7; 115(13): 2900-2912). Theoretical and experimental data on the ionization energies of many of these molecules is sparse. Considering each atom of the amino acid as a potential departing site for the electron gives insight on how the three ionizable groups affect the ionization process of the molecule and the dynamic coupling between the vibrational modes. In the following study, we optimized the structure of each acidic and basic amino acid then exported the three dimensional coordinates of the amino acids. We used ORCA to calculate single point energies for a region near the optimized coordinates and systematically went through the x, y, and z coordinates of each atom in the neutral and ionized forms of the amino acid. With the calculations, we were able to graph energy potential curves to better understand the quantum dynamic properties of the amino acids. The authors thank Pacific Union College Student Association for providing funds.

  7. Photo-physical properties of 1-hydroxy-2-naphthaldehyde: A combined fluorescence spectroscopy and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Singh, Rupashree Balia; Mahanta, Subrata; Kar, Samiran; Guchhait, Nikhil

    2007-01-01

    The ground and excited state properties of 1-hydroxy-2-naphthaldehyde (HN12) towards proton transfer reaction have been elaborately investigated on the basis of steady state absorption and emission, time-resolved fluorescence spectroscopy and quantum chemical calculations by ab initio (Hartree-Fock) and density functional theory (DFT) methods. The molecule HN12 exists as closed (intramolecular hydrogen bonded) and open conformer and their anions, and the hydrogen bonded solvated cluster in the ground state. The closed conformer on excitation undergoes photo-induced keto-enol tautomerism across the pre-existing intramolecular hydrogen bond (IMHB) and shows a red shifted emission band for the keto tautomer. Theoretically a significant change of some structural parameters such as O d-H 1 bond length, O d⋯H 1⋯O a bond angle and charge distribution at the proton translocation site in the excited state favours intramolecular proton transfer process. Calculated potential energy curves along the proton transfer coordinate at the pre-existing hydrogen bonding site by DFT level account well for the feasibility of a barrierless ultrafast excited state intramolecular proton transfer reaction in HN12 molecule.

  8. Theoretical calculation of a composite pulse for 2H broadband excitation by average Hamiltonian theory

    PubMed Central

    Shen, Ming; Roopchand, Rabia; Amoureux, Jean-Paul; Chen, Qun

    2015-01-01

    Quadrupolar echo NMR spectroscopy of solids often requires RF pulse excitation that covers spectral widths exceeding 100 kHz. In a recent work we found out that a four pulse, composite pulse COM-II ( 90180¯90135¯45 ), provided robust broadband excitation for deuterium quadrupolar echo spectroscopy. Moreover, when combined with an eight step phase cycle, spectral distortions arising from finite pulse widths were greatly supressed. In this paper we report on a theoretical analysis COM-II with 8-step phase cycle by average Hamiltonian theory. This treatment is combined with the fictitious spin-1 operator formalism, and the mechanism of the 8-step phase cycling that minimizes the spectral distortions is discussed. PMID:26681896

  9. On the prediction of thermal stability of nitroaromatic compounds using quantum chemical calculations.

    PubMed

    Fayet, Guillaume; Rotureau, Patricia; Joubert, Laurent; Adamo, Carlo

    2009-11-15

    This work presents a new approach to predict thermal stability of nitroaromatic compounds based on quantum chemical calculations and on quantitative structure-property relationship (QSPR) methods. The data set consists of 22 nitroaromatic compounds of known decomposition enthalpy (taken as a macroscopic property related to explosibility) obtained from differential scanning calorimetry. Geometric, electronic and energetic descriptors have been selected and computed using density functional theory (DFT) calculation to describe the 22 molecules. First approach consisted in looking at their linear correlations with the experimental decomposition enthalpy. Molecular weight, electrophilicity index, electron affinity and oxygen balance appeared as the most correlated descriptors (respectively R(2)=0.76, 0.75, 0.71 and 0.64). Then multilinear regression was computed with these descriptors. The obtained model is a six-parameter equation containing descriptors all issued from quantum chemical calculations. The prediction is satisfactory with a correlation coefficient R(2) of 0.91 and a predictivity coefficient R(cv)(2) of 0.84 using a cross validation method. PMID:19616889

  10. Molecular modeling study of dihydrofolate reductase inhibitors. Molecular dynamics simulations, quantum mechanical calculations, and experimental corroboration.

    PubMed

    Tosso, Rodrigo D; Andujar, Sebastian A; Gutierrez, Lucas; Angelina, Emilio; Rodríguez, Ricaurte; Nogueras, Manuel; Baldoni, Héctor; Suvire, Fernando D; Cobo, Justo; Enriz, Ricardo D

    2013-08-26

    A molecular modeling study on dihydrofolate reductase (DHFR) inhibitors was carried out. By combining molecular dynamics simulations with semiempirical (PM6), ab initio, and density functional theory (DFT) calculations, a simple and generally applicable procedure to evaluate the binding energies of DHFR inhibitors interacting with the human enzyme is reported here, providing a clear picture of the binding interactions of these ligands from both structural and energetic viewpoints. A reduced model for the binding pocket was used. This approach allows us to perform more accurate quantum mechanical calculations as well as to obtain a detailed electronic analysis using the quantum theory of atoms in molecules (QTAIM) technique. Thus, molecular aspects of the binding interactions between inhibitors and the DHFR are discussed in detail. A significant correlation between binding energies obtained from DFT calculations and experimental IC₅₀ values was obtained, predicting with an acceptable qualitative accuracy the potential inhibitor effect of nonsynthesized compounds. Such correlation was experimentally corroborated synthesizing and testing two new inhibitors reported in this paper. PMID:23834278

  11. Comparison of analytical formulae and quantum calculations for differential cross sections in e-Ar

    NASA Astrophysics Data System (ADS)

    Janssen, J. F. J.; Zatsarinny, O.; Bartschat, K.; Hagelaar, G. J. M.; Pitchford, L. C.

    2014-10-01

    We have previously shown that the fully ab initio, quantum mechanical B-spline R-matrix calculations of Zatsarinny and Bartschat for e-Ar cross sections yield accurate values of swarm parameters (transport and rate coefficients vs. reduced electric field strength, for uniform and constant E/N) when used as input in a Boltzmann solver. These comparisons were made by employing the calculated angle-integrated elastic momentum transfer and total inelastic cross sections (usually sufficient for accurate calculations of swarm parameters). The theory, however, also provides fully differential scattering information, which is now available for argon on the open access website LXCat (www.lxcat.net). In this presentation, we compare predictions from several previously proposed analytical formulae for the angular dependence of the cross sections with the quantum predictions. Such comparisons are of interest, for example, in PIC-MC simulations where, due to lack of information, some approximations about the angular dependence must be made and thus the use of analytical formulae is common. Work supported, in part, by the United States National Science Foundation (OZ and KB).

  12. Calculating Floquet states of large quantum systems: A parallelization strategy and its cluster implementation

    NASA Astrophysics Data System (ADS)

    Laptyeva, T. V.; Kozinov, E. A.; Meyerov, I. B.; Ivanchenko, M. V.; Denisov, S. V.; Hänggi, P.

    2016-04-01

    We present a numerical approach to calculate non-equilibrium eigenstates of a periodically time-modulated quantum system. The approach is based on the use of a chain of single-step propagating operators. Each operator is time-specific and constructed by combining the Magnus expansion of the time-dependent system Hamiltonian with the Chebyshev expansion of an operator exponent. The construction of the unitary Floquet operator, which evolves a system state over the full modulation period, is performed by propagating the identity matrix over the period. The independence of the evolution of basis vectors makes the propagation stage suitable for realization on a parallel cluster. Once the propagation stage is completed, a routine diagonalization of the Floquet matrix is performed. Finally, an additional propagation round, now involving the eigenvectors as the initial states, allows to resolve the time-dependence of the Floquet states and calculate their characteristics. We demonstrate the accuracy and scalability of the algorithm by applying it to calculate the Floquet states of two quantum models, namely (i) a synthesized random-matrix Hamiltonian and (ii) a many-body Bose-Hubbard dimer, both of the size up to 104 states.

  13. Path-integral virial estimator for reaction rate calculation basedon the quantum instanton aproximation

    SciTech Connect

    Yang, Sandy; Yamamoto, Takeshi; Miller, William H.

    2005-11-28

    The quantum instanton approximation is a type of quantum transition state theory that calculates the chemical reaction rate using the reactive flux correlation function and its low order derivatives at time zero. Here we present several path-integral estimators for the latter quantities, which characterize the initial decay profile of the flux correlation function. As with the internal energy or heat capacity calculation, different estimators yield different variances (and therefore different convergence properties) in a Monte Carlo calculation. Here we obtain a virial(-type) estimator by using a coordinate scaling procedure rather than integration by parts, which allows more computational benefits. We also consider two different methods for treating the flux operator, i.e., local-path and global-path approaches, in which the latter achieves a smaller variance at the cost of using second-order potential derivatives. Numerical tests are performed for a one-dimensional Eckart barrier and a model proton transfer reaction in a polar solvent, which illustrates the reduced variance of the virial estimator over the corresponding thermodynamic estimator.

  14. Theoretical Calculation of Molecular Structure, Vibrational Spectra, and Molecular Electrostatic Potential of Metolazone

    NASA Astrophysics Data System (ADS)

    Boopathi, M.; Udhayakala, P.; Rajendiran, T. V.; Gunasekaran, S.

    2016-03-01

    In the present investigation, a vibration spectral analysis was carried out using FT-Raman and FT-IR spectroscopy in the range 100-4000 and 400-4000 cm-1 respectively, for 7-chloro-1,2,3,4-tetrahydro-2-methyl-3-(2-methylphenyl)-4-oxo-6-quinazoline sulfonamide (metolazone). The molecular structure, fundamental vibration frequencies, and intensity of the vibration bands are interpreted with the help of structure optimizations by density functional theory (DFT) types of the electronic structure method in the B3LYP/6-311++G(d,p) basis set. The results of the calculations were applied to simulated spectra of the title compound, which showed good agreement with observed spectra. The overestimations of the calculated harmonic wave numbers were efficiently corrected with the aid of a specific scaling procedure. A molecular electrostatic potential (MEP) map of the titled compound has been plotted in order to predict the electron rich and poor centers.

  15. Theoretical Calculations of Refractive Properties for Hg3Te2Cl2 Crystals.

    PubMed

    Bokotey, O V

    2016-12-01

    This paper reviews the optical properties, such as refractive index, optical dielectric constant, and reflection coefficient of the Hg3Te2Cl2 crystals. The applications of the Hg3X2Y2 crystals as electronic, optical, and optoelectronic devices are very much determined by the nature and magnitude of these fundamental material properties. The origin of chemical bonding in the crystals is very important for definition of the physical and chemical properties. The main structural feature of the Hg3X2Y2 crystals is the presence of covalent pyramids [XHg3] and linear X-Hg-X groups. Optical properties are calculated according to the model proposed by Harrison. The refractive index in the spectral region far from the absorption edge is determined within the generalized single-oscillator model. The calculated results are found to be in good agreement with experimental data. PMID:27184964

  16. Laboratory measurements and theoretical calculations of O{sub 2} A band electric quadrupole transitions

    SciTech Connect

    Long, D. A.; Okumura, M.; Havey, D. K.; Hodges, J. T.; Pickett, H. M.; Miller, C. E.

    2009-10-15

    Frequency-stabilized cavity ring-down spectroscopy was utilized to measure electric quadrupole transitions within the {sup 16}O{sub 2} A band, b {sup 1}{sigma}{sub g}{sup +}(leftarrow)X {sup 3}{sigma}{sub g}{sup -}(0,0). We report quantitative measurements (relative uncertainties in intensity measurements from 4.4% to 11%) of nine ultraweak transitions in the {sup N}O, {sup P}O, {sup R}S, and {sup T}S branches with line intensities ranging from 3x10{sup -30} to 2x10{sup -29} cm molec.{sup -1}. A thorough discussion of relevant noise sources and uncertainties in this experiment and other cw-cavity ring-down spectrometers is given. For short-term averaging (t<100 s), we estimate a noise-equivalent absorption of 2.5x10{sup -10} cm{sup -1} Hz{sup -1/2}. The detection limit was reduced further by co-adding up to 100 spectra to yield a minimum detectable absorption coefficient equal to 1.8x10{sup -11} cm{sup -1}, corresponding to a line intensity of {approx}2.5x10{sup -31} cm molec.{sup -1}. We discuss calculations of electric quadrupole line positions based on a simultaneous fit of the ground and upper electronic state energies which have uncertainties <3 MHz, and we present calculations of electric quadrupole matrix elements and line intensities. The electric quadrupole line intensity calculations and measurements agreed on average to 5%, which is comparable to our average experimental uncertainty. The calculated electric quadrupole band intensity was 1.8(1)x10{sup -27} cm molec.{sup -1} which is equal to only {approx}8x10{sup -6} of the magnetic dipole band intensity.

  17. Theoretical calculations on the adhesion, stability, electronic structure and bonding of SiC/W interface

    NASA Astrophysics Data System (ADS)

    Jin, Na; Yang, Yanqing; Luo, Xian; Li, Jian; Huang, Bin; Liu, Shuai; Xiao, Zhiyuan

    2014-09-01

    The ?-SiC(1 1 1)/?-W(1 1 0) interfaces were studied by first-principles calculations based on density functional theory (DFT). The ideal work of adhesion (Wad) and interface energy (?int) were calculated for six different interfacial structures, taking into account both Si- and C-terminations of ?-SiC(1 1 1) surfaces, and three different stacking sequences. The interfacial electronic structures including charge density distribution and difference, and density of states (DOS) were simulated to determine the nature of SiC/W bonding. The results show that the Si-terminated top-site interface is the most stable interface, yielding the highest Wad and the lowest ?int. During the optimization, the Si-terminated top-site interface will transform into the center-site structure, resulting in the interaction among the interfacial W and Si atoms, and subinterfacial C atoms. In addition, the calculated interface energies show that an interdiffusion layer will form on the SiC/W interface. The experimental results also have verified the existence of an interdiffusion layer on the SiC/W interface in a CVD-SiC fiber.

  18. Quantum mechanical binding free energy calculation for phosphopeptide inhibitors of the Lck SH2 domain.

    PubMed

    Anisimov, Victor M; Cavasotto, Claudio N

    2011-07-30

    The accurate and efficient calculation of binding free energies is essential in computational biophysics. We present a linear-scaling quantum mechanical (QM)-based end-point method termed MM/QM-COSMO to calculate binding free energies in biomolecular systems, with an improved description of entropic changes. Molecular dynamics trajectories are re-evaluated using a semiempirical Hamiltonian and a continuum solvent model; translational and rotational entropies are calculated using configurational integrals, and internal entropy is calculated using the harmonic oscillator approximation. As an application, we studied the binding of a series of phosphotyrosine tetrapeptides to the human Lck SH2 domain, a key component in intracellular signal transduction, modulation of which can have therapeutic relevance in the treatment of cancer, osteoporosis, and autoimmune diseases. Calculations with molecular mechanics Poisson-Boltzmann, and generalized Born surface area methods showed large discrepancies with experimental data stemming from the enthalpic component, in agreement with an earlier report. The empirical force field-based solvent interaction energy scoring function yielded improved results, with average unsigned error of 3.6 kcal/mol, and a better ligand ranking. The MM/QM-COSMO method exhibited the best agreement both for absolute (average unsigned error = 0.7 kcal/mol) and relative binding free energy calculations. These results show the feasibility and promise of a full QM-based end-point method with an adequate balance of accuracy and computational efficiency. PMID:21484840

  19. From quantum chemistry and the classical theory of polar liquids to continuum approximations in molecular mechanics calculations

    NASA Astrophysics Data System (ADS)

    Hassan, Sergio A.; Mehler, Ernest L.

    Biological macromolecules and other polymers belong to the class of mesoscopic systems, with characteristic length scale of the order of a nanometer. Although microscopic models would be the preferred choice in theoretical calculations, their use in computer simulations becomes prohibitive for large systems or long simulation times. On the other hand, the use of purely macroscopic models in the mesoscopic domain may introduce artifacts, with effects that are difficult to assess and that may compromise the reliability of the calculations. Here is proposed an approach with the aim of minimizing the empirical nature of continuum approximations of solvent effects within the scope of molecular mechanics (MM) approximations in mesoscopic systems. Using quantum chemical methods, the potential generated by the molecular electron density is first decomposed in a multicenter-multipole expansion around predetermined centers. The monopole and dipole terms of the expansion at each site create electric fields that polarize the surrounding aqueous medium whose dielectric properties can be described by the classical theory of polar liquids. Debye's theory allows a derivation of the dielectric profiles created around isolated point charges and dipoles that can incorporate Onsager reaction field corrections. A superposition of screened Coulomb potentials obtained from this theory makes possible a simple derivation of a formal expression for the total electrostatic energy and the polar component of the solvation energy of the system. A discussion is presented on the physical meaning of the model parameters, their transferability, and their convergence to calculable quantities in the limit of simple systems. The performance of this continuum approximation in computer calculations of amino acids in the context of an atomistic force field is discussed. Applications of a continuum model based on screened Coulomb potentials in multinanosecond simulations of peptides and proteins are briefly reviewed.

  20. Determination of two structural forms of catalytic bridging ligand in zinc-phosphotriesterase by molecular dynamics simulation and quantum chemical calculation

    SciTech Connect

    Zhan, C.G.; Souza, O.N. de; Rittenhhouse, R.; Ornstein, R.L.

    1999-08-18

    Although a three-dimensional X-ray crystal structure of zinc-substituted phosphotriesterase was recently reported, it is uncertain whether a critical bridging ligand in the active site is a water molecule or a hydroxide ion. The identity of this bridging ligand is theoretically determined by performing both molecular dynamics simulations and quantum mechanical calculations. All of the results obtained indicate that this critical ligand in the active site of the reported X-ray crystal structure is a hydroxide anion rather than a water molecule and allow us to propose a dynamic ping-pong model in which both kinds of structures might exist.

  1. Hidden variables in quantum mechanics: Generic models, set-theoretic forcing, and the appearance of probability

    SciTech Connect

    Van Wesep, Robert A. . E-mail: rvanwesep@verizon.net

    2006-10-15

    The hidden-variables premise is shown to be equivalent to the existence of generic filters for systems of commuting observables of a quantum system. The significance of this equivalence is interpreted in light of the theory of generic filters and boolean-valued models in set theory. The apparent stochastic nature of quantum observation is derived for these hidden-variables models.

  2. An approximate framework for quantum transport calculation with model order reduction

    SciTech Connect

    Chen, Quan; Li, Jun; Yam, Chiyung; Zhang, Yu; Wong, Ngai; Chen, Guanhua

    2015-04-01

    A new approximate computational framework is proposed for computing the non-equilibrium charge density in the context of the non-equilibrium Green's function (NEGF) method for quantum mechanical transport problems. The framework consists of a new formulation, called the X-formulation, for single-energy density calculation based on the solution of sparse linear systems, and a projection-based nonlinear model order reduction (MOR) approach to address the large number of energy points required for large applied biases. The advantages of the new methods are confirmed by numerical experiments.

  3. Optimized preconditioners for Green function evaluation in quantum reactive scattering calculations

    NASA Astrophysics Data System (ADS)

    Poirier, Bill; Miller, William H.

    1997-01-01

    The optimal separable basis methodology is suggested for the efficient quantum-mechanical calculation of reactive and inelastic scattering amplitudes. The method gives rise to an optimally convergent distorted wave Born expansion of the Green's function. Computationally, this corresponds to an optimized DVR matrix preconditioning scheme. State-to-state and cumulative reactive scattering results are presented for the benchmark collinear H + H 2 → H 2 + H system. CPU time and memory requirements are drastically reduced in comparison with other methods, and results are obtained for previously prohibitive energy regimes.

  4. Path-integral calculation of the third virial coefficient of quantum gases at low temperatures

    SciTech Connect

    Garberoglio, Giovanni; Harvey, Allan H.

    2011-04-07

    We derive path-integral expressions for the second and third virial coefficients of monatomic quantum gases. Unlike previous work that considered only Boltzmann statistics, we include exchange effects (Bose-Einstein or Fermi-Dirac statistics). We use state-of-the-art pair and three-body potentials to calculate the third virial coefficient of {sup 3}He and {sup 4}He in the temperature range 2.6-24.5561 K. We obtain uncertainties smaller than those of the limited experimental data. Inclusion of exchange effects is necessary to obtain accurate results below about 7 K.

  5. Diffusion Rates for Hydrogen on Pd(111) from Molecular Quantum Dynamics Calculations.

    PubMed

    Firmino, Thiago; Marquardt, Roberto; Gatti, Fabien; Dong, Wei

    2014-12-18

    The van Hove formula for the dynamical structure factor (DSF) related to particle scattering at mobile adsorbates is extended to include the relaxation of the adsorbates' vibrational states. The total rate obtained from the DSF is assumed to be the sum of a diffusion and a relaxation rate. A simple kinetic model to support this assumption is presented. To illustrate its potential applicability, the formula is evaluated using wave functions, energies, and lifetimes of vibrational states obtained for H/Pd(111) from first-principle calculations. Results show that quantum effects can be expected to be important even at room temperature. PMID:26273973

  6. The calculation of theoretical chromospheric models and the interpretation of solar spectra from rockets and spacecraft

    NASA Technical Reports Server (NTRS)

    Avrett, E. H.

    1985-01-01

    Solar chromospheric models are described. The models included are based on the observed spectrum, and on the assumption of hydrostatic equilibrium. The calculations depend on realistic solutions of the radiative transfer and statistical equilibrium equations for optically thick lines and continua, and on including the effects of large numbers of lines throughout the spectrum. Although spectroheliograms show that the structure of the chromosphere is highly complex, one-dimensional models of particular features are reasonably successful in matching observed spectra. Such models were applied to the interpretation of chromospheric observations.

  7. Correlation of theoretical calculations and experimental measurements of damage around a shaft in salt

    SciTech Connect

    Munson, D.E.; Holcomb, D.J.; DeVries, K.L.; Brodsky, N.S.

    1994-12-31

    Cross-hole ultrasonic measurements were made in the immediate wall of the Air Intake Shaft of the Waste Isolation Pilot Plant facility. These measurements show that compressional wave speed markedly decreases at the shaft wall and then increases with radial distance from the shaft to eventually become that of solid or undamaged salt. This behavior is indicative of deformation damage or microfractures in the salt. These in situ data are compared to both laboratory measurements of wave speed as a function of volume dilatancy and to calculations based on the Multimechanism Deformation Coupled Fracture model, with reasonable agreement.

  8. Proton transfer in acetaldehyde and acetaldehyde-water clusters: Vacuum ultraviolet photoionization experiment and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Kostko, Oleg; Troy, Tyler P.; Bandyopadhyay, Biswajit; Ahmed, Musahid

    2015-03-01

    Acetaldehyde, a probable human carcinogen and of environmental importance, upon solvation provides a test bed for understanding proton transfer pathways and catalytic mechanisms. In this study, we report on single photon vacuum ultraviolet photoionization of small acetaldehyde and acetaldehyde-water clusters. Appearance energies of protonated clusters are extracted from the experimental photoionization efficiency curves and compared to electronic structure calculations. The comparison of experimental data to computational results provides mechanistic insight into the fragmentation mechanisms of the observed mass spectra. Using deuterated water for isotopic tagging, we observe that proton transfer is mediated via acetaldehyde and not water in protonated acetaldehyde-water clusters.

  9. Theoretical and numerical calculation of the Eddy viscosity in smooth and rough turbulent boundary layers

    NASA Astrophysics Data System (ADS)

    Bailon-Cuba, Jorge

    2005-11-01

    A numerical implementation of the theory of George and Castillo (GC-97) for smooth and Seo (2003) for rough, is being done for the computation of the Reynolds shear stresses, -, and the eddy viscosity <νT>/ν. Starting with the similarity solutions of the Navier Stockes equations for the inner and outer flow, the resulting partial differential equations are integrated considering asymptotic boundary conditions consistent with the physics of the inner and outer flow. The empirical and theoretical velocity profiles proposed by GC-97 are used for the inner and outer flow respectively. The results are compared with experimental data showing an excellent agreement in the inner region, and a reasonable accuracy in the outer region, for hydraulically smooth surfaces (k^+ <=5). Comparison with LES of Bohr et al., is also done, showing an excellent agreement, despite of the method simplicity. Influence on the physics of the Reynolds number, &+circ;, and the roughness parameter, k^+, are also discussed. The accuracy of the computed , allows the resulting eddy viscosity, <νT>, can be used in turbulence modeling and simulations (i.e. LES subgrid scale model).

  10. The calculation of theoretical chromospheric models and the interpretation of solar spectra from rockets and spacecraft

    NASA Technical Reports Server (NTRS)

    Avrett, E. H.

    1986-01-01

    Calculated results based on two chromospheric flare models F1 and F2 of Machado, et al., (1980) are presented. Two additional models are included: F1*, which has enhanced temperatures relative to the weak-flare model F1 in the upper photosphere and low chromosphere, and F3 which has enhanced temperatures relative to the strong flare model F2 in the upper chromosphere. Each model is specified by means of a given variation of the temperature as a function of column mass. The corresponding variation of particle density and the geometrical height scale are determined by assuming hydrostatic equilibrium. The coupled equations of statistical equilibrium is solved as is radiative transfer for H, H-, He I-II, C I-IV, Si I-II, Mg I-II, Fe, Al, O I-II, Na, and Ca II. The overall absorption and emission of radiation by lines throughout the spectrum is determined by means of a reduced set of opacities sampled from a compilation of over 10 to the 7th power individual lines. That the white flight flare continuum may arise by extreme chromospheric overheating as well as by an enhancement of the minimum temperature region is also shown. The radiative cooling rate calculations for our brightest flare model suggest that chromospheric overheating provides enhanced radiation that could cause significant heating deep in the flare atmosphere.

  11. Zinc and cadmium dihydroxide molecules: matrix infrared spectra and theoretical calculations.

    PubMed

    Wang, Xuefeng; Andrews, Lester

    2005-05-01

    Laser-ablated zinc and cadmium atoms were mixed uniformly with H2 and O2 in excess argon or neon and with O2 in pure hydrogen or deuterium during deposition at 8 or 4 K. UV irradiation excites metal atoms to insert into O2 producing OMO molecules (M = Zn, Cd), which react further with H2 to give the metal hydroxides M(OH)2 and HMOH. The M(OH)2 molecules were identified through O-H and M-O stretching modes with appropriate HD, D2, (16,18)O2, and (18)O2 isotopic shifts. The HMOH molecules were characterized by O-H, M-H, and M-O stretching modes and an M-O-H bending mode, which were particularly strong in pure H2/D2. Analogous Zn and Cd atom reactions with H2O2 in excess argon produced the same M(OH)2 absorptions. Density functional theory and MP2 calculations reproduce the IR spectra of these molecules. The bonding of Group 12 metal dihydroxides and comparison to Group 2 dihydroxides are discussed. Although the Group 12 dihydroxide O-H stretching frequencies are lower, calculated charges show that the Group 2 dihydroxide molecules are more ionic. PMID:16833701

  12. New triterpenes from Maytenus robusta: structural elucidation based on NMR experimental data and theoretical calculations.

    PubMed

    Sousa, Grasiely F; Duarte, Lucienir P; Alcântara, Antônio F C; Silva, Grácia D F; Vieira-Filho, Sidney A; Silva, Roqueline R; Oliveira, Djalma M; Takahashi, Jacqueline A

    2012-01-01

    Leaves of Maytenus robusta (Celastraceae) were subjected to phytochemical investigation mainly directed at the isolation of pentacyclic triterpenes. The compounds friedelin (1), β-friedelinol (2), 3-oxo-21β-H-hop-22(29)-ene (7), 3,4-seco-friedelan-3,11β-olide (8), 3β-hydroxy-21β-H-hop-22(29)-ene (9), 3,4-seco-21β-H-hop-22(29)-en-3-oic acid (10), 3,4-seco-friedelan-3-oic acid (11), and sitosterol were identified in the hexane extract of M. robusta leaves. Compounds 8 and 9 are described herein for the first time. The structure and stereochemistry of both compounds were experimentally established by IR, HRLC-MS, and 1D (1H, 13C, and DEPT 135) and 2D (HSQC, HMBC and COSY) NMR data and supported by correlations with carbon chemical shifts calculated using the DFT method (BLYP/6-31G* level). Compounds 7 and 10 are also described for the first time, and their chemical structures were established by comparison with NMR data of similar structures described in the literature and correlations with BLYP/6-31G* calculated carbon chemical shifts. Compound 9, a mixture of 11 and sitosterol, and 3β,11β-dihydroxyfriedelane (4) were evaluated by the Ellman’s method and all these compounds showed acethylcholinesterase inhibitory properties. PMID:23147402

  13. ``Phantom'' Modes in Ab Initio Tunneling Calculations: Implications for Theoretical Materials Optimization, Tunneling, and Transport

    NASA Astrophysics Data System (ADS)

    Barabash, Sergey V.; Pramanik, Dipankar

    2015-03-01

    Development of low-leakage dielectrics for semiconductor industry, together with many other areas of academic and industrial research, increasingly rely upon ab initio tunneling and transport calculations. Complex band structure (CBS) is a powerful formalism to establish the nature of tunneling modes, providing both a deeper understanding and a guided optimization of materials, with practical applications ranging from screening candidate dielectrics for lowest ``ultimate leakage'' to identifying charge-neutrality levels and Fermi level pinning. We demonstrate that CBS is prone to a particular type of spurious ``phantom'' solution, previously deemed true but irrelevant because of a very fast decay. We demonstrate that (i) in complex materials, phantom modes may exhibit very slow decay (appearing as leading tunneling terms implying qualitative and huge quantitative errors), (ii) the phantom modes are spurious, (iii) unlike the pseudopotential ``ghost'' states, phantoms are an apparently unavoidable artifact of large numerical basis sets, (iv) a presumed increase in computational accuracy increases the number of phantoms, effectively corrupting the CBS results despite the higher accuracy achieved in resolving the true CBS modes and the real band structure, and (v) the phantom modes cannot be easily separated from the true CBS modes. We discuss implications for direct transport calculations. The strategy for dealing with the phantom states is discussed in the context of optimizing high-quality high- κ dielectric materials for decreased tunneling leakage.

  14. DFT-based Theoretical Calculation of Nb- and W-doped Anatase TiO2

    NASA Astrophysics Data System (ADS)

    Suenaga, Takahiro; Kamisaka, Hideyuki; Nakamura, Hisao; Yamashita, Koichi

    2010-03-01

    The structure and electronic states in the Nb-doped TiO2 (TNO) and W-doped TiO2 (TWO) in anatase phase were investigated from the first-principle using DFT-based band structure method. In addition to the cases where the dopant substituting a Ti atom, cells containing a dopant (MTi; M = Nb, W) and an oxygen vacancy (VO) were calculated in order to clarify the role of the oxygen vacancy in the system. Furthermore, cells containing two dopants and an oxygen vacancy (2MTi--VO), and cells with a dopant and two oxygen vacancies (MTi--2VO) were calculated. Energetically stable structures were found among the sampled 2WTi--VO and WTi--2VO cells, while the corresponding structures in TNO did not show any significant energy stabilization. Impurity states were found in the stable 2WTi--VO and WTi--2VO structures, and an approach of the two WTi atoms was observed in the former. The present results rationalize the lower electronic conductivity of TWO than that of TNO, and suggest possible formation of complex structures consisting of the WTi dopants and the oxygen vacancies.

  15. The reaction mechanism of allene oxide synthase: Interplay of theoretical QM/MM calculations and experimental investigations.

    PubMed

    Cho, Kyung-Bin; Lai, Wenzhen; Hamberg, Mats; Raman, C S; Shaik, Sason

    2011-03-01

    A combined theoretical and experimental study highlights the reaction mechanism of allene oxide synthase (AOS) and its possible link to hydroperoxide lyase (HPL) pathway. A previously published study (Lee et al., Nature 455 (2008) 363) has shown that the F137 residue is of central importance in differentiating between the AOS and HPL pathways after initial identical steps. In the experimental part of this study, we show that wild-type AOS from Arabidopsis or rice in fact produces both AOS and HPL products in a ratio of about 80:15, something that was found only in trace amounts before. Theoretical calculations successfully map the whole AOS pathway with 13(S)-hydroperoxy linolenic and linoleic acid as substrates. Subsequent calculations investigated the effects of in silico F137L mutation at the suggested diverging point of the two pathways. The results show that QM/MM calculations can reasonably reproduce three out of four experimentally available cases, and confirm that the pathways are energetically very close to each other, thus making a switch from one path to other plausible under different circumstances. PMID:20654573

  16. Quantum Monte Carlo calculations of neutron matter with chiral three-body forces

    NASA Astrophysics Data System (ADS)

    Tews, I.; Gandolfi, S.; Gezerlis, A.; Schwenk, A.

    2016-02-01

    Chiral effective field theory (EFT) enables a systematic description of low-energy hadronic interactions with controlled theoretical uncertainties. For strongly interacting systems, quantum Monte Carlo (QMC) methods provide some of the most accurate solutions, but they require as input local potentials. We have recently constructed local chiral nucleon-nucleon (NN) interactions up to next-to-next-to-leading order (N2LO ). Chiral EFT naturally predicts consistent many-body forces. In this paper, we consider the leading chiral three-nucleon (3N) interactions in local form. These are included in auxiliary field diffusion Monte Carlo (AFDMC) simulations. We present results for the equation of state of neutron matter and for the energies and radii of neutron drops. In particular, we study the regulator dependence at the Hartree-Fock level and in AFDMC and find that present local regulators lead to less repulsion from 3N forces compared to the usual nonlocal regulators.

  17. Progesterone and testosterone studies by neutron scattering and nuclear magnetic resonance methods and quantum chemistry calculations

    NASA Astrophysics Data System (ADS)

    Szyczewski, A.; Hołderna-Natkaniec, K.; Natkaniec, I.

    2004-05-01

    Inelastic incoherent neutron scattering spectra of progesterone and testosterone measured at 20 and 290 K were compared with the IR spectra measured at 290 K. The Phonon Density of States spectra display well resolved peaks of low frequency internal vibration modes up to 1200 cm -1. The quantum chemistry calculations were performed by semiempirical PM3 method and by the density functional theory method with different basic sets for isolated molecule, as well as for the dimer system of testosterone. The proposed assignment of internal vibrations of normal modes enable us to conclude about the sequence of the onset of the torsion movements of the CH 3 groups. These conclusions were correlated with the results of proton molecular dynamics studies performed by NMR method. The GAUSSIAN program had been used for calculations.

  18. Parallelizing the QUDA Library for Multi-GPU Calculations in Lattice Quantum Chromodynamics

    SciTech Connect

    Ronald Babich, Michael Clark, Balint Joo

    2010-11-01

    Graphics Processing Units (GPUs) are having a transformational effect on numerical lattice quantum chromodynamics (LQCD) calculations of importance in nuclear and particle physics. The QUDA library provides a package of mixed precision sparse matrix linear solvers for LQCD applications, supporting single GPUs based on NVIDIA's Compute Unified Device Architecture (CUDA). This library, interfaced to the QDP++/Chroma framework for LQCD calculations, is currently in production use on the "9g" cluster at the Jefferson Laboratory, enabling unprecedented price/performance for a range of problems in LQCD. Nevertheless, memory constraints on current GPU devices limit the problem sizes that can be tackled. In this contribution we describe the parallelization of the QUDA library onto multiple GPUs using MPI, including strategies for the overlapping of communication and computation. We report on both weak and strong scaling for up to 32 GPUs interconnected by InfiniBand, on which we sustain in excess of 4 Tflops.

  19. Spin Density Functional Calculations for Quantum Dots: How Much Can We Trust Them?

    NASA Astrophysics Data System (ADS)

    Ullmo, Denis; Jiang, Hong; Yang, Weitao; Baranger, H. U.

    2004-03-01

    We introduce a Strutinsky-type approximation to spin density functional theory (SDFT) which makes it possible to discuss SDFT results within a Landau Fermi liquid like framework. SDFT is, of course, a method of choice for quantitative predictions of the ground state of a specific quantum dot (addition energy and spin polarization). Since it is necessary to describe correctly the spin degree of freedom, we have in mind a treatment in which the spin up and spin down densities are independent variables. Such calculations have been shown, however, to give rise to an unexpected qualitative picture: compared to previous analysis, spin density functional theory predicts higher spins and less odd/even asymmetry in addition spectra. From the Strutinsky approach, when second order terms are included, the qualitative properties of the SDFT calculations, and in particular the origin of the higher spins and reduction of odd/even asymmetry, can be understood.

  20. Synthesis, crystal structure, biological activity and theoretical calculations of novel isoxazole derivatives

    NASA Astrophysics Data System (ADS)

    Jin, R. Y.; Sun, X. H.; Liu, Y. F.; Long, W.; Chen, B.; Shen, S. Q.; Ma, H. X.

    2016-01-01

    Series of isoxazole derivatives were synthesized by substituted chalcones and 2-chloro-6-fluorobenzene formaldehyde oxime with 1,3-dipolar cycloaddition. The target compounds were determined by melting point, IR, 1H NMR, elemental analyses and HRMS. The crystal structure of compound 3a was detected by X-ray diffraction and it crystallizes in the triclinic space group p2(1)/c with z = 4. The molecular geometry of compound 3a was optimized using density functional theory (DFT/B3LYP) method with the 6-31G+(d,p) basis set in the ground state. From the optimized geometry of the molecule, FT-IR, FT-Raman, HOMO-LUMO and natural bond orbital (NBO) were calculated at B3LYP/6-31G+(d,p) level. Finally, the antifungal activity of the synthetic compounds were evaluated against Pythium solani, Gibberella nicotiancola, Fusarium oxysporium f.sp. niveum and Gibberella saubinetii.

  1. Calculation of stress intensity factors in an isotropic multicracked plate. Part 1: Theoretical development

    NASA Technical Reports Server (NTRS)

    Binienda, W. K.; Arnold, S. M.; Tan, H. Q.

    1992-01-01

    An essential part of describing the damage state and predicting the damage growth in a multicracked plate is the accurate calculation of stress intensity factors (SIF's). Here, a methodology and rigorous solution formulation for SIF's of a multicracked plate, with fully interacting cracks, subjected to a far-field arbitrary stress state is presented. The fundamental perturbation problem is derived, and the steps needed to formulate the system of singular integral equations whose solution gives rise to the evaluation of the SIF's are identified. This analytical derivation and numerical solution are obtained by using intelligent application of symbolic computations and automatic FORTRAN generation capabilities (described in the second part of this paper). As a result, a symbolic/FORTRAN package, named SYMFRAC, that is capable of providing accurate SIF's at each crack tip was developed and validated.

  2. Synthesis, crystal structure, biological activity and theoretical calculations of novel isoxazole derivatives.

    PubMed

    Jin, R Y; Sun, X H; Liu, Y F; Long, W; Chen, B; Shen, S Q; Ma, H X

    2016-01-01

    Series of isoxazole derivatives were synthesized by substituted chalcones and 2-chloro-6-fluorobenzene formaldehyde oxime with 1,3-dipolar cycloaddition. The target compounds were determined by melting point, IR, (1)H NMR, elemental analyses and HRMS. The crystal structure of compound 3a was detected by X-ray diffraction and it crystallizes in the triclinic space group p2(1)/c with z=4. The molecular geometry of compound 3a was optimized using density functional theory (DFT/B3LYP) method with the 6-31G+(d,p) basis set in the ground state. From the optimized geometry of the molecule, FT-IR, FT-Raman, HOMO-LUMO and natural bond orbital (NBO) were calculated at B3LYP/6-31G+(d,p) level. Finally, the antifungal activity of the synthetic compounds were evaluated against Pythium solani, Gibberella nicotiancola, Fusarium oxysporium f.sp. niveum and Gibberella saubinetii. PMID:26218917

  3. Theoretical method for calculating relative joint geometry of assembled robot arms

    NASA Technical Reports Server (NTRS)

    Barker, L. K.; Moore, M. C.

    1983-01-01

    Equations are developed to extract the relative joint parameters of an assembled robot arm. Specifically, the Denavit-Hartenberg parameters, which completely characterize the relative joint geometry, are calculated. These parameters are needed to control the hand of the robot arm by resolved rate. As an example, the parameter extraction equations are used with perfect simulated data (no measurement noise) obtained from a mathematical model of a six-degree-of-freedom robot arm. For an actual application, measurement data needed to estimate the relative joint parameters can be generated by moving a robot arm to different positions, measuring the location of the hand (or other extension) in base coordinates, and recording the corresponding joint angles.

  4. Accuracy of Theoretical OAMO Calculations for Electron-Impact Ionization of Molecules

    NASA Astrophysics Data System (ADS)

    Chaluvadi, Hari

    2013-09-01

    The study of electron impact single ionization of atoms and molecules has provided valuable information about fundamental collisions. The most detailed information is obtained from triple differential cross sections (TDCS) in which the energy and momentum of all three final state particles are determined. These cross sections are much more difficult for theory since the detailed kinematics of the experiment become important. There are many theoretical approximations for ionization of molecules. One of the successful methods is the distorted wave (DW) approximation. One of the strengths of the DW approximation is that it can be applied for any energy and any size molecule. One of the approximations that has been made to significantly reduce the required computer time is the OAMO (orientation averaged molecular orbital) approximation. Surprisingly, the M3DW-OAMO approximation yields reasonably good agreement with experiment for ionization of H2 by both low and intermediate energy incident electrons. On the other hand, the M3DW-OAMO results for ionization of CH4 and NH3 did not agree very well with experiment. Consequently, we decided to check the validity of the OAMO approximation by performing a proper average over orientations and we found much better agreement with experimental data. In this talk we will show the current status of agreement between experiment and theory for low and intermediate energy single ionization of small, medium, and large molecules. This work is supported by the US National Science Foundation under Grant. No. PHY - 1068237. Computational work was performed with Institutional resources made available through Los Alamos National Laboratory.

  5. Molecular structure of caffeine as determined by gas electron diffraction aided by theoretical calculations

    NASA Astrophysics Data System (ADS)

    Egawa, Toru; Kamiya, Akemi; Takeuchi, Hiroshi; Konaka, Shigehiro

    2006-12-01

    The molecular structure of caffeine (3,7-dihydro-1,3,7-trimethyl-1H-purine-2,6-dione) was determined by means of gas electron diffraction. The nozzle temperature was 185 °C. The results of MP2 and B3LYP calculations with the 6-31G ∗∗ basis set were used as supporting information. These calculations predicted that caffeine has only one conformer and some of the methyl groups perform low frequency internal rotation. The electron diffraction data were analyzed on this basis. The determined structural parameters ( rg and ∠ α) of caffeine are as follows: < r(N sbnd C) ring> = 1.382(3) Å; r(C dbnd C) = 1.382(←) Å; r(C sbnd C) = 1.446(18) Å; r(C dbnd N) = 1.297(11) Å; < r(N sbnd C methyl)> = 1.459(13) Å; < r(C dbnd O)> = 1.206(5) Å; < r(C sbnd H)> = 1.085(11) Å; ∠N 1sbnd C 2sbnd N 3 = 116.5(11)°; ∠N 3sbnd C 4dbnd C 5 = 121. 5(13)°; ∠C 4dbnd C 5sbnd C 6 = 122.9(10)°; ∠C 4dbnd C 5sbnd N 7 = 104.7(14)°; ∠N 9-C 4=C 5 = 111.6(10)°; <∠N sbnd C sbnd H methyl> = 108.5(28)°. Angle brackets denote average values; parenthesized values are the estimated limits of error (3 σ) referring to the last significant digit; left arrow in parentheses means that this parameter is bound to the preceding one.

  6. Hybrid theory and calculation of e-N2 scattering. [quantum mechanics - nuclei (nuclear physics)

    NASA Technical Reports Server (NTRS)

    Chandra, N.; Temkin, A.

    1975-01-01

    A theory of electron-molecule scattering was developed which was a synthesis of close coupling and adiabatic-nuclei theories. The theory is shown to be a close coupling theory with respect to vibrational degrees of freedom but is a adiabatic-nuclei theory with respect to rotation. It can be applied to any number of partial waves required, and the remaining ones can be calculated purely in one or the other approximation. A theoretical criterion based on fixed-nuclei calculations and not on experiment can be given as to which partial waves and energy domains require the various approximations. The theory allows all cross sections (i.e., pure rotational, vibrational, simultaneous vibration-rotation, differential and total) to be calculated. Explicit formulae for all the cross sections are presented.

  7. Thermochemistry and Charge Delocalization in Cyclization Reactions Using Accurate Quantum Monte Carlo Calculations

    NASA Astrophysics Data System (ADS)

    Saritas, Kayahan; Grossman, Jeffrey C.

    2015-03-01

    Molecules that undergo pericyclic isomerization reactions find interesting optical and energy storage applications, because of their usually high quantum yields, large spectral shifts and small structural changes upon light absorption. These reactions induce a drastic change in the conjugated structure such that substituents that become a part of the conjugated system upon isomerization can play an important role in determining properties such as enthalpy of isomerization and HOMO-LUMO gap. Therefore, theoretical investigations dealing with such systems should be capable of accurately capturing the interplay between electron correlation and exchange effects. In this work, we examine the dihydroazulene isomerization as an example conjugated system. We employ the highly accurate quantum Monte Carlo (QMC) method to predict thermochemical properties and to benchmark results from density functional theory (DFT) methods. Although DFT provides sufficient accuracy for similar systems, in this particular system, DFT predictions of ground state and reaction paths are inconsistent and non-systematic errors arise. We present a comparison between QMC and DFT results for enthalpy of isomerization, HOMO-LUMO gap and charge densities with a range of DFT functionals.

  8. Ab-Initio Calculations of Electronic Properties and Quantum Transport in U-Shaped Graphene Nanoribbons

    NASA Astrophysics Data System (ADS)

    Cuong, Nguyen Tien; Mizuta, Hiroshi; Cong, Bach Thanh; Otsuka, Nobuo; Chi, Dam Hieu

    2012-09-01

    Graphene is a promising candidate as a material used in nano-scale devices because of recent developments in advanced experimental techniques. Motivated by recent successful fabrications of U-shaped graphene channel transistors by using the gallium focused ion beam technology, we have performed ab-initio calculations to investigate the electronic properties and quantum transport in U-shaped graphene nanoribbons. The electronic properties are calculated using a numerical atomic orbital basis set in the framework of the density functional theory. The transport properties are investigated using the non-equilibrium Green's function method. The transmission spectra of U-shaped graphenes are analyzed in order to reveal the quantum transport of the systems. We found that the graphene nanoribbons tend to open a band gap when U-shaped structures are formed in both armchair and zigzag cases. The geometrical structures of U-shaped GNRs had enormous influences on the electron transport around the Fermi energy due to the formation of quasi-bound states at zigzag edges. The obtained results have provided valuable information for designing potential nano-scale devices based on graphenes.

  9. Critical comparison of electrode models in density functional theory based quantum transport calculations

    NASA Astrophysics Data System (ADS)

    Jacob, D.; Palacios, J. J.

    2011-01-01

    We study the performance of two different electrode models in quantum transport calculations based on density functional theory: parametrized Bethe lattices and quasi-one-dimensional wires or nanowires. A detailed account of implementation details in both the cases is given. From the systematic study of nanocontacts made of representative metallic elements, we can conclude that the parametrized electrode models represent an excellent compromise between computational cost and electronic structure definition as long as the aim is to compare with experiments where the precise atomic structure of the electrodes is not relevant or defined with precision. The results obtained using parametrized Bethe lattices are essentially similar to the ones obtained with quasi-one-dimensional electrodes for large enough cross-sections of these, adding a natural smearing to the transmission curves that mimics the true nature of polycrystalline electrodes. The latter are more demanding from the computational point of view, but present the advantage of expanding the range of applicability of transport calculations to situations where the electrodes have a well-defined atomic structure, as is the case for carbon nanotubes, graphene nanoribbons, or semiconducting nanowires. All the analysis is done with the help of codes developed by the authors which can be found in the quantum transport toolbox ALACANT and are publicly available.

  10. Quantum Calculation of Inelastic CO Collisions with H. II. Pure Rotational Quenching of High Rotational Levels

    NASA Astrophysics Data System (ADS)

    Walker, Kyle M.; Song, L.; Yang, B. H.; Groenenboom, G. C.; van der Avoird, A.; Balakrishnan, N.; Forrey, R. C.; Stancil, P. C.

    2015-09-01

    Carbon monoxide is a simple molecule present in many astrophysical environments, and collisional excitation rate coefficients due to the dominant collision partners are necessary to accurately predict spectral line intensities and extract astrophysical parameters. We report new quantum scattering calculations for rotational deexcitation transitions of CO induced by H using the three-dimensional potential energy surface (PES) of Song et al. State-to-state cross sections for collision energies from 10-5 to 15,000 cm-1 and rate coefficients for temperatures ranging from 1 to 3000 K are obtained for CO (v = 0, j) deexcitation from j=1-45 to all lower j‧ levels, where j is the rotational quantum number. Close-coupling and coupled-states calculations were performed in full-dimension for j=1-5, 10, 15, 20, 25, 30, 35, 40, and 45 while scaling approaches were used to estimate rate coefficients for all other intermediate rotational states. The current rate coefficients are compared with previous scattering results using earlier PESs. Astrophysical applications of the current results are briefly discussed.

  11. Quantum Monte Carlo calculation of the binding energy of the beryllium dimer.

    PubMed

    Deible, Michael J; Kessler, Melody; Gasperich, Kevin E; Jordan, Kenneth D

    2015-08-28

    The accurate calculation of the binding energy of the beryllium dimer is a challenging theoretical problem. In this study, the binding energy of Be2 is calculated using the diffusion Monte Carlo (DMC) method, using single Slater determinant and multiconfigurational trial functions. DMC calculations using single-determinant trial wave functions of orbitals obtained from density functional theory calculations overestimate the binding energy, while DMC calculations using Hartree-Fock or CAS(4,8), complete active space trial functions significantly underestimate the binding energy. In order to obtain an accurate value of the binding energy of Be2 from DMC calculations, it is necessary to employ trial functions that include excitations outside the valence space. Our best estimate DMC result for the binding energy of Be2, obtained by using configuration interaction trial functions and extrapolating in the threshold for the configurations retained in the trial function, is 908 cm(-1), only slightly below the 935 cm(-1) value derived from experiment. PMID:26328827

  12. Absorption of laser radiation in a H-He plasma. I - Theoretical calculation of the absorption coefficient

    NASA Technical Reports Server (NTRS)

    Stallcop, J. R.

    1974-01-01

    The theory for calculating the absorption of laser radiation by hydrogen is outlined for the temperatures and pressures of common laboratory plasmas. Nonhydrogenic corrections for determining the absorption by helium are also included. The coefficients for the absorption of He-Ne laser radiation at the wavelengths of 0.633, 1.15, and 3.39 microns in a H plasma is presented for temperatures in the range from 10,000 to 40,000 K and electron number densities in the range from 10 to the 15th power to 10 to the 18th power per cu cm. The total absorption of a H-He plasma calculated from this theory is compared with the measured absorption. The theoretical composition of the H-He absorption is analyzed with respect to the significant absorption processes, inverse bremsstrahlung, photoionization, resonance excitation, and photodetachment.

  13. A theoretical study of CO adsorption on gold by Hückel theory and density functional theory calculations.

    PubMed

    Sun, Keju; Kohyama, Masanori; Tanaka, Shingo; Takeda, Seiji

    2011-11-30

    It is crucial to understand the nature of CO adsorption on gold so as to elucidate the mechanism of low-temperature CO oxidation on nanogold catalysts. We performed theoretical analysis of CO adsorption on gold by using Hückel theory and density functional theory (DFT) calculations. Hückel theory indicates that CO adsorption on gold is dominated by the electron distribution at the Au atom, which is greatly affected by neighboring Au atoms, coadsorbed or doping species. The increase of σ-bonding electrons should weaken the CO adsorption, while the increase of π-electrons should strengthen the adsorption. DFT calculations proved this prediction quantitatively for various systems, including CO adsorption on a Au(100)-hex surface with locally varying subsurface configurations and CO coadsorption with acceptor or donor species. PMID:21953561

  14. Calculated and experimental NMR chemical shifts of p-menthane-3,9-diols. A combination of molecular dynamics and quantum mechanics to determine the structure and the solvent effects.

    PubMed

    Casanovas, J; Namba, A M; León, S; Aquino, G L; da Silva, G V; Alemán, C

    2001-06-01

    NMR chemical shifts have been experimentally measured and theoretically estimated for all the carbon atoms of (1R,3S,4S,8S)-p-menthane-3,9-diol in chloroform solution. Theoretical estimations were performed using a combination of molecular dynamics simulations and quantum mechanical calculations. Molecular dynamics simulations were used to obtain the most populated conformations of the (1R,3S:4S,8S)-p-menthane-3,9-diol as well as the distribution of the solvent molecules around it. Quantum mechanical calculations of NMR chemical shifts were performed on the most relevant conformations employing the GIAO-DFT formalism. A special emphasis was put in evaluating the effects of the surrounding solvent molecules. For this purpose, supermolecule calculations were performed on complexes constituted by the solute and n chloroform molecules, where n ranges from 3 to 16. An excellent agreement with experimental data has been obtained following this computational strategy. PMID:11374997

  15. Experimental and theoretical studies of band gap alignment in GaAs{sub 1−x}Bi{sub x}/GaAs quantum wells

    SciTech Connect

    Kudrawiec, R. Kopaczek, J.; Polak, M. P.; Scharoch, P.; Gladysiewicz, M.; Misiewicz, J.; Richards, R. D.; Bastiman, F.; David, J. P. R.

    2014-12-21

    Band gap alignment in GaAs{sub 1−x}Bi{sub x}/GaAs quantum wells (QWs) was studied experimentally by photoreflectance (PR) and theoretically, ab initio, within the density functional theory in which the supercell based calculations are combined with the alchemical mixing approximation applied to a single atom in a supercell. In PR spectra, the optical transitions related to the excited states in the QW (i.e., the transition between the second heavy-hole and the second electron subband) were clearly observed in addition to the ground state QW transition and the GaAs barrier transition. This observation is clear experimental evidence that this is a type I QW with a deep quantum confinement in the conduction and valence bands. From the comparison of PR data with calculations of optical transitions in GaAs{sub 1−x}Bi{sub x}/GaAs QW performed for various band gap alignments, the best agreement between experimental data and theoretical calculations has been found for the valence band offset of 52 ± 5%. A very similar valence band offset was obtained from ab initio calculations. These calculations show that the incorporation of Bi atoms into GaAs host modifies both the conduction and the valence band. For GaAs{sub 1−x}Bi{sub x} with 0 < x < 0.074, the conduction band shifts lineary at a rate of ∼33 meV per % Bi, which only slightly decreases with Bi concentration. Whereas the valance band shift is clearly non-linear. Reducing initially at a rate of ∼51 meV per % Bi for low concentrations of Bi and then at a significantly reduced rate of ∼20 meV per % Bi near the end of the studied composition range. The overall reduction rate of the band gap is parabolic and the reduction rates change from ∼84 to ∼53 meV per % Bi for lower and higher Bi concentrations, respectively. The calculated shifts of valence and conduction bands give the variation of valence (conduction) band offset between GaAs{sub 1−x}Bi{sub x} and GaAs in the range of ∼60%–40% (∼40%–60%), which is in good agreement with our conclusion derived from PR measurements.

  16. ELECTRON-ION RECOMBINATION OF Fe XII FORMING Fe XI: LABORATORY MEASUREMENTS AND THEORETICAL CALCULATIONS

    SciTech Connect

    Novotny, O.; Hahn, M.; Lestinsky, M.; Savin, D. W.; Badnell, N. R.; Bernhardt, D.; Mueller, A.; Schippers, S.; Grieser, M.; Krantz, C.; Repnow, R.; Wolf, A.

    2012-07-01

    We have measured electron-ion recombination for Fe XII forming Fe XI using a merged-beam configuration at the heavy-ion storage ring TSR located at the Max Planck Institute for Nuclear Physics in Heidelberg, Germany. The measured merged-beam recombination rate coefficient (MBRRC) for collision energies from 0 to 1500 eV is presented. This work uses a new method for determining the absolute MBRRC based on a comparison of the ion beam decay rate with and without the electron beam on. For energies below 75 eV, the spectrum is dominated by dielectronic recombination (DR) resonances associated with 3s {yields} 3p and 3p {yields} 3d core excitations. At higher energies, we observe contributions from 3 {yields} N' and 2 {yields} N' core excitation DR. We compare our experimental results to state-of-the-art multi-configuration Breit-Pauli (MCBP) calculations and find significant differences, both in resonance energies and strengths. We have extracted the DR contributions from the measured MBRRC data and transformed them into a plasma recombination rate coefficient (PRRC) for temperatures in the range of 10{sup 3}-10{sup 7} K. We show that the previously recommended DR data for Fe XII significantly underestimate the PRRC at temperatures relevant for both photoionized plasmas (PPs) and collisionally ionized plasmas (CPs). This is contrasted with our MCBP PRRC results, which agree with the experiment to within 30% at PP temperatures and even better at CP temperatures. We find this agreement despite the disagreement shown by the detailed comparison between our MCBP and experimental MBRRC results. Last, we present a simple parameterized form of the experimentally derived PRRC for easy use in astrophysical modeling codes.

  17. Benchmarking quantum mechanical calculations with experimental NMR chemical shifts of 2-HADNT

    NASA Astrophysics Data System (ADS)

    Liu, Yuemin; Junk, Thomas; Liu, Yucheng; Tzeng, Nianfeng; Perkins, Richard

    2015-04-01

    In this study, both GIAO-DFT and GIAO-MP2 calculations of nuclear magnetic resonance (NMR) spectra were benchmarked with experimental chemical shifts. The experimental chemical shifts were determined experimentally for carbon-13 (C-13) of seven carbon atoms for the TNT degradation product 2-hydroxylamino-4,6-dinitrotoluene (2-HADNT). Quantum mechanics GIAO calculations were implemented using Becke-3-Lee-Yang-Parr (B3LYP) and other six hybrid DFT methods (Becke-1-Lee-Yang-Parr (B1LYP), Becke-half-and-half-Lee-Yang-Parr (BH and HLYP), Cohen-Handy-3-Lee-Yang-Parr (O3LYP), Coulomb-attenuating-B3LYP (CAM-B3LYP), modified-Perdew-Wang-91-Lee-Yang-Parr (mPW1LYP), and Xu-3-Lee-Yang-Parr (X3LYP)) which use the same correlation functional LYP. Calculation results showed that the GIAO-MP2 method gives the most accurate chemical shift values, and O3LYP method provides the best prediction of chemical shifts among the B3LYP and other five DFT methods. Three types of atomic partial charges, Mulliken (MK), electrostatic potential (ESP), and natural bond orbital (NBO), were also calculated using MP2/aug-cc-pVDZ method. A reasonable correlation was discovered between NBO partial charges and experimental chemical shifts of carbon-13 (C-13).

  18. Quantum scattering calculations of energy transfer and dissociation of HCO in collisions with Ar

    SciTech Connect

    Pan, B.; Bowman, J.M.

    1995-12-08

    We report a quantum scattering calculation of energy transfer and collision-induced dissociation of HCO in collisions with Ar. The HCO rotation is treated in the infinite order sudden approximation, and the HCO vibrations are treated by the coupled-channel method. Sixty {ital L}{sup 2} HCO vibrational wave functions are included in the coupled-channel basis, of which 15 correspond to bound HCO states for zero HCO angular momentum, and the remainder represent a discretized continuum, which includes ten resonances. A simple ``sum-of-pairs`` potential is used to describe the Ar--HCO interaction, and the HCO intramolecular potential is the previous Legendre polynomial fit to {ital ab} {ital initio} calculations. Vibrational state-specific and state-to-state cross sections, averaged over the orientation of Ar relative to the CO-bond axis, are calculated over a range of translational energies. Collision-induced dissociation cross sections to form H+CO from all HCO bound states are presented, and decomposed into components corresponding to dissociation via HCO resonances and dissociation via no``nresonance states. The energy transfer from selected initial states is also calculated as a function of initial relative translational energy. {copyright} {ital 1995} {ital American} {ital Institute} {ital of} {ital Physics}.

  19. Calculations of Solvation Free Energy through Energy Reweighting from Molecular Mechanics to Quantum Mechanics.

    PubMed

    Jia, Xiangyu; Wang, Meiting; Shao, Yihan; König, Gerhard; Brooks, Bernard R; Zhang, John Z H; Mei, Ye

    2016-02-01

    In this work, the solvation free energies of 20 organic molecules from the 4th Statistical Assessment of the Modeling of Proteins and Ligands (SAMPL4) have been calculated. The sampling of phase space is carried out at a molecular mechanical level, and the associated free energy changes are estimated using the Bennett Acceptance Ratio (BAR). Then the quantum mechanical (QM) corrections are computed through the indirect Non-Boltzmann Bennett's acceptance ratio (NBB) or the thermodynamics perturbation (TP) method. We show that BAR+TP gives a minimum analytic variance for the calculated solvation free energy at the Gaussian limit and performs slightly better than NBB in practice. Furthermore, the expense of the QM calculations in TP is only half of that in NBB. We also show that defining the biasing potential as the difference of the solute-solvent interaction energy, instead of the total energy, can converge the calculated solvation free energies much faster but possibly to different values. Based on the experimental solvation free energies which have been published before, it is discovered in this study that BLYP yields better results than MP2 and some other later functionals such as B3LYP, M06-2X, and ωB97X-D. PMID:26731197

  20. A quantitative analysis of weak intermolecular interactions & quantum chemical calculations (DFT) of novel chalcone derivatives

    NASA Astrophysics Data System (ADS)

    Chavda, Bhavin R.; Gandhi, Sahaj A.; Dubey, Rahul P.; Patel, Urmila H.; Barot, Vijay M.

    2016-05-01

    The novel chalcone derivatives have widespread applications in material science and medicinal industries. The density functional theory (DFT) is used to optimized the molecular structure of the three chalcone derivatives (M-I, II, III). The observed discrepancies between the theoretical and experimental (X-ray data) results attributed to different environments of the molecules, the experimental values are of the molecule in solid state there by subjected to the intermolecular forces, like non-bonded hydrogen bond interactions, where as isolated state in gas phase for theoretical studies. The lattice energy of all the molecules have been calculated using PIXELC module in Coulomb -London -Pauli (CLP) package and is partitioned into corresponding coulombic, polarization, dispersion and repulsion contributions. Lattice energy data confirm and strengthen the finding of the X-ray results that the weak but significant intermolecular interactions like C-H…O, Π- Π and C-H… Π plays an important role in the stabilization of crystal packing.

  1. Calculation of gain and luminescence spectra of quantum-cascade laser structures taking into account asymmetric emission line broadening

    SciTech Connect

    Ushakov, D V; Manak, I S; Kononenko, V K

    2010-05-26

    The energy levels, wave functions, and matrix elements of optical dipole transitions are calculated numerically for superlattice quantum-cascade structures. The effect of spectral broadening on the shape of emission spectra is estimated and semiphenomenological asymmetric profiles of emission line broadening are proposed. It is shown that the electroluminescence spectra well agree with the calculated spontaneous recombination spectra. (lasers)

  2. Analysis and calculation of electronic properties and light absorption of defective sulfur-doped silicon and theoretical photoelectric conversion efficiency.

    PubMed

    Jiang, He; Chen, Changshui

    2015-04-23

    Most material properties can be traced to electronic structures. Black silicon produced from SF6 or sulfur powder via irradiation with femtosecond laser pulses displays decreased infrared absorption after annealing, with almost no corresponding change in visible light absorption. The high-intensity laser pulses destroy the original crystal structure, and the doping element changes the material performance. In this work, the structural and electronic properties of several sulfur-doped silicon systems are investigated using first principle calculations. Depending on the sulfur concentration (level of doping) and the behavior of the sulfur atoms in the silicon lattice, different states or an absence of states are exhibited, compared with the undoped system. Moreover, the visible-infrared light absorption intensities are structure specific. The results of our theoretical calculations show that the conversion efficiency of sulfur-doped silicon solar cells depends on the sulfur concentrations. Additionally, two types of defect configurations exhibit light absorption characteristics that differ from the other configurations. These two structures produce a rapid increase in the theoretical photoelectric conversion efficiency in the range of the specific chemical potential studied. By controlling the positions of the atomic sulfur and the sulfur concentration in the preparation process, an efficient photovoltaic (PV) material may be obtainable. PMID:25798659

  3. Theoretical calculation and experiment of microwave electromagnetic property of Ni(C) nanocapsules

    NASA Astrophysics Data System (ADS)

    Dan-Feng, Zhang; Zhi-Feng, Hao; Bi, Zeng; Yan-Nan, Qian; Ying-Xin, Huang; Zhen-Da, Yang

    2016-04-01

    With the combination of the dielectric loss of the carbon layer with the magnetic loss of the ferromagnetic metal core, carbon-coated nickel (Ni(C)) nanoparticles are expected to be the promising microwave absorbers. Microwave electromagnetic parameters and reflection loss in a frequency range of 2 GHz–18 GHz for paraffin-Ni(C) composites are investigated. The values of relative complex permittivity and permeability, the dielectric and magnetic loss tangent of paraffin-Ni(C) composites are measured, respectively, when the weight ratios of Ni(C) nanoparticles are equal to 10 wt%, 40 wt%, 50 wt%, 70 wt%, and 80 wt% in paraffin-Ni(C) composites. The results reveal that Ni(C) nanoparticles exhibit a peak of magnetic loss at about 13 GHz, suggesting that magnetic loss and a natural resonance could be found at that frequency. Based on the measured complex permittivity and permeability, the reflection losses of paraffin-Ni(C) composites with different weight ratios of Ni(C) nanoparticles and coating thickness values are simulated according to the transmission line theory. An excellent microwave absorption is obtained. To be proved by the experimental results, the reflection loss of composite with a coating thickness of 2 mm is measured by the Arch method. The results indicate that the maximum reflection loss reaches ‑26.73 dB at 12.7 GHz, and below ‑10 dB, the bandwidth is about 4 GHz. The fact that the measured absorption position is consistent with the calculated results suggests that a good electromagnetic match and a strong microwave absorption can be established in Ni(C) nanoparticles. The excellent Ni(C) microwave absorber is prepared by choosing an optimum layer number and the weight ratio of Ni(C) nanoparticles in paraffin-Ni(C) composites. Project supported by the Science and Technology Program of Guangdong Province, China (Grant Nos. 2014B010106005, 2013B051000077, and 2015A050502047) and the Science and Technology Program of Guangzhou City, China (Grant No. 201508030018).

  4. Analytical calculation of the quantum 1/f coherence parameter for HFETs

    NASA Astrophysics Data System (ADS)

    Handel, Peter H.; Sherif, Taher S.

    2010-03-01

    The ratio s of the coherent magnetic energy term and the incoherent mechanical kinetic energy terms of the drift motion in the hamiltonian of a current carrying system is calculated for the special cases of a HFET or FET. This ratio defines the resulting quantum 1/f noise from the coherent and conventional quantum 1/f effects. In this case of FETs and HFETs of much larger width w>>LDS>t, the kinetic energy Ek of average motion with drift velocity vd per unit length in the direction of the drain-source distance LDS in the channel of thickness t, is still given by Nmvd 2/2, but the magnetic energy Em per unit length in the direction of LDS is roughly proportional with the first power of w only, instead of w2, and can be approximated by Em = π[ln(w/2LDS)]LDS[nevS/c]2/w. Here S=wt is the cross section though which current flows this indicates field-decoherence along the large device width w. This yields a coherence ratio of s ≡ Em/Ek ~ πnrotLDSln(w/2LDS), which shows that only an effective width w=weff about equal to LDS should be used in the calculation of s in this special case; larger widths are subject to de-coherence. This favors lower, mainly conventional, quantum 1/f noise in these devices, in spite of the large values of w. It also explains for the first time why the huge widths are possible with impunity, i.e., without causing the much larger coherent quantum 1/f noise to appear. For non-uniform current distribution across t, and for piezoelectric coupling, improved forms are derived for s. Specifically, the coherence parameter, called s' for the piezo case, is given by s' = (gN'h/m*vs)( vs/u)3F(u/vs)t/12w, where F(u/vs) = (2/3)(u/vs) for small drift velocity u, much smaller than the sound velocity vs in the semiconductor. Here N'=nwt.

  5. Structural determination of vanillin, isovanillin and ethylvanillin by means of gas electron diffraction and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Egawa, Toru; Kameyama, Akiyo; Takeuchi, Hiroshi

    2006-08-01

    The molecular structures of vanillin (4-hydroxy-3-methoxybenzaldehyde), isovanillin (3-hydroxy-4-methoxybenzaldehyde) and ethylvanillin (3-ethoxy-4-hydroxybenzaldehyde) were determined by means of gas electron diffraction. Among them, vanillin and ethylvanillin have a vanilla odor but isovanillin smells differently. The nozzle temperatures were 125, 173 and 146 °C, for vanillin, isovanillin and ethylvanillin, respectively. The results of MP2 and B3LYP calculations with the 6-31G** basis set were used as supporting information. The MP2 calculations predicted that vanillin and isovanillin have two stable conformers and ethylvanillin has four stable conformers. The electron diffraction data were found to be consistent with these conformational compositions. The determined structural parameters ( rg and ∠ α) of vanillin are as follows: < r(C-C) ring>=1.397(4) Å; r(C 1-C aldehyde)=1.471(←) Å; r(C 3-O Me)=1.374(9) Å; r(C 4-O H)=1.361(←) Å; r(O-C Me)=1.428(←) Å; r(C dbnd6 O)=1.214(8) Å; < r(C-H)>=1.110(11) Å; r(O-H)=0.991(←) Å; ∠C 6-C 1-C 2=120.6(2)°; ∠C 1-C 2-C 3=118.8(←)°; ∠C 1-C 6-C 5=120.1(←)°; ∠C 2-C 1-C aldehyde=122.7(18)°; ∠C 1-C dbnd6 O=119.4(16)°; ∠C 4-C 3-O Me=112.2(12)°; ∠C 3-C 4-O H=119.1(←)°; ∠C 3-O-C=121.7(29)°. Those of isovanillin are as follows: < r(C-C) ring>=1.402(4) Å; r(C 1-C aldehyde)=1.479(←) Å; r(C 4-O Me)=1.369(9) Å; r(C 3-O H)=1.357(←) Å; r(O-C Me)=1.422(←) Å; r(C dbnd6 O)=1.221(9) Å; < r(C-H)>=1.114(14) Å; r(O-H)=0.995(←) Å; ∠C 6-C 1-C 2=120.2(3)°; ∠C 1-C 2-C 3=119.0(←)°; ∠C 1-C 6-C 5=119.9(←)°; ∠C 2-C 1-C aldehyde=124.6(25)°; ∠C 1-C dbnd6 O=121.3(24)°; ∠C 3-C 4-O Me=114.4(12)°; ∠C 4-C 3-O H=121.2(←)°; ∠C 4-O-C=123.8(26)°. Those of ethylvanillin are as follows: < r(C-C) ring>=1.397(6) Å; r(C 1-C aldehyde)=1.471(←) Å; r(C 3-O Et)=1.365(13) Å; r(C 4-O H)=1.352(←) Å; r(O-C Et)=1.427(←) Å; r(C-C Et)=1.494(21) Å; r(C dbnd6 O)=1.206(9) Å; < r(C-H)>=1.109(10) Å; r(O-H)=0.990(←) Å; ∠C 6-C 1-C 2=120.2(3)°; ∠C 1-C 2-C 3=118.4(←)°; ∠C 1-C 6-C 5=119.7(←)°; ∠C 2-C 1-C aldehyde=121.7(21)°; ∠C 1-C dbnd6 O=128.8(22)°; ∠C 4-C 3-O Et=112.8(14)°; ∠C 3-C 4-O H=119.6(←)°; ∠C 3-O-C=115.1(27)°; ∠O-C-C Et=102.7(28)°. Angle brackets denote average values; parenthesized values are the estimated limits of error (3 σ) referring to the last significant digit; left arrows in the parentheses mean that these parameters are bound to the preceding one.

  6. Characterizing attractors using local intrinsic dimensions calculated by singular-value decomposition and information-theoretic criteria

    NASA Astrophysics Data System (ADS)

    Hediger, T.; Passamante, A.; Farrell, Mary Eileen

    1990-05-01

    An algorithm to estimate the average local intrinsic dimension () of an attractor using signal versus noise separation methods based on information-theoretic criteria is explored in this work. Using noisy sample data the is computed from an eigenanalysis of local attractor regions, indicating the local orthogonal directions along which the data are clustered. The algorithm requires the separation of signal eigenvalues, i.e., the dominant eigenvalues, from the noise eigenvalues for which thresholding mechanisms based on two information-theoretic criteria are used. Singular-value decomposition is used to calculate the eigenvalues as well as to determine the rank of the local-phase-space data matrix. The two specific information-theoretic criteria which we consider to separate signal and noise are the Akaike information criterion (AIC) [H. Akaike, IEEE Trans. Auto. Control 19, 716 (1974)] and the minimum description length (MDL) of Rissanen [Automatica 14, 465 (1978)] and Schwarz [Ann. Stat. 6, 461 (1978)]. Several test cases are presented demonstrating the use of the AIC and MDL to calculate . Results are then compared to the correlation dimension as computed by the Grassberger-Procaccia method [Physica D9, 189 (1983)]. The AIC and MDL separation techniques are found to be inappropriate at higher signal-to-noise ratios (SNR), above ~12 dB, and the MDL produces results in good overall agreement with the accepted correlation dimension in the range of SNR between 5 and 12 dB. Two of the primary benefits of the technique are that it will yield reasonable and fairly accurate estimates of the dimension of attractors and that it can probe small length scales on the attractor even for moderate SNR. Other thresholding schemes are being pursued for SNR's above 12 dB.

  7. Unusual mechanism for H{sub 3}{sup +} formation from ethane as obtained by femtosecond laser pulse ionization and quantum chemical calculations

    SciTech Connect

    Kraus, Peter M.; Schwarzer, Martin C.; Schirmel, Nora; Urbasch, Gunter; Frenking, Gernot; Weitzel, Karl-Michael

    2011-03-21

    The formation of H{sub 3}{sup +} from saturated hydrocarbon molecules represents a prototype of a complex chemical process, involving the breaking and the making of chemical bonds. We present a combined theoretical and experimental investigation providing for the first time an understanding of the mechanism of H{sub 3}{sup +} formation at the molecular level. The experimental approach involves femtosecond laser pulse ionization of ethane leading to H{sub 3}{sup +} ions with kinetic energies on the order of 4 to 6.5 eV. The theoretical approach involves high-level quantum chemical calculation of the complete reaction path. The calculations confirm that the process takes place on the potential energy surface of the ethane dication. A surprising result of the theoretical investigation is, that the transition state of the process can be formally regarded as a H{sub 2} molecule attached to a C{sub 2}H{sub 4}{sup 2+} entity but IRC calculations show that it belongs to the reaction channel yielding C{sub 2}H{sub 3}{sup +}+ H{sub 3}{sup +}. Experimentally measured kinetic energies of the correlated H{sub 3}{sup +} and C{sub 2}H{sub 3}{sup +} ions confirm the reaction path suggested by theory.

  8. An improved fragment-based quantum mechanical method for calculation of electrostatic solvation energy of proteins

    SciTech Connect

    Jia, Xiangyu; Wang, Xianwei; Liu, Jinfeng; Mei, Ye E-mail: xiaohe@phy.ecnu.edu.cn; He, Xiao E-mail: xiaohe@phy.ecnu.edu.cn; Zhang, John Z. H.; Joint Research Center for Computational Chemistry at NYU Shanghai, Shanghai 200062

    2013-12-07

    An efficient approach that combines the electrostatically embedded generalized molecular fractionation with conjugate caps (EE-GMFCC) method with conductor-like polarizable continuum model (CPCM), termed EE-GMFCC-CPCM, is developed for ab initio calculation of the electrostatic solvation energy of proteins. Compared with the previous MFCC-CPCM study [Y. Mei, C. G. Ji, and J. Z. H. Zhang, J. Chem. Phys. 125, 094906 (2006)], quantum mechanical (QM) calculation is applied to deal with short-range non-neighboring interactions replacing the classical treatment. Numerical studies are carried out for proteins up to 3837 atoms at the HF/6-31G* level. As compared to standard full system CPCM calculations, EE-GMFCC-CPCM shows clear improvement over the MFCC-CPCM method for both the total electrostatic solvation energy and its components (the polarized solute-solvent reaction field energy and wavefunction distortion energy of the solute). For large proteins with 1000–4000 atoms, where the standard full system ab initio CPCM calculations are not affordable, the EE-GMFCC-CPCM gives larger relative wavefunction distortion energies and weaker relative electrostatic solvation energies for proteins, as compared to the corresponding energies calculated by the Divide-and-Conquer Poisson-Boltzmann (D and C-PB) method. Notwithstanding, a high correlation between EE-GMFCC-CPCM and D and C-PB is observed. This study demonstrates that the linear-scaling EE-GMFCC-CPCM approach is an accurate and also efficient method for the calculation of electrostatic solvation energy of proteins.

  9. Quantum theory of molecular collisions in a magnetic field: Efficient calculations based on the total angular momentum representation

    NASA Astrophysics Data System (ADS)

    Tscherbul, T. V.; Dalgarno, A.

    2010-11-01

    An efficient method is presented for rigorous quantum calculations of atom-molecule and molecule-molecule collisions in a magnetic field. The method is based on the expansion of the wave function of the collision complex in basis functions with well-defined total angular momentum in the body-fixed coordinate frame. We outline the general theory of the method for collisions of diatomic molecules in the ?2 and ?3 electronic states with structureless atoms and with unlike ?2 and ?3 molecules. The cross sections for elastic scattering and Zeeman relaxation in low-temperature collisions of CaH(?+2) and NH(?-3) molecules with H3e atoms converge quickly with respect to the number of total angular momentum states included in the basis set, leading to a dramatic (>10-fold) enhancement in computational efficiency compared to the previously used methods [A. Volpi and J. L. Bohn, Phys. Rev. A 65, 052712 (2002); R. V. Krems and A. Dalgarno, J. Chem. Phys. 120, 2296 (2004)]. Our approach is thus well suited for theoretical studies of strongly anisotropic molecular collisions in the presence of external electromagnetic fields.

  10. Effects of strain and quantum confinement in optically pumped nuclear magnetic resonance in GaAs: Interpretation guided by spin-dependent band structure calculations

    DOE PAGESBeta

    Wood, R. M.; Saha, D.; McCarthy, L. A.; Tokarski, III, J. T.; Sanders, G. D.; Kuhns, P. L.; McGill, S. A.; Reyes, A. P.; Reno, J. L.; Stanton, C. J.; et al

    2014-10-29

    A combined experimental-theoretical study of optically pumped NMR (OPNMR) has been performed in a GaAs/Al0.1Ga0.9As quantum well film with thermally induced biaxial strain. The photon energy dependence of the Ga-71 OPNMR signal was recorded at magnetic fields of 4.9 and 9.4 T at a temperature of 4.8-5.4 K. The data were compared to the nuclear spin polarization calculated from differential absorption to spin-up and spin-down states of the conduction band using a modified Pidgeon Brown model. Reasonable agreement between theory and experiment is obtained, facilitating assignment of features in the OPNMR energy dependence to specific interband transitions. Despite the approximationsmore » made in the quantum-mechanical model and the inexact correspondence between the experimental and calculated observables, the results provide insight into how effects of strain and quantum confinement are manifested in OPNMR signals« less

  11. Effects of strain and quantum confinement in optically pumped nuclear magnetic resonance in GaAs: Interpretation guided by spin-dependent band structure calculations

    SciTech Connect

    Wood, R. M.; Saha, D.; McCarthy, L. A.; Tokarski, III, J. T.; Sanders, G. D.; Kuhns, P. L.; McGill, S. A.; Reyes, A. P.; Reno, J. L.; Stanton, C. J.; Bowers, C. R.

    2014-10-29

    A combined experimental-theoretical study of optically pumped NMR (OPNMR) has been performed in a GaAs/Al0.1Ga0.9As quantum well film with thermally induced biaxial strain. The photon energy dependence of the Ga-71 OPNMR signal was recorded at magnetic fields of 4.9 and 9.4 T at a temperature of 4.8-5.4 K. The data were compared to the nuclear spin polarization calculated from differential absorption to spin-up and spin-down states of the conduction band using a modified Pidgeon Brown model. Reasonable agreement between theory and experiment is obtained, facilitating assignment of features in the OPNMR energy dependence to specific interband transitions. Despite the approximations made in the quantum-mechanical model and the inexact correspondence between the experimental and calculated observables, the results provide insight into how effects of strain and quantum confinement are manifested in OPNMR signals

  12. A Theoretical Study of Bulk and Surface Diffusion Processes for Semiconductor Materials Using First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Roehl, Jason L.

    Diffusion of point defects on crystalline surfaces and in their bulk is an important and ubiquitous phenomenon affecting film quality, electronic properties and device functionality. A complete understanding of these diffusion processes enables one to predict and then control those processes. Such understanding includes knowledge of the structural, energetic and electronic properties of these native and non-native point defect diffusion processes. Direct experimental observation of the phenomenon is difficult and microscopic theories of diffusion mechanisms and pathways abound. Thus, knowing the nature of diffusion processes, of specific point defects in given materials, has been a challenging task for analytical theory as well as experiment. The recent advances in computing technology have been a catalyst for the rise of a third mode of investigation. The advent of tremendous computing power, breakthroughs in algorithmic development in computational applications of electronic density functional theory now enables direct computation of the diffusion process. This thesis demonstrates such a method applied to several different examples of point defect diffusion on the (001) surface of gallium arsenide (GaAs) and the bulk of cadmium telluride (CdTe) and cadmium sulfide (CdS). All results presented in this work are ab initio, total-energy pseudopotential calculations within the local density approximation to density-functional theory. Single particle wavefunctions were expanded in a plane-wave basis and reciprocal space k-point sampling was achieved by Monkhorst-Pack generated k-point grids. Both surface and bulk computations employed a supercell approach using periodic boundary conditions. Ga adatom adsorption and diffusion processes were studied on two reconstructions of the GaAs(001) surface including the c(4x4) and c(4x4)-heterodimer surface reconstructions. On the GaAs(001)- c(4x4) surface reconstruction, two distinct sets of minima and transition sites were discovered for a Ga adatom relaxing from heights of 3 and 0.5 A from the surface. These two sets show significant differences in the interaction of the Ga adatom with surface As dimers and an electronic signature of the differences in this interaction was identified. The energetic barriers to diffusion were computed between various adsorption sites. Diffusion profiles for native Cd and S, adatom and vacancy, and non-native interstitial adatoms of Te, Cu and Cl were investigated in bulk wurtzite CdS. The interstitial diffusion paths considered in this work were chosen parallel to c-axis as it represents the path encountered by defects diffusing from the CdTe layer. Because of the lattice mismatch between zinc-blende CdTe and hexagonal wurtzite CdS, the c-axis in CdS is normal to the CdTe interface. The global minimum and maximum energy positions in the bulk unit cell vary for different diffusing species. This results in a significant variation, in the bonding configurations and associated strain energies of different extrema positions along the diffusion paths for various defects. The diffusion barriers range from a low of 0.42 eV for an S interstitial to a high of 2.18 eV for a S vacancy. The computed 0.66 eV barrier for a Cu interstitial is in good agreement with experimental values in the range of 0.58 - 0.96 eV reported in the literature. There exists an electronic signature in the local density of states for the s- and d-states of the Cu interstitial at the global maximum and global minimum energy position. The work presented in this thesis is an investigation into diffusion processes for semiconductor bulk and surfaces. The work provides information about these processes at a level of control unavailable experimentally giving an elaborate description into physical and electronic properties associated with diffusion at its most basic level. Not only does this work provide information about GaAs, CdTe and CdS, it is intended to contribute to a foundation of knowledge that can be extended to other systems to expand our overall understanding into the diffusion process. (Abstract shortened by UMI.)

  13. Time-dependent wave packet quantum scattering and quasi-classical trajectory calculations of the H + FCl(v=0,j=0) → HF + Cl/HCl + F reaction.

    PubMed

    Zhao, Juan; Miao, Xiangyang; Luo, Yi

    2013-11-14

    The dynamics of the title reaction are investigated using both time-dependent wave packet quantum scattering and quasi-classical trajectory (QCT) methods on adiabatic ground 1(2)A' potential energy surface (PES). Compared with the quantum results of reaction probabilities of H + FCl(J=0) → HF + Cl/HCl + F, the QCT method is proven feasible and further employed to produce integral cross sections and rate constants. Significant resonance structures are observed in the reaction probabilities using the quantum method; however, there are some undulations in the calculated QCT integral cross sections for both product channels. A comparison between the quantum mechanical coupled-channel (CC) calculation and centrifugal sudden approximation calculation reveals the very important role of Coriolis coupling effects in the quantum calculation. Comparisons between the calculated thermal rate constants for both reactions and the previous theoretical and experimental results have been done. HCl product formation is favored over the HF product in the reactive system. Finally, the HF products are found to be mainly forward scattering, and the HCl products are mainly backward scattering. PMID:24125031

  14. Quantum Darwinism Requires an Extra-Theoretical Assumption of Encoding Redundancy

    NASA Astrophysics Data System (ADS)

    Fields, Chris

    2010-10-01

    Observers restricted to the observation of pointer states of apparatus cannot conclusively demonstrate that the pointer of an apparatus mathcal{A} registers the state of a system of interest S without perturbing S. Observers cannot, therefore, conclusively demonstrate that the states of a system S are redundantly encoded by pointer states of multiple independent apparatus without destroying the redundancy of encoding. The redundancy of encoding required by quantum Darwinism must, therefore, be assumed from outside the quantum-mechanical formalism and without the possibility of experimental demonstration.

  15. The optical properties and quantum chemical calculations of thienyl and furyl derivatives of pyrene.

    PubMed

    Idzik, Krzysztof R; Cywiński, Piotr J; Kuznik, Wojciech; Frydel, Jaroslaw; Licha, Tobias; Ratajczyk, Tomasz

    2015-09-21

    A detailed electrochemical, photophysical and theoretical study is presented for various new thienyl and furyl derivatives of pyrene. Their optical properties are described based on UV-VIS absorption and both steady-state and time-resolved fluorescence spectroscopy. DFT and TDDFT calculations are also presented to support experimental data. The calculations results show that HOMO-LUMO orbitals are delocalized uniformly between aromatic core and aryl substituents. Good electrochemical stability of thienyl and furyl hybrids of pyrene confirm their potential application for light emitting electrochemical cells or spintronics mainly due to their beneficial optical and charge transport properties in electrochromic devices. In order to demonstrate this potential, an OLED device is presented. Synthesized compounds included in this OLED device both facilitate electron transport and act as a light emitting layer. PMID:26257127

  16. Phenylazoindole dyes - Part I: The syntheses, characterizations, crystal structures, quantum chemical calculations and antimicrobial properties

    NASA Astrophysics Data System (ADS)

    Seferoğlu, Zeynel; Yalçın, Ergin; Babür, Banu; Seferoğlu, Nurgül; Hökelek, Tuncer; Yılmaz, Ebru; Şahin, Ertan

    2013-09-01

    In this study, the synthesis of four new phenylazo indole dyes (dye 1-4) were carried out by diazotization of 4-aminoacetophenone and coupling with various 2- and 1,2-disubstituted indole derivatives. The dyes were characterized by UV-vis, FT-IR, 1H NMR, HRMS and X-ray single crystal diffraction methods. Azo-hydrazone tautomeric bahavior of the dyes in different solvents (DMSO, methanol, acetic acid and chloroform) was investigated by using 1H NMR and UV-vis results. The experimental results were compared with the corresponding calculated values. The results of experimental data and theoretical calculations showed that the azo tautomer is more stable than hydrazone tautomer. In addition to this, the antimicrobial activity of the dyes was also evaluated.

  17. Atomistic calculation of electronic and optical properties of a single InAs quantum dots

    NASA Astrophysics Data System (ADS)

    Zielinski, M.; Korkusinski, M.; Sheng, W.; Hawrylak, P.

    2008-03-01

    We present an atomistic tight-binding (TB) theory of electronic structure and optical properties of a single self-assembled InAs quantum dot (SAD). In previous work an effective-bond-orbital model (EBOM) was used to calculate electron and hole states of the SAD. The strain distribution was calculated using the continuum elasticity theory and EBOM was coupled to the strain via the Bir-Pikus Hamiltonian. However, the properties of these multimillion-atom systems are influenced by the presence of crystal facets and the symmetry of underlying zinc-blende lattice. In current work we present a fully atomistic TB model, accounting for the atomistic symmetry, and extended to include d-orbitals for proper treatment of interband/intervalley couplings. Strain is included in the Hamiltonian via Slater-Koster rules and a generalized Harrison law, with the equilibrium positions of atoms calculated using the valence force field method. Coulomb matrix elements are found using the TB functions, and electronic properties of N confined excitons (N=1-6) are determined in the CI approach. Emission spectra of multiexcitons are also obtained. Comparison with the previous approach and the experimental results is presented.

  18. Fluorescent substituted amidines of benzanthrone: Synthesis, spectroscopy and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Gonta, Svetlana; Utinans, Maris; Kirilov, Georgii; Belyakov, Sergey; Ivanova, Irena; Fleisher, Mendel; Savenkov, Valerij; Kirilova, Elena

    2013-01-01

    Several new substituted amidine derivatives of benzanthrone were synthesized by a condensation reaction from 3-aminobenzo[de]anthracen-7-one and appropriate aromatic and aliphatic amides. The obtained derivatives have a bright yellow or orange fluorescence in organic solvents and in solid state. The novel benzanthrone derivatives were characterized by TLC analysis, 1H NMR, IR, MS, UV/vis, and fluorescence spectroscopy. The solvent effect on photophysical behaviors of these dyes was investigated, and the results showed that the Stoke's shift increased, whereas quantum yield decreased with the growth of the solvent polarity. The structure of some dyes was confirmed by the X-ray single crystal structure analysis. AM1, ZINDO/S and ab initio calculations using Gaussian software were carried out to estimate the electron system of structures. The calculations show planar configurations for the aromatic core of these compounds and two possible orientations of amidine substituents. The calculation results correlate well with red-shifted absorption and emission spectra of compounds.

  19. Intramolecular hydrogen bonds involving organic fluorine in the derivatives of hydrazides: an NMR investigation substantiated by DFT based theoretical calculations.

    PubMed

    Mishra, Sandeep Kumar; Suryaprakash, N

    2015-06-21

    The rare examples of intramolecular hydrogen bonds (HB) of the type the N-H∙∙∙F-C, detected in a low polarity solvent in the derivatives of hydrazides, by utilizing one and two-dimensional solution state multinuclear NMR techniques, are reported. The observation of through-space couplings, such as, (1h)JFH, and (1h)JFN, provides direct evidence for the existence of intra-molecular HB. Solvent induced perturbations and the variable temperature NMR experiments unambiguously establish the presence of intramolecular HB. The existence of multiple conformers in some of the investigated molecules is also revealed by two dimensional HOESY and (15)N-(1)H HSQC experiments. The (1)H DOSY experimental results discard any possibility of self or cross dimerization of the molecules. The derived NMR experimental results are further substantiated by Density Function Theory (DFT) based Non Covalent Interaction (NCI), and Quantum Theory of Atom in Molecule (QTAIM) calculations. The NCI calculations served as a very sensitive tool for detection of non-covalent interactions and also confirm the presence of bifurcated HBs. PMID:25993543

  20. One-loop calculations in quantum field theory: from Feynman diagrams to unitarity cuts

    SciTech Connect

    Ellis, R. Keith; Kunszt, Zoltan; Melnikov, Kirill; Zanderighi, Giulia

    2012-09-01

    The success of the experimental program at the Tevatron re-inforced the idea that precision physics at hadron colliders is desirable and, indeed, possible. The Tevatron data strongly suggests that one-loop computations in QCD describe hard scattering well. Extrapolating this observation to the LHC, we conclude that knowledge of many short-distance processes at next-to-leading order may be required to describe the physics of hard scattering. While the field of one-loop computations is quite mature, parton multiplicities in hard LHC events are so high that traditional computational techniques become inefficient. Recently new approaches based on unitarity have been developed for calculating one-loop scattering amplitudes in quantum field theory. These methods are especially suitable for the description of multi-particle processes in QCD and are amenable to numerical implementations. We present a systematic pedagogical description of both conceptual and technical aspects of the new methods.

  1. Electronic structure calculations of PbS quantum rods and tubes

    SciTech Connect

    Pimachev, Artem; Dahnovsky, Yuri

    2014-01-28

    We study absorption spectra, optical and HOMO-LUMO gaps, and the density of states for PbS quantum rods (QRs) and tubes (QTs). We find some similarities and also differences in QR and QT properties. For both QRs and QTs, the optical and HOMO-LUMO gaps reach the plateaus for small lengths. We find that tubes are as stable as rods. The optical spectra exhibit a peak that can be due to the electron-hole interaction or be a prototype of an S{sub e}–S{sub h} transition in the effective mass approximation. We also calculate the density of states by the density functional theory (DFT) and time-dependent density functional theory (TDDFT) methods. The TDDFT density of states function is shifted towards the red side by 0.5 eV indicating the strong e-h interaction.

  2. Scaled quantum chemical calculations and FTIR, FT-Raman spectral analysis of 2-Methylpyrazine.

    PubMed

    Krishnakumar, V; Prabavathi, N

    2009-05-01

    The mid and far FTIR and Raman spectra of 2-Methylpyrazine (2MP) were measured in the liquid state. The fundamental vibrational frequencies and intensity of vibrational bands were evaluated using density functional theory (DFT) and standard B3LYP/6-311+G** basis set combination. The vibrational spectra were interpreted, with the aid of normal coordinate analysis based on a scaled quantum mechanical (SQM) force field. The infrared and Raman spectra were also predicted from the calculated intensities. Comparison of simulated spectra with the experimental spectra provides important information about the ability of the computational method to describe the vibrational modes. Unambiguous vibrational assignment of all the fundamentals was made using the total energy distribution (TED). PMID:19121975

  3. Variational quantum Monte Carlo calculation of electronic and structural properties of crystals

    SciTech Connect

    Louie, S.G.

    1989-09-01

    Calculation of the electronic and structural properties of solids using a variational quantum Monte Carlo nonlocal pseudopotential approach is described. Ionization potentials and electron affinities for atoms, and binding energies and structural properties for crystals are found to be in very good agreement with experiment. The approach employs a correlated many-electron wavefunction of the Jastrow-Slater form and the exact Coulomb interaction between valence electrons. One- and two-body terms in the Jastrow factor are used and found necessary for an accurate description of the electron-electron energy for the systems considered. The method has further been applied to compute various single-particle properties for solids including the single-particle orbital occupancy, electron pair correlation functions, and quasiparticle excitation energies. 23 refs., 3 figs., 3 tabs.

  4. Quantum three-body calculation of nonresonant triple-{alpha} reaction rate at low temperatures

    SciTech Connect

    Ogata, Kazuyuki; Kan, Masataka; Kamimura, Masayasu

    2010-08-12

    Triple-{alpha} reaction rate is re-evaluated by directly solving the three-body Schroedinger equation. The resonant and nonresonant processes are treated on the same footing using the continuum-discretized coupled-channels method for three-body scattering. An accurate description of the {alpha}-{alpha} nonresonant states significantly quenches the Coulomb barrier between the first two {alpha}-particles and the third {alpha}-particle. Consequently, the{alpha}-{alpha} nonresonant continuum states give a markedly larger contribution at low temperatures than that reported in previous studies. We show that Nomoto's method for three-body nonresonant capture processes, which is adopted in the NACRE compilation and many other studies, is a crude approximation of the accurate quantum three-body model calculation. We find an increase in triple-{alpha} reaction rate by about 20 orders of magnitude around 10{sup 7} K compared with the rate of NACRE.

  5. Quantum-mechanical calculation of carrier distribution in MOS accumulation and strong inversion layers

    SciTech Connect

    Lee, Chien-Wei; Hwu, Jenn-Gwo

    2013-10-15

    We derive a statistical physics model of two-dimensional electron gas (2DEG) and propose an accurate approximation method for calculating the quantum-mechanical effects of metal-oxide-semiconductor (MOS) structure in accumulation and strong inversion regions. We use an exponential surface potential approximation in solving the quantization energy levels and derive the function of density of states in 2D to 3D transition region by applying uncertainty principle and Schrödinger equation in k-space. The simulation results show that our approximation method and theory of density of states solve the two major problems of previous researches: the non-negligible error caused by the linear potential approximation and the inconsistency of density of states and carrier distribution in 2D to 3D transition region.

  6. A new theoretical method for calculating temperature and water vapor saturation ratio in an expansion cloud chamber

    NASA Astrophysics Data System (ADS)

    Moteki, Nobuhiro; Kondo, Yutaka

    2013-06-01

    The expansion cloud chamber is a widely used apparatus for investigating the dynamics of condensational growth of aerosols and clouds. Theoretical calculations of temperature T and water vapor saturation ratio S are necessary for quantitative interpretations of experimental data obtained from the expansion cloud chamber. In this paper, we revisit the thermodynamics associated with the underlying assumptions for calculating the time-dependent temperature T(t) and saturation ratio S(t) in an expansion chamber as a function of experimentally observable parameters. We introduce an intuitive and robust method, the virtual path (VP) method, by which changes in the thermodynamic state of a moist air parcel containing cloud droplets are schematically represented on a thermodynamic diagram. The validity of the VP method is confirmed by comparisons with the differential equation (DE) method, which is a numerical simulation of real physical processes according to the time evolution equations involving T and S. In contrast to the conventional DE method, the governing equations of the VP method do not involve time t, an irrelevant parameter in the framework of classical thermodynamics. The VP method is advantageous compared to the DE method because the former is applicable to the raw experimental data acquired with a finite time resolution, allowing a robust calculation of the T and S values and the errors that are only caused by the measurement errors of the input data.

  7. One pot synthesis of biologically active pregnane derivatives, their single crystal structures, spectroscopic characterization and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Sethi, Arun; Bhatia, Akriti; Bhatia, Gitika; Shrivastava, Atul; Prakash, Rohit

    2013-11-01

    One pot allylic oxidation of 3β-acetoxypregna-5,16-diene-20-one (2) and nucleophilic addition at C-16 position of 3β-hydroxypregna-5,16-diene-20-one (3) yielded 3β-acetoxypregna-5,16-diene-7,20-dione (4) and 3β-hydroxy-16α-(5'-hydroxypentyloxy)-pregn-5-ene-20-one (5) respectively in high yield. A detailed theoretical study supported by X-ray analysis of compounds 4 and 5 has been carried out. Conformational analysis of compounds 4 and 5 was done with the help of crystal structure, which crystallize out in orthorhombic form having P212121 space group. Structural characterization of compounds 4 and 5 was done with the aid of 1H, 13C NMR, IR, UV, ESI-MS and ESI-HRMS. The molecular geometries and vibrational frequencies for compounds 4 and 5 in the ground state were calculated using the Density functional theory (DFT) with 6-31G(d,p) basis set and compared with experimental data. 1H and 13C nuclear magnetic resonance magnetic shifts of 4 and 5 were calculated using GIAO method and compared with the experimental data. UV-Vis spectra of both the compounds were recorded and electronic properties such as HOMO-LUMO energies were calculated by time dependent TD-DFT approach. The compounds were screened for their anti-hyperlipidemic and anti-oxidant activity.

  8. Calculation of metamorphic two-dimensional quantum energy system: Application to wetting layer states in InAs/InGaAs metamorphic quantum dot nanostructures

    SciTech Connect

    Seravalli, L.; Trevisi, G.; Frigeri, P.

    2013-11-14

    In this work, we calculate the two-dimensional quantum energy system of the In(Ga)As wetting layer that arises in InAs/InGaAs/GaAs metamorphic quantum dot structures. Model calculations were carried on the basis of realistic material parameters taking in consideration their dependence on the strain relaxation of the metamorphic buffer; results of the calculations were validated against available literature data. Model results confirmed previous hypothesis on the extrinsic nature of the disappearance of wetting layer emission in metamorphic structures with high In composition. We also show how, by adjusting InGaAs metamorphic buffer parameters, it could be possible: (i) to spatially separate carriers confined in quantum dots from wetting layer carriers, (ii) to create an hybrid 0D-2D system, by tuning quantum dot and wetting layer levels. These results are interesting not only for the engineering of quantum dot structures but also for other applications of metamorphic structures, as the two design parameters of the metamorphic InGaAs buffer (thickness and composition) provide additional degrees of freedom to control properties of interest.

  9. The Impact of Quantum Theoretical Models of Consciousness on the Study of Education.

    ERIC Educational Resources Information Center

    Andris, James F.

    This paper abstracts and discusses the approaches of five educational theorists who have used quantum theory as a model for educational phenomena, sets forth and uses metatheoretical criteria to evaluate the work of these theorists, and states guidelines for further work in this domain. The paper abstracts and discusses the works of the following…

  10. Derivation of the Rules of Quantum Mechanics from Information-Theoretic Axioms

    NASA Astrophysics Data System (ADS)

    Fivel, Daniel I.

    2012-02-01

    Conventional quantum mechanics with a complex Hilbert space and the Born Rule is derived from five axioms describing experimentally observable properties of probability distributions for the outcome of measurements. Axioms I, II, III are common to quantum mechanics and hidden variable theories. Axiom IV recognizes a phenomenon, first noted by von Neumann (in Mathematical Foundations of Quantum Mechanics, Princeton University Press, Princeton, 1955) and independently by Turing (Teuscher and Hofstadter, Alan Turing: Life and Legacy of a Great Thinker, Springer, Berlin, 2004), in which the increase in entropy resulting from a measurement is reduced by a suitable intermediate measurement. This is shown to be impossible for local hidden variable theories. Axiom IV, together with the first three, almost suffice to deduce the conventional rules but allow some exotic, alternatives such as real or quaternionic quantum mechanics. Axiom V recognizes a property of the distribution of outcomes of random measurements on qubits which holds only in the complex Hilbert space model. It is then shown that the five axioms also imply the conventional rules for any finite dimension.

  11. Proposal of a Communications Theory of Quantum Mechanics. Theoretical Examination of the 'Gyromagnetic Ratio'

    SciTech Connect

    Coogan, Anthony

    2009-03-09

    Is the 'Two-Slit' experiment best explained by aliasing, first solved by Harry Nyquist (1926)? Does light reflected by an electron rotate through double the angle through which the electron itself rotates? Can a barchart represent the uncertainty principle?A very simple model of quantum mechanics is presented.

  12. Quantum-Mechanical Calculation of Ionization-Potential Lowering in Dense Plasmas

    NASA Astrophysics Data System (ADS)

    Son, Sang-Kil; Thiele, Robert; Jurek, Zoltan; Ziaja, Beata; Santra, Robin

    2014-07-01

    The charged environment within a dense plasma leads to the phenomenon of ionization-potential depression (IPD) for ions embedded in the plasma. Accurate predictions of the IPD effect are of crucial importance for modeling atomic processes occurring within dense plasmas. Several theoretical models have been developed to describe the IPD effect, with frequently discrepant predictions. Only recently, first experiments on IPD in Al plasma have been performed with an x-ray free-electron laser, where their results were found to be in disagreement with the widely used IPD model by Stewart and Pyatt. Another experiment on Al, at the Orion laser, showed disagreement with the model by Ecker and Kröll. This controversy shows a strong need for a rigorous and consistent theoretical approach to calculate the IPD effect. Here, we propose such an approach: a two-step Hartree-Fock-Slater model. With this parameter-free model, we can accurately and efficiently describe the experimental Al data and validate the accuracy of standard IPD models. Our model can be a useful tool for calculating atomic properties within dense plasmas with wide-ranging applications to studies on warm dense matter, shock experiments, planetary science, inertial confinement fusion, and nonequilibrium plasmas created with x-ray free-electron lasers.

  13. Far-infrared collision-induced absorption in rare gas mixtures: Quantum and semi-classical calculations

    SciTech Connect

    Buryak, Ilya; Obukhov Institute of Atmospheric Physics, Russian Academy of Sciences, 3 Pyzhevsky per., 119017 Moscow ; Frommhold, Lothar; Vigasin, Andrey A.

    2014-04-21

    We compare calculations of the translational collision-induced spectra and their integrated intensities of both He–Ar and Ne–Ar collisional complexes, using the quantum mechanical and a semiclassical formalism. Advanced potential energy and induced dipole functions are used for the calculations. The quantum method used is as described previously [L. Frommhold, Collision-induced Absorption in Gases (Cambridge University Press, 1993 and 2006)]. The semiclassical method is based on repeated classical atom-atom scattering calculations to simulate an ensemble average; subsequent Fourier transform then renders the binary absorption coefficient as a function of frequency. The problem of classical calculations is the violation of the principle of detailed balance, which may be introduced only artificially in classical calculations. Nevertheless, it is shown that the use of classical trajectories permits a fairly accurate reproduction of the experimental spectra, comparable to the quantum mechanical results at not too low temperatures and for collisional pairs of not too small reduced mass. Inexpensive classical calculations may thus be promising to compute spectra also of molecular pairs, or even of polyatomic collisional pairs with anisotropic intermolecular interactions, for which the quantum approach is still inefficient or impractical.

  14. Non-zone-folded transition-energy calculations for quantum-confined Stark effect in Si1 - xGex/Si quantum wells

    NASA Astrophysics Data System (ADS)

    Chowdhury, Andalib A.; Jung, K. H.; Kwong, D. L.; Maziar, C. M.

    1991-10-01

    We report calculated bound-state transition energies at 77 K for symmetrically strained Si1-xGex/Si quantum wells grown on (100) Si substrates. The red shift in transition energies with bias due to the quantum-confined Stark effect is also examined. Transition energies are plotted as a function of Ge concentration, quantum-well thickness, and applied electric field. The calculations are based on phenomenological deformation potential theory and the envelope function method popularized by G. Bastard [Phys. Rev. B 24, 4714 (1981)]. The results presented here are useful for the design of Si1-xGexSi optoelectronic modulators operating at 1.3 and 1.55 μm.

  15. Quantum and quasiclassical calculations on the OH+CO[r arrow]CO[sub 2]+H reaction

    SciTech Connect

    Clary, D.C. ); Schatz, G.C. )

    1993-09-15

    Scattering calculations on the OH+CO[r arrow]CO[sub 2]+H reaction are reported using both quantum and quasiclassical methods. The rotating bond approximation is used in the quantum calculations. This method explicitly treats the OH vibration and CO rotation in the reactants and the bending vibration and a local CO stretch in the CO[sub 2] product. Analogous quasiclassical trajectory computations are also reported. A potential energy surface obtained as a fit to [ital ab] [ital initio] data is used. The quantum reaction probabilities are dominated by sharp resonances corresponding to vibrationally excited states of the HOCO complex formed in the reaction. The quantum and quasiclassical lifetimes of these resonances compare quite well with measurements made by Wittig [ital et] [ital al]. Calculations of differential cross sections, rate coefficients, and CO[sub 2] vibrational product distributions are also compared with experimental data. The comparisons of quantum and quasiclassical calculations for models that treat explicitly different numbers of degrees of freedom provide detailed insight into the dynamics of the OH+CO reaction.

  16. Adsorption configuration of sodium 2-quinoxalinecarboxylate on iron substrate: Investigation by in situ SERS, XPS and theoretical calculation

    NASA Astrophysics Data System (ADS)

    Huo, Sheng-Juan; He, Jin-Mei; Chen, Li-Hong; Fang, Jian-Hui

    2016-03-01

    The adsorption geometry of sodium 2-quinoxalinecarboxylate (2-QC) on iron surface was investigated by in situ surface-enhanced Raman scattering spectroscopy (SERS) and X-ray photoelectron spectroscopy (XPS) measurements. The density functional theory (DFT) calculations predicted that 2-QC ion was a highly efficient inhibitor and N as well as O atoms were the possible adsorption centers, and theoretically offered the Raman-active band position and intensity. Potential-dependent SERS results suggested that the 2-QC strongly bonded to the iron surface via the lone pair electrons of the two O atoms of the carboxylate group in a bidentate configuration with a vertical orientation at more positive potentials; However, at - 1.0 V, only one O atom of the carboxylate and the neighboring N1 atom (or very close to surface) adsorbed on the iron surface forming an unidentate configuration with a titled orientation. The ions did not remain on the iron surface at more negative potentials.

  17. Structural determination of carvone, a component of spearmint, by means of gas electron diffraction augmented by theoretical calculations

    NASA Astrophysics Data System (ADS)

    Egawa, Toru; Kachi, Yukari; Takeshima, Tsuguhide; Takeuchi, Hiroshi; Konaka, Shigehiro

    2003-10-01

    The molecular structure and conformation of carvone, a compound with a minty odor, were investigated by means of gas electron diffraction supported by theoretical calculations. Electron diffraction patterns were recorded by heating the nozzle up to 128 °C to obtain enough scattering intensity. The infrared spectrum was also measured by using an absorption cell with a path length of 10 m. The obtained molecular scattering intensities were analyzed with the aid of theoretical calculations and infrared spectroscopy. It was revealed that the experimental data are well reproduced by assuming that carvone consists of a mixture of three conformers that have the isopropenyl group in the equatorial position and mutually differ in the torsional angle around the single bond connecting the ring and the isopropenyl group. It was also found that the puckering amplitude of the ring of carvone is close to those of menthol and isomenthol, a minty compound and its nonminty isomer. The determined structural parameters ( rg and ∠ α) of the most abundant conformer of carvone are as follows: < r(C-C)>=1.520(3) Å; < r(CC)>=1.360(5) Å; r(CO)=1.225(5) Å; < r(C-H)>=1.104(4)Å; <∠CC-C>=121.1(5)°; <∠C-C-C>=110.4(5)°; ∠C-CO-C=117.1(14)°; <∠C-C-H>=111.1(13)°. Angle brackets denote average values and parenthesized values are the estimated limits of error (3 σ) referring to the last significant digit.

  18. Theoretical X-ray photoelectron spectra of polymers by deMon DFT calculations using the model dimers

    NASA Astrophysics Data System (ADS)

    Otsuka, T.; Endo, K.; Suhara, M.; Chong, D. P.

    2000-04-01

    Core-electron spectra of 15 polymers [(CH 2CH 2) n (PE), (CH 2CH(CH 3)) n (PP), (CH 2CH 2NH) n (PEI), (CH 2CH 2O) n (PEG), (CH 2CH(OCH 3)) n (PVME), (CH 2CHF) n (PVF), (CH 2CF 2) n (PVDF), (CF 2CF 2) n (PTFE), (CH 2CH(CN)) n (PAN), (CH 2C(CH 3)(CN)) n (PMAN), (CH 2CH 2S) n (PETHS), (CH 2CHCl) n (PVC), (CH 2CCl 2) n (PVDC), (Si(CH 3) 2) n (PDMS), (Si(CH 3) 2O) n (PDMSO)], and valence photoelectron spectra (XPS) of the six polymers (PP, PEI, PAN, PMAN, PVME, PTFE) were obtained by deMon density-functional theory (DFT) calculations using the model dimers. The core-electron spectra were simulated with the Gaussian lineshape functions with fixed linewidths of 0.5, and 1.0 eV for each C1s, and (N1s, O1s, F1s) MO value, respectively, and calculated Al-Kα valence photoelectron spectra were obtained using Gaussian lineshape functions of an approximate linewidth (0.08 Ik): Ik( IFL)= I' k-WD, as indicated in previous works. The vertical ionization potential I' k and each core-electron binding energy (CEBE) were calculated by restricted generalized diffuse ionization (rGDI) and unrestricted generalized transition-state (uGTS) models, respectively. The theoretical core-electron spectra showed better agreement with the experimental ones of the polymers than those due to Koopmans' theorem. The difference between the calculated and the experimental CEBEs reflected the reasonable WDs of the polymers.

  19. Quantum mechanical calculation of aqueuous uranium complexes: carbonate, phosphate, organic and biomolecular species

    PubMed Central

    Kubicki, James D; Halada, Gary P; Jha, Prashant; Phillips, Brian L

    2009-01-01

    Background Quantum mechanical calculations were performed on a variety of uranium species representing U(VI), U(V), U(IV), U-carbonates, U-phosphates, U-oxalates, U-catecholates, U-phosphodiesters, U-phosphorylated N-acetyl-glucosamine (NAG), and U-2-Keto-3-doxyoctanoate (KDO) with explicit solvation by H2O molecules. These models represent major U species in natural waters and complexes on bacterial surfaces. The model results are compared to observed EXAFS, IR, Raman and NMR spectra. Results Agreement between experiment and theory is acceptable in most cases, and the reasons for discrepancies are discussed. Calculated Gibbs free energies are used to constrain which configurations are most likely to be stable under circumneutral pH conditions. Reduction of U(VI) to U(IV) is examined for the U-carbonate and U-catechol complexes. Conclusion Results on the potential energy differences between U(V)- and U(IV)-carbonate complexes suggest that the cause of slower disproportionation in this system is electrostatic repulsion between UO2 [CO3]35- ions that must approach one another to form U(VI) and U(IV) rather than a change in thermodynamic stability. Calculations on U-catechol species are consistent with the observation that UO22+ can oxidize catechol and form quinone-like species. In addition, outer-sphere complexation is predicted to be the most stable for U-catechol interactions based on calculated energies and comparison to 13C NMR spectra. Outer-sphere complexes (i.e., ion pairs bridged by water molecules) are predicted to be comparable in Gibbs free energy to inner-sphere complexes for a model carboxylic acid. Complexation of uranyl to phosphorus-containing groups in extracellular polymeric substances is predicted to favor phosphonate groups, such as that found in phosphorylated NAG, rather than phosphodiesters, such as those in nucleic acids. PMID:19689800

  20. Quantum Calculations on Salt Bridges with Water: Potentials, Structure, and Properties

    SciTech Connect

    Liao, Sing; Green, Michael E.

    2011-01-01

    Salt bridges are electrostatic links between acidic and basic amino acids in a protein; quantum calculations are used here to determine the energetics and other properties of one form of these species, in the presence of water molecules. The acidic groups are carboxylic acids (aspartic and glutamic acids); proteins have two bases with pK above physiological pH: one, arginine, with a guanidinium basic group, the other lysine, which is a primary amine. Only arginine is modeled here, by ethyl guanidinium, while propionic acid is used as a model for either carboxylic acid. The salt bridges are accompanied by 0-12 water molecules; for each of the 13 systems, the energy-bond distance relation, natural bond orbitals (NBO), frequency calculations allowing thermodynamic corrections to room temperature, and dielectric constant dependence, were all calculated. The water molecules were found to arrange themselves in hydrogen bonded rings anchored to the oxygens of the salt bridge components. This was not surprising in itself, but it was found that the rings lead to a periodicity in the energy, and to a 'water addition' rule. The latter shows that the initial rings, with four oxygen atoms, become five member rings when an additional water molecule becomes available, with the additional water filling in at the bond with the lowest Wiberg index, as calculated using NBO. The dielectric constant dependence is the expected hyperbola, and the fit of the energy to the inverse dielectric constant is determined. There is an energy periodicity related to ring formation upon addition of water molecules. When 10 water molecules have been added, all spaces near the salt bridge are filled, completing the first hydration shell, and a second shell starts to form. The potentials associated with salt bridges depend on their hydration, and potentials assigned without regard to local hydration are likely to cause errors as large as or larger than kBT, thus suggesting a serious problem if these potentials are used in Molecular Dynamics simulations.

  1. Communication: Ro-vibrational control of chemical reactivity in H+CH{sub 4}→ H{sub 2}+CH{sub 3} : Full-dimensional quantum dynamics calculations and a sudden model

    SciTech Connect

    Welsch, Ralph Manthe, Uwe

    2014-08-07

    The mode-selective chemistry of the title reaction is studied by full-dimensional quantum dynamics simulation on an accurate ab initio potential energy surface for vanishing total angular momentum. Using a rigorous transition state based approach and multi-configurational time-dependent Hartree wave packet propagation, initial state-selected reaction probabilities for many ro-vibrational states of methane are calculated. The theoretical results are compared with experimental trends seen in reactions of methane. An intuitive interpretation of the ro-vibrational control of the chemical reactivity provided by a sudden model based on the quantum transition state concept is discussed.

  2. Insights into the high-pressure behavior of kaolinite from infrared spectroscopy and quantum-mechanical calculations

    NASA Astrophysics Data System (ADS)

    Welch, Mark D.; Montgomery, Wren; Balan, Etienne; Lerch, Philippe

    2012-02-01

    The high-pressure behavior of Keokuk kaolinite has been studied to 9.5 GPa by infrared spectroscopy using synchrotron radiation. The kaolinite-I → kaolinite-II and kaolinite-II → kaolinite-III transformations have clear spectroscopic expression, with discontinuities coinciding with the transformation pressures bracketed by X-ray diffraction (Welch and Crichton in Am Mineral 95:651-654, 2010). The experimental spectra have been interpreted from band assignments derived from density functional theory for the structures of kaolinite-II and kaolinite-III, using as starting models the ab initio structures reported by Mercier and Le Page (Acta Crystallogr A B64:131-143, 2008, Mater Sci Technol 25:437-442, 2009) and unit-cell parameters from Welch and Crichton (Am Mineral 95:651-654, 2010). The relaxed theoretical structures are very similar to those reported by Mercier and Le Page (Acta Crystallogr A B64:131-143, 2008, Mater Sci Technol 25:437-442, 2009) in their theoretical investigation of kaolinite polytypes at high pressure. The vibrational spectra calculated from the quantum-mechanical analysis allow band assignments of the IR spectra to be made and provide insights into the behavior of different OH environments in the two high-pressure polytypes. The single perpendicular-interlayer OH group of kaolinite-III has a distinctive spectroscopic signature that is diagnostic of this polytype (ν = 3,595 cm-1 at 9.5 GPa) and is sensitive to the compression/expansion of the interlayer space. This OH group also has a distinctive signature in the calculated spectra. The spectra collected on decompression are those of kaolinite-III and persist largely unchanged to 4.6 GPa, except for a continuous blue shift of the 3,595 cm-1 band to 3,613 cm-1. Finally, kaolinite-I is recovered at 0.6 GPa, confirming the kaolinite-III → kaolinite-I transformation previously observed by X-ray diffraction, and the irreversibility of the kaolinite-II → kaolinite-III transformation. The ambient spectra collected at the start and finish of the experiment are those of kaolinite-I, and start/finish band frequencies agree to within 6 cm-1.

  3. Theoretical basis for quantum simulation with a planar ionic crystal in a Penning trap using a triangular rotating wall

    NASA Astrophysics Data System (ADS)

    Khan, A.; Yoshimura, B.; Freericks, J. K.

    2015-10-01

    One of the challenges with quantum simulation in ion traps is that the effective spin-spin exchange couplings are not uniform across the lattice. This can be particularly important in Penning-trap realizations where the presence of an ellipsoidal boundary at the edge of the trap leads to dislocations in the crystal. By adding an additional anharmonic potential to better control interion spacing, and a triangular-shaped rotating wall potential to reduce the appearance of dislocations, one can achieve better uniformity of the ionic positions. In this work, we calculate the axial phonon frequencies and the spin-spin interactions driven by a spin-dependent optical dipole force, and discuss what effects the more uniform ion spacing have on the spin simulation properties of Penning-trap quantum simulators. Indeed, we find that the spin-spin interactions behave more like a power law for a wide range of parameters.

  4. Accurate band gaps of semiconductors and insulators from Quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Nazarov, Roman; Hood, Randolph; Morales, Miguel

    2015-03-01

    Ab initio calculations are useful tools in developing materials with targeted band gaps for semiconductor industry. Unfortunately, the main workhorse of ab initio calculations - density functional theory (DFT) in local density approximation (LDA) or generalized gradient approximation (GGA) underestimates band gaps. Several approaches have been proposed starting from empirical corrections to more elaborate exchange-correlation functionals to deal with this problem. But none of these work well for the entire range of semiconductors and insulators. Deficiencies of DFT as a mean field method can be overcome using many-body techniques. Quantum Monte Carlo (QMC) methods can obtain a nearly exact numerical solutions of both total energies and spectral properties. Diffusion Monte Carlo (DMC), the most widely used QMC method, has been shown to provide gold standard results for different material properties, including spectroscopic constants of dimers and clusters, equation of state for solids, accurate descriptions of defects in metals and insulators. To test DMC's accuracy in a wider range of semiconductors and insulators we have computed band gaps of several semiconductors and insulators. We show that DMC can provide superior agreement with experiment compared with more traditional DFT approaches including high level exchange-correlation functionals (e.g. HSE).

  5. Progesterone and testosterone studies by neutron-scattering methods and quantum chemistry calculations

    NASA Astrophysics Data System (ADS)

    Holderna-Natkaniec, K.; Szyczewski, A.; Natkaniec, I.; Khavryutchenko, V. D.; Pawlukojc, A.

    Inelastic incoherent neutron scattering (IINS) and neutron diffraction spectra of progesterone and testosterone were measured simultaneously on the NERA spectrometer at the IBR-2 pulsed reactor in Dubna. Both studied samples do not indicate any phase transition in the temperature range from 20 to 290K. The IINS spectra have been transformed to the phonon density of states (PDS) in the one-phonon scattering approximation. The PDS spectra display well-resolved peaks of low-frequency internal vibration modes up to 600cm-1. The assignment of these modes was proposed taking into account the results of calculations of the structure and dynamics of isolated molecules of the investigated substances. The quantum chemistry calculations were performed by the semi-empirical PM3 method and at the restricted Hartree-Fock level with the 6-31* basis set. The lower internal modes assigned to torsional vibration of the androstane skeleton mix with the lattice vibrations. The intense bands in the PDS spectra in the frequency range from 150 to 300cm-1 are related to librations of structurally inequivalent methyl groups.

  6. Accurate quantum dynamics calculations using symmetrized Gaussians on a doubly dense Von Neumann lattice

    SciTech Connect

    Halverson, Thomas; Poirier, Bill

    2012-12-14

    In a series of earlier articles [B. Poirier, J. Theor. Comput. Chem. 2, 65 (2003); B. Poirier and A. Salam, J. Chem. Phys. 121, 1690 (2004); and ibid. 121, 1704 (2004)], a new method was introduced for performing exact quantum dynamics calculations. The method uses a 'weylet' basis set (orthogonalized Weyl-Heisenberg wavelets) combined with phase space truncation, to defeat the exponential scaling of CPU effort with system dimensionality-the first method ever able to achieve this long-standing goal. Here, we develop another such method, which uses a much more convenient basis of momentum-symmetrized Gaussians. Despite being non-orthogonal, symmetrized Gaussians are collectively local, allowing for effective phase space truncation. A dimension-independent code for computing energy eigenstates of both coupled and uncoupled systems has been created, exploiting massively parallel algorithms. Results are presented for model isotropic uncoupled harmonic oscillators and coupled anharmonic oscillators up to 27 dimensions. These are compared with the previous weylet calculations (uncoupled harmonic oscillators up to 15 dimensions), and found to be essentially just as efficient. Coupled system results are also compared to corresponding exact results obtained using a harmonic oscillator basis, and also to approximate results obtained using first-order perturbation theory up to the maximum dimensionality for which the latter may be feasibly obtained (four dimensions).

  7. Accurate quantum dynamics calculations using symmetrized Gaussians on a doubly dense Von Neumann lattice

    NASA Astrophysics Data System (ADS)

    Halverson, Thomas; Poirier, Bill

    2012-12-01

    In a series of earlier articles [B. Poirier, J. Theor. Comput. Chem. 2, 65 (2003);, 10.1142/S0219633603000380 B. Poirier and A. Salam, J. Chem. Phys. 121, 1690 (2004);, 10.1063/1.1767511 B. Poirier and A. Salam, J. Chem. Phys. 121, 1704 (2004), 10.1063/1.1767512], a new method was introduced for performing exact quantum dynamics calculations. The method uses a "weylet" basis set (orthogonalized Weyl-Heisenberg wavelets) combined with phase space truncation, to defeat the exponential scaling of CPU effort with system dimensionality—the first method ever able to achieve this long-standing goal. Here, we develop another such method, which uses a much more convenient basis of momentum-symmetrized Gaussians. Despite being non-orthogonal, symmetrized Gaussians are collectively local, allowing for effective phase space truncation. A dimension-independent code for computing energy eigenstates of both coupled and uncoupled systems has been created, exploiting massively parallel algorithms. Results are presented for model isotropic uncoupled harmonic oscillators and coupled anharmonic oscillators up to 27 dimensions. These are compared with the previous weylet calculations (uncoupled harmonic oscillators up to 15 dimensions), and found to be essentially just as efficient. Coupled system results are also compared to corresponding exact results obtained using a harmonic oscillator basis, and also to approximate results obtained using first-order perturbation theory up to the maximum dimensionality for which the latter may be feasibly obtained (four dimensions).

  8. Quantum Monte Carlo calculation of the singlet--triplet splitting in methylene

    SciTech Connect

    Reynolds, P.J.; Dupuis, M.; Lester W.A. Jr.

    1985-02-15

    The fixed-node quantum Monte Carlo (QMC) method is used to calculate the total energy of CH/sub 2/ in the /sup 3/B/sub 1/ and /sup 1/A/sub 1/ states. For both states, the best QMC variationally bounded energies lie more than 15 kcal/mol (0.024 h) below the best previous variational calculations. Subtracting these energies to obtain the singlet--triplet splitting yields T/sub e/ = 9.4 +- 2.2 kcal/mol. Adjusting for zero-point energies and relativistic effects, we obtain T/sub 0/ = 8.9 +- 2.2 kcal/mol. This result is in excellent agreement with the recent direct measurements of McKellar et al. of T/sub 0/ = 9.05 +- 0.06 kcal/mol, and of Leopold et al. of approx.9 kcal/mol, as well as with recent threoretical investigations which indicate an energy gap of 9--11 kcal/mol. We summarize the QMC method, discuss a possible scheme for iteratively correcting the procedure, and note that the present results were obtained using only single determinant functions for both states, in contrast to conventional ab initio approaches which must use at least two configurations to properly describe the singlet state.

  9. Intramolecular hydrogen bonding in 5-nitrosalicylaldehyde: IR spectrum and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Moosavi-Tekyeh, Zainab; Taherian, Fatemeh; Tayyari, Sayyed Faramarz

    2016-05-01

    The structural parameters, and vibrational frequencies of 5-nitrosalicylaldehyde (5NSA) were studied by the FT-IR and Raman spectra and the quantum chemical calculations carried out at the B3LYP/6-311++G(d,p) level of theory in order to investigate the intramolecular hydrogen bonding (IHB) present in its structure. The strength and nature of IHB in the optimized structure of 5NSA were studied in detail by means of the atoms in molecules (AIM) and the natural bond orbital (NBO) approaches. The results obtained were then compared with the corresponding data for its parent molecule, salicylaldehyde (SA). Comparisons made between the geometrical structures for 5NSA and SA, their OH/OD stretching and out-of-plane bending modes, their enthalpies for the hydrogen bond, and their AIM parameters demonstrated a stronger H-bonding in 5NSA compared with that in SA. The calculated binding enthalpy (ΔHbind) for 5NSA was -10.92 kcal mol-1. The observed νOH and γOH appeared at about 3120 cm-1 and 786 cm-1 respectively. The stretching frequency shift of H-bond formation was 426 cm-1 which is consistent with ΔHbind and the strength of H-bond in 5NSA. The delocalization energies and electron delocalization indices derived by the NBO and AIM approaches indicate that the resonance effects were responsible for the stronger IHB in 5NSA than in SA.

  10. Band structure calculations for dilute nitride quantum wells under compressive or tensile strain

    NASA Astrophysics Data System (ADS)

    Carrère, H.; Marie, X.; Barrau, J.; Amand, T.; Ben Bouzid, S.; Sallet, V.; Harmand, J.-C.

    2004-08-01

    We have calculated the band structure of InGaAsN/GaAs(N)/GaAs compressively strained quantum wells (QW) emitting at 1.3 µm using the band anticrossing model and an eight-band \\mathbf {k}\\bdot \\mathbf {p} Hamiltonian. The calculated interband optical transition energies have been compared to the experimental ones deduced from photocurrent, photoluminescence and excitation of photoluminescence spectroscopy experiments and measured laser characteristics extracted from the recent literature. Because of the high compressive strain in the QW, strain-compensated structures may be required in order to grow stable multiple QWs; in view of this we have studied the band structure of InGaAsN/GaAsP/GaAs QWs emitting at 1.3 µm. Dilute nitride structures also offer the possibility of growing tensile strained QW lasers on InP substrate emitting in the 1.55 µm emission wavelength range. In order to evaluate the potentialities of such structures we have determined the band characteristics of InGaAsN/InGaAsP/InP heterostructures with a TM polarized fundamental transition.

  11. Theoretical study of a potential ultraviolet avalanching detector based on impact ionization out of confined quantum states

    NASA Astrophysics Data System (ADS)

    Wang, Yang; Brennan, Kevin F.; Ruden, P. Paul

    1991-02-01

    A detailed analysis is given of a possible new ultraviolet photodetector based on impact ionization out of confined quantum states using a GaN-AlxGa1-xN multiple quantum well array. The GaN-AlGaN materials system is continuously gradeable in composition and has a large conduction-band-edge discontinuity, which makes it an attractive candidate for asymmetric confined quantum state photomultipliers. The impact-excitation rate is determined for various device geometries and doping concentrations. As the carrier concentration increases in a quantum confined structure, the excitation probability increases. The ionization rate increase is due in part to the increase in the number of carriers within the high-energy subbands of the well with the resulting reduction of the carrier ionization threshold energy. The presence of significant carriers in energy levels near the top of the well, however, acts to increase the thermionic dark current and therefore reduce performance of the device. Hence, an interesting tradeoff in the design of the structure exists; a large carrier concentration in the well is favorable in terms of of device gain but at the potential risk of increased dark current. The calculated total impact-ionization rate, thermionic, and tunneling dark currents are presented for various asymmetric multiple-quantum-well arrays. It is predicted that an appreciable ionization rate, about 10 to the 10th/s, can be realized in a device with a 200/400-A (well/well and barrier) width and a free carrier concentration of 5.0 x 10 to the 19th/cu cm within the well region.

  12. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Nagabalasubramanian, P. B.; Periandy, S.; Karabacak, Mehmet; Govindarajan, M.

    2015-06-01

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100 cm-1. The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated.

  13. Molecular structure, vibrational, electronic and thermal properties of 4-vinylcyclohexene by quantum chemical calculations.

    PubMed

    Nagabalasubramanian, P B; Periandy, S; Karabacak, Mehmet; Govindarajan, M

    2015-06-15

    The solid phase FT-IR and FT-Raman spectra of 4-vinylcyclohexene (abbreviated as 4-VCH) have been recorded in the region 4000-100cm(-1). The optimized molecular geometry and vibrational frequencies of the fundamental modes of 4-VCH have been precisely assigned and analyzed with the aid of structure optimizations and normal coordinate force field calculations based on density functional theory (DFT) method at 6-311++G(d,p) level basis set. The theoretical frequencies were properly scaled and compared with experimentally obtained FT-IR and FT-Raman spectra. Also, the effect due the substitution of vinyl group on the ring vibrational frequencies was analyzed and a detailed interpretation of the vibrational spectra of this compound has been made on the basis of the calculated total energy distribution (TED). The time dependent DFT (TD-DFT) method was employed to predict its electronic properties, such as electronic transitions by UV-Visible analysis, HOMO and LUMO energies, molecular electrostatic potential (MEP) and various global reactivity and selectivity descriptors (chemical hardness, chemical potential, softness, electrophilicity index). Stability of the molecule arising from hyper conjugative interaction, charge delocalization has been analyzed using natural bond orbital (NBO) analysis. Atomic charges obtained by Mulliken population analysis and NBO analysis are compared. Thermodynamic properties (heat capacity, entropy and enthalpy) of the title compound at different temperatures are also calculated. PMID:25795608

  14. Calculation of theoretical capacitance-voltage characteristics of 6H-SiC metal-oxide-semiconductor structures

    NASA Astrophysics Data System (ADS)

    Raynaud, C.

    2000-07-01

    The effect of nonuniform interface trap distributions on capacitance-voltage (C-V) characteristics of 6H-silicon carbide metal-oxide-semiconductor (MOS) capacitors has been investigated. Theoretical C-V curves have been calculated in order to study the influence of: (i) the nature (donor or acceptor) of the traps, (ii) the interface state density peak in the band gap and the peak magnitude. The incomplete ionization of dopants and the depletion in the polysilicon gate have also been taken into account to fit experimental data. A good agreement is observed between the interface state spectrum obtained in our calculation and the one obtained by the Terman's method. Thus, exact parameters of the MOS structures can be obtained. A peak of donor states is detected at Ev+0.65 eV, and an effective oxide charge is measured to 4.9×1012cm-2, which denotes a poor SiO2-SiC interface quality.

  15. A comparison between theoretical and experimental state-to-state charge transfer cross sections for H(+) + H2 at 20 eV: Evidence for quantum effects

    NASA Astrophysics Data System (ADS)

    Baer, Michael; Niedner, Gereon; Toennies, J. Peter

    1988-06-01

    A 3-D quantum mechanical close coupling study for the system H(+) +H2 is communicated. The quantum calculations, caried out in the finite order swiden approximation, show a better fit to previous experiments than the classical trajectory surface hopping (TSH) calculations, and provide direct evidence for the usefulness of a quantum treatment in predicting charge transfer (CT) processes. The total differential cross sections (summed over all final vibrational states) for the CT processes were calculated, in good agreement with experimental results. It is shown that a quantum mechanical treatment of both the inelastic and the charge transfer nonadiabatic processes is feasible and provides a superior description of the experiments compared to the TSH treatment. This demonstrates the importance of quantum effects in ion-molecule charge transfer.

  16. Efficiency enhancement calculations of state-of-the-art solar cells by luminescent layers with spectral shifting, quantum cutting, and quantum tripling function

    NASA Astrophysics Data System (ADS)

    ten Kate, O. M.; de Jong, M.; Hintzen, H. T.; van der Kolk, E.

    2013-08-01

    Solar cells of which the efficiency is not limited by the Shockley-Queisser limit can be obtained by integrating a luminescent spectral conversion layer into the cell structure. We have calculated the maximum efficiency of state-of-the-art c-Si, pc-Si, a-Si, CdTe, GaAs, CIS, CIGS, CGS, GaSb, and Ge solar cells with and without an integrated spectral shifting, quantum cutting, or quantum tripling layer using their measured internal quantum efficiency (IQE) curves. Our detailed balance limit calculations not only take into account light in-coupling efficiency of the direct AM1.5 spectral irradiance but also wavelength dependence of the refractive index and the IQEs of the cells and the angular dependent light in-coupling of the indirect spectral irradiance. An ideal quantum cutting layer enhances all cell efficiencies ranging from a modest 2.9% for c-Si to much larger values of 4.0%, 7.7%, and 11.2% for CIGS, Ge, and GaSb, respectively. A quantum tripling layer also enhances cell efficiencies, but to a lesser extent. These efficiency enhancements are largest for small band gap cells like GaSb (7.5%) and Ge (3.8%). Combining a quantum tripling and a quantum cutting layer would enhance efficiency of these cells by a factor of two. Efficiency enhancement by a simple spectral shifting layer is limited to less than 1% in case the IQE is high for blue and UV lights. However, for CdTe and GaSb solar cells, efficiency enhancements are as high as 4.6% and 3.5%, respectively. A shifting layer based on available red LED phosphors like Sr2Si5N8:Eu will raise CdTe efficiency by 3.0%.

  17. Calculation of intermolecular interaction strengths in the P beta' phase in lipid bilayers. Implications for theoretical models.

    PubMed Central

    Scott, H L; Pearce, P A

    1989-01-01

    The existence of the P beta' phase in certain lipid bilayers is evidence that molecular interactions between lipids are capable of producing unusual large-scale structures at or near biological conditions. The problem of identifying the specific intermolecular interactions responsible for the structures requires construction of theoretical models capable of clear predictions of the observable consequences of postulated intermolecular interactions. To this end we have carried out a twofold modeling effort aimed at understanding the ripple phase. First, we have performed detailed numerical calculations of potential energies of interaction between pairs and triplets of lipid molecules having different chain tilt angles and relative vertical alignments. The calculations support the notion that chain tilting in the gel phase is a result of successive 3-5-A displacements of neighboring molecules perpendicular to the bilayer plane rather than long-range cooperative chain tilting. Secondly, we have used these results as a guide to formulate a new lattice model for lipid bilayer condensed phases. The new model is less complex than our earlier model and it includes interactions which are, based on the energy calculations, more likely to be responsible for the ripple phase. In a certain limit the model maps onto the chiral clock model, a model of much interest in condensed matter theory. In this limit the model exhibits a chain-tilted ordered phase followed by (as temperature increases) a modulated phase followed by a disordered phase. Within this limit we discuss the properties of the model and compare structures of the modulated phase exhibited by the model with experimental data for the P beta' phase in lipid bilayers. PMID:2713447

  18. Low-rank spectral expansions of two electron excitations for the acceleration of quantum chemistry calculations

    NASA Astrophysics Data System (ADS)

    Schwerdtfeger, Christine A.; Mazziotti, David A.

    2012-12-01

    Treatment of two-electron excitations is a fundamental but computationally expensive part of ab initio calculations of many-electron correlation. In this paper we develop a low-rank spectral expansion of two-electron excitations for accelerated electronic-structure calculations. The spectral expansion differs from previous approaches by relying upon both (i) a sum of three expansions to increase the rank reduction of the tensor and (ii) a factorization of the tensor into geminal (rank-two) tensors rather than orbital (rank-one) tensors. We combine three spectral expansions from the three distinct forms of the two-electron reduced density matrix (2-RDM), (i) the two-particle 2D, (ii) the two-hole 2Q, and the (iii) particle-hole 2G matrices, to produce a single spectral expansion with significantly accelerated convergence. While the resulting expansion is applicable to any quantum-chemistry calculation with two-particle excitation amplitudes, it is employed here in the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)], 10.1103/PhysRevLett.101.253002. The low-rank parametric 2-RDM method scales quartically with the basis-set size, but like its full-rank version it can capture multi-reference correlation effects that are difficult to treat efficiently by traditional single-reference wavefunction methods. Applications are made to computing potential energy curves of HF and triplet OH+, equilibrium bond distances and frequencies, the HCN-HNC isomerization, and the energies of hydrocarbon chains. Computed 2-RDMs nearly satisfy necessary N-representability conditions. The low-rank spectral expansion has the potential to expand the applicability of the parametric 2-RDM method as well as other ab initio methods to large-scale molecular systems that are often only treatable by mean-field or density functional theories.

  19. Low-rank spectral expansions of two electron excitations for the acceleration of quantum chemistry calculations.

    PubMed

    Schwerdtfeger, Christine A; Mazziotti, David A

    2012-12-28

    Treatment of two-electron excitations is a fundamental but computationally expensive part of ab initio calculations of many-electron correlation. In this paper we develop a low-rank spectral expansion of two-electron excitations for accelerated electronic-structure calculations. The spectral expansion differs from previous approaches by relying upon both (i) a sum of three expansions to increase the rank reduction of the tensor and (ii) a factorization of the tensor into geminal (rank-two) tensors rather than orbital (rank-one) tensors. We combine three spectral expansions from the three distinct forms of the two-electron reduced density matrix (2-RDM), (i) the two-particle (2)D, (ii) the two-hole (2)Q, and the (iii) particle-hole (2)G matrices, to produce a single spectral expansion with significantly accelerated convergence. While the resulting expansion is applicable to any quantum-chemistry calculation with two-particle excitation amplitudes, it is employed here in the parametric 2-RDM method [D. A. Mazziotti, Phys. Rev. Lett. 101, 253002 (2008)]. The low-rank parametric 2-RDM method scales quartically with the basis-set size, but like its full-rank version it can capture multi-reference correlation effects that are difficult to treat efficiently by traditional single-reference wavefunction methods. Applications are made to computing potential energy curves of HF and triplet OH(+), equilibrium bond distances and frequencies, the HCN-HNC isomerization, and the energies of hydrocarbon chains. Computed 2-RDMs nearly satisfy necessary N-representability conditions. The low-rank spectral expansion has the potential to expand the applicability of the parametric 2-RDM method as well as other ab initio methods to large-scale molecular systems that are often only treatable by mean-field or density functional theories. PMID:23277924

  20. Conformational landscape of diisopropyl ketone: quantum chemical calculations validated by microwave spectroscopy.

    PubMed

    Zhao, Yueyue; Mouhib, Halima; Stahl, Wolfgang

    2013-01-17

    We report on the gas-phase structure of the most abundant conformer of diisopropyl ketone, (CH(3))(2)HC-CO-CH(CH(3))(2), as observed by molecular beam Fourier transform microwave spectroscopy. The gas-phase structures of five conformers of diisopropyl ketone were optimized using ab initio calculations at the MP2/6-311++G(d,p) level of theory. The natures of the stationary points were verified using harmonic frequency calculations. The only conformer observed in the supersonic jet possesses C(2) symmetry and appears as an enantiomeric pair. From the microwave spectrum, a set of three highly accurate rotational constants, five centrifugal distortion constants, and three sextic centrifugal distortion constants were determined. The structure of the observed conformer was optimized again at different levels of theory using the HF, MP2, and B3LYP methods. The theoretical constants of the C(2) conformer were subsequently validated using the experimental constants. To understand the transitions of one conformer to the others, the isopropyl groups were rotated against each other. The resulting two-dimensional potential energy surface shows nicely the symmetry of the conformational landscape and also indicates the enantiomeric pairs of the conformers. The barriers to internal rotation of the methyl groups were determined to be 1052 and 905 cm(-1) at the MP2/6-311++G(d,p) and the B3LYP/6-311++G(d,p) levels, respectively. In agreement with the theoretical predictions, no internal rotation patterns could be observed in the microwave spectrum. PMID:23181488

  1. Theoretical and experimental investigation of the nonlinear dynamical trends of passively mode-locked quantum dot lasers

    NASA Astrophysics Data System (ADS)

    Raghunathan, Ravi

    In recent years, passively mode-locked quantum dot lasers have shown great promise as compact, efficient and reliable pulsed sources of light for a range of precision and high performance applications, such as high bit-rate optical communications, diverse waveform generation, metrology, and clock distribution in high-performance computing (HPC) processors. For such applications, stable optical pulses with short picosecond pulse durations and multi-gigahertz repetition rates are required. In addition, a low pulse-to-pulse timing jitter is also necessary to prevent errors arising from the ambiguity between neighboring pulses. In order to optimize pulse quality in terms of optical characteristics such as pulse shape and pulse train behavior, as well as RF characteristics such as phase noise and timing jitter, understanding the nonlinear output dynamics of such devices is of critical importance, not only to get a sense of the regimes of operation where device output might be stable or unstable, but also to gain insight into the parameters that influence the output characteristics the most, and how they can be accessed and exploited to optimize design and performance for next generation applications. In this dissertation, theoretical and experimental studies have been combined to investigate the dynamical trends of two-section passively mode-locked quantum dot lasers. On the theoretical side, a novel numerical modeling scheme is presented as a powerful and versatile framework to study the nonlinear dynamics specific to a device, with device-specific parameters extracted over a range of operating conditions. The practical utility of this scheme is then demonstrated, first, in an analytical capability to interpret and explain dynamical trends observed in experiment, and subsequently, as a predictive tool to guide experiment to operate in a desired dynamical regime. Modeling results are compared to experimental findings where possible. Finally, optical feedback from an external reflector is experimentally studied as an additional control mechanism over the output dynamics of the device, and shown to enable invaluable insight into the behavior of the RF and optical spectra of the output. Together, the theoretical and experimental findings of this dissertation are shown to offer a systematic approach to understand, control and exploit the dynamical trends of passively mode-locked two-section quantum dot lasers.

  2. Quantum mechanics calculation of catalytic properties of a copper sensor for prediction of flow characteristics in plasmatron

    NASA Astrophysics Data System (ADS)

    Kovalev, V. L.; Kroupnov, A. A.; Vetchinkin, А. S.

    2015-12-01

    Basing on quantum-mechanical calculations within cluster models, rate coefficients of elementary steps of the complete system of heterogeneous catalytic recombination of dissociated oxygen on the copper oxide surface were determined. They were used for calculation of dependence of the effective coefficient of oxygen atom heterogeneous catalytic recombination on the temperature and partial pressure in a wide range of conditions at the surface. It has been established that its value substantially varies depending on the conditions at the surface.

  3. Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

    NASA Astrophysics Data System (ADS)

    Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

    2014-05-01

    The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

  4. Comparison between semiclassical and quantum mechanical calculations for collisional broadening and shift of HCO{sup +} rotational lines

    SciTech Connect

    Buffa, G.

    2007-10-15

    For eight HCO{sup +} rotational transitions we compare semiclassical and quantum calculations of the line broadening and shift induced by collisions with argon and helium atoms. A detailed analysis of the results allows better insights into the problem of the accuracy of the semiclassical model commonly used in most line shape studies.

  5. From C60 to Infinity: Large-Scale Quantum Chemistry Calculations of the Heats of Formation of Higher Fullerenes.

    PubMed

    Chan, Bun; Kawashima, Yukio; Katouda, Michio; Nakajima, Takahito; Hirao, Kimihiko

    2016-02-01

    We have carried out large-scale computational quantum chemistry calculations on the K computer to obtain heats of formation for C60 and some higher fullerenes with the DSD-PBE-PBE/cc-pVQZ double-hybrid density functional theory method. Our best estimated values are 2520.0 ± 20.7 (C60), 2683.4 ± 17.7 (C70), 2862.0 ± 18.5 (C76), 2878.8 ± 13.3 (C78), 2946.4 ± 14.5 (C84), 3067.3 ± 15.4 (C90), 3156.6 ± 16.2 (C96), 3967.7 ± 33.4 (C180), 4364 (C240) and 5415 (C320) kJ mol(-1). In our assessment, we also find that the B3-PW91-D3BJ and BMK-D3(BJ) functionals perform reasonably well. Using the convergence behavior for the calculated per-atom heats of formation, we obtained the formula ΔfH per carbon = 722n(-0.72) + 5.2 kJ mol(-1) (n = the number of carbon atoms), which enables an estimation of ΔfH for higher fullerenes more generally. A slow convergence to the graphene limit is observed, which we attribute to the relatively small proportion of fullerene carbons that are in "low-strain" regions. We further propose that it would take tens, if not hundreds, of thousands of carbons for a fullerene to roughly approach the limit. Such a distinction may be a contributing factor to the discrete properties between the two types of nanomaterials. During the course of our study, we also observe a fairly reliable means for the theoretical calculation of heats of formation for medium-sized fullerenes. This involves the use of isodesmic-type reactions with fullerenes of similar sizes to provide a good balance of the chemistry and to minimize the use of accompanying species. PMID:26799740

  6. Theoretical Study of Ultra-Relativistic Laser Electron Interaction with Radiation Reaction by Quantum Description

    NASA Astrophysics Data System (ADS)

    Seto, Keita; Nagatomo, Hideo; Koga, James; Mima, Kunioki

    In the near future, the intensity of the ultra-short pulse laser will reach to 1022 W/cm2. When an electron is irradiated by this laser, the electron's behavior is relativistic with significant bremsstrahlung. This radiation from the electron is regarded as the energy loss of electron. Therefore, the electron's motion changes because of the kinetic energy changing. This radiation effect on the charged particle is the self-interaction, called the “radiation reaction” or the “radiation damping”. For this reason, the radiation reaction appears in laser electron interactions with an ultra-short pulse laser whose intensity becomes larger than 1022 W/cm2. In the classical theory, it is described by the Lorentz-Abraham-Dirac (LAD) equation. But, this equation has a mathematical difficulty, which we call the “run-away”. Therefore, there are many methods for avoiding this problem. However, Dirac's viewpoint is brilliant, based on the idea of quantum electrodynamics. We propose a new equation of motion in the quantum theory with radiation reaction in this paper.

  7. Spin-orbit effects in quantum mechanical rate constant calculations for the F+H2→HF+H reaction

    NASA Astrophysics Data System (ADS)

    Aoiz, F. J.; Bañares, L.; Castillo, J. F.

    1999-09-01

    Exact and approximate quantum mechanical calculations of reaction probabilities and cumulative reaction probabilities have been carried out for the F+H2 reaction on the ab initio adiabatic potential energy surfaces by Stark and Werner (SW) and by Hartke, Stark, and Werner (HSW), the latter including spin-orbit corrections in the entrance channel. These data have been employed to obtain thermal rate constants for the title reaction in the temperature range 200-700 K. The exact and approximate results have been compared with experimental determinations and previous theoretical predictions. In particular, the reaction probabilities obtained on the HSW surface are found to be in very good agreement with recent calculations by Alexander et al. [J. Chem. Phys. 109, 5710 (1998)] based on the exact treatment of spin-orbit and Coriolis coupling for this system. However, the rate constants calculated on the HSW PES are systematically lower than the experimental values, which indicates that the height of the adiabatic potential energy surface is too high. Furthermore, an estimate of cross sections from the reaction probabilities calculated by Alexander et al. shows that the contribution to the low temperature rate constants from spin-orbit excited F(2P1/2) atoms through nonadiabatic channels is very small and, thus, nonadiabatic effects are not sufficient to bring the calculated rate constants to a better agreement with the experimental measurements.

  8. Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling.

    PubMed

    Busch, Anna; González-García, Núria; Lendvay, György; Olzmann, Matthias

    2015-07-16

    The thermal decomposition of cyanonitrene, NCN, was studied behind reflected shock waves in the temperature range 1790-2960 K at pressures near 1 and 4 bar. Highly diluted mixtures of NCN3 in argon were shock-heated to produce NCN, and concentration-time profiles of C atoms as reaction product were monitored with atomic resonance absorption spectroscopy at 156.1 nm. Calibration was performed with methane pyrolysis experiments. Rate coefficients for the reaction (3)NCN + M → (3)C + N2 + M (R1) were determined from the initial slopes of the C atom concentration-time profiles. Reaction R1 was found to be in the low-pressure regime at the conditions of the experiments. The temperature dependence of the bimolecular rate coefficient can be expressed with the following Arrhenius equation: k1(bim) = (4.2 ± 2.1) × 10(14) exp[-242.3 kJ mol(-1)/(RT)] cm(3) mol(-1) s(-1). The rate coefficients were analyzed by using a master equation with specific rate coefficients from RRKM theory. The necessary molecular data and energies were calculated with quantum chemical methods up to the CCSD(T)/CBS//CCSD/cc-pVTZ level of theory. From the topography of the potential energy surface, it follows that reaction R1 proceeds via isomerization of NCN to CNN and subsequent C-N bond fission along a collinear reaction coordinate without a tight transition state. The calculations reproduce the magnitude and temperature dependence of the rate coefficient and confirm that reaction R1 is in the low-pressure regime under our experimental conditions. PMID:25853321

  9. Quantum Monte Carlo calculations of structural and electronic properties in the correlated oxide NiO

    NASA Astrophysics Data System (ADS)

    Mitra, Chandrima; Krogel, Jaron; Santana Palacio, Juan A.; Reboredo, Fernando A.

    2015-03-01

    Transition metal oxides pose difficulties for condensed matter theories due to the presence of strong electronic correlations. The complex interplay among correlation and exchange in d subshells, crystal field effects, p-d hybridization and charge transfer gives rise to a rich variety of structural and electronic phases. NiO is one such challenging d system, where conventional band theory fails. Compared to the experimental value, the cohesive energy of bulk NiO computed within DFT-LDA differs by almost a factor of 18 %. Band gap computed within standard local or semi-local functionals are off by a factor of 80 %. A quasi-particle correction like the G0W0 approach cannot correct the band gap and is still by far too low. In this work we adopt the Diffusion Quantum Monte (DMC) approach to study the structural and electronic properties of NiO. Trial wave-functions were self consistently generated in a Slater-Jastrow form. To test pseudopotentials used, DMC calculations were done on atomic Ni and O and their computed ionization potentials showed excellent agreement with experiments (within 0.04%). The equilibrium bond length and binding energy of the NiO dimer were also computed that were 0.001% and 0.03%, respectively, from experimental values. DMC calculations of equation of state and band gap of bulk NiO will be presented. We gratefully acknowledge support from U.S Department of Energy, Basic Energy Sciences, Materials Science and Engineering Division.

  10. Relevance of silicate surface morphology in interstellar H2 formation. Insights from quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Navarro-Ruiz, Javier; Martínez-González, José Ángel; Sodupe, Mariona; Ugliengo, Piero; Rimola, Albert

    2015-10-01

    The adsorption of H atoms and their recombination to form an H2 molecule on slab models of the crystalline Mg2SiO4 forsterite (001) and (110) surfaces was studied by means of quantum mechanical calculations based on periodic density functional theory (DFT). Present results are compared with those previously reported for the most stable (010) surface, showing the relevance of the surface morphology and their stability on the H2 formation. Different H chemisorption states were identified, mostly on the outermost O atoms of the surfaces. In agreement with the higher instability of the (001) and (110) surfaces, the calculated adsorption energies are larger than those for the (010) surface. Computed energy barriers for the H hopping on these surfaces are exceedingly high to occur at the very low temperatures of deep space. For the adsorption of two H atoms, the most stable complexes are those in which the H atoms form Mg-H and SiOH surface groups. From these complexes, we did not identify energetically feasible paths for H2 formation through a Langmuir-Hinshelwood mechanism on the (001) surface because the initial states are more stable than the final products. However, on the (110) surface one path was found to be exoergic with very low energy barriers. This differs to that observed for the (010) surface, for which two feasible Langmuir-Hinshelwood-based channels were identified. H2 formation through the Eley-Rideal mechanism was also simulated, in which an incoming H atom impinges on a pre-adsorbed H atom at the (001) and (110) surfaces in a barrierless way.

  11. Schwarzschild radius from Monte Carlo calculation of the Wilson loop in supersymmetric matrix quantum mechanics.

    PubMed

    Hanada, Masanori; Miwa, Akitsugu; Nishimura, Jun; Takeuchi, Shingo

    2009-05-01

    In the string-gauge duality it is important to understand how the space-time geometry is encoded in gauge theory observables. We address this issue in the case of the D0-brane system at finite temperature T. Based on the duality, the temporal Wilson loop W in gauge theory is expected to contain the information of the Schwarzschild radius RSch of the dual black hole geometry as log(W)=RSch/(2pialpha'T). This translates to the power-law behavior log(W)=1.89(T/lambda 1/3)-3/5, where lambda is the 't Hooft coupling constant. We calculate the Wilson loop on the gauge theory side in the strongly coupled regime by performing Monte Carlo simulations of supersymmetric matrix quantum mechanics with 16 supercharges. The results reproduce the expected power-law behavior up to a constant shift, which is explainable as alpha' corrections on the gravity side. Our conclusion also demonstrates manifestly the fuzzball picture of black holes. PMID:19518857

  12. Properties of Solar Thermal Fuels by Accurate Quantum Monte Carlo Calculations

    NASA Astrophysics Data System (ADS)

    Saritas, Kayahan; Ataca, Can; Grossman, Jeffrey C.

    2014-03-01

    Efficient utilization of the sun as a renewable and clean energy source is one of the major goals of this century due to increasing energy demand and environmental impact. Solar thermal fuels are materials that capture and store the sun's energy in the form of chemical bonds, which can then be released as heat on demand and charged again. Previous work on solar thermal fuels faced challenges related to the cyclability of the fuel over time, as well as the need for higher energy densities. Recently, it was shown that by templating photoswitches onto carbon nanostructures, both high energy density as well as high stability can be achieved. In this work, we explore alternative molecules to azobenzene in such a nano-templated system. We employ the highly accurate quantum Monte Carlo (QMC) method to predict the energy storage potential for each molecule. Our calculations show that in many cases the level of accuracy provided by density functional theory (DFT) is sufficient. However, in some cases, such as dihydroazulene, the drastic change in conjugation upon light absorption causes the DFT predictions to be inconsistent and incorrect. For this case, we compare our QMC results for the geometric structure, band gap and reaction enthalpy with different DFT functionals.

  13. GPU Linear Algebra Libraries and GPGPU Programming for Accelerating MOPAC Semiempirical Quantum Chemistry Calculations.

    PubMed

    Maia, Julio Daniel Carvalho; Urquiza Carvalho, Gabriel Aires; Mangueira, Carlos Peixoto; Santana, Sidney Ramos; Cabral, Lucidio Anjos Formiga; Rocha, Gerd B

    2012-09-11

    In this study, we present some modifications in the semiempirical quantum chemistry MOPAC2009 code that accelerate single-point energy calculations (1SCF) of medium-size (up to 2500 atoms) molecular systems using GPU coprocessors and multithreaded shared-memory CPUs. Our modifications consisted of using a combination of highly optimized linear algebra libraries for both CPU (LAPACK and BLAS from Intel MKL) and GPU (MAGMA and CUBLAS) to hasten time-consuming parts of MOPAC such as the pseudodiagonalization, full diagonalization, and density matrix assembling. We have shown that it is possible to obtain large speedups just by using CPU serial linear algebra libraries in the MOPAC code. As a special case, we show a speedup of up to 14 times for a methanol simulation box containing 2400 atoms and 4800 basis functions, with even greater gains in performance when using multithreaded CPUs (2.1 times in relation to the single-threaded CPU code using linear algebra libraries) and GPUs (3.8 times). This degree of acceleration opens new perspectives for modeling larger structures which appear in inorganic chemistry (such as zeolites and MOFs), biochemistry (such as polysaccharides, small proteins, and DNA fragments), and materials science (such as nanotubes and fullerenes). In addition, we believe that this parallel (GPU-GPU) MOPAC code will make it feasible to use semiempirical methods in lengthy molecular simulations using both hybrid QM/MM and QM/QM potentials. PMID:26605718

  14. The (impossible?) formation of acetaldehyde on the grain surfaces: insights from quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Enrique-Romero, J.; Rimola, A.; Ceccarelli, C.; Balucani, N.

    2016-02-01

    Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesised by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.

  15. On the Systematic Error in the Quantum Mechanical Calculations to the Periodic Table of Elements

    NASA Astrophysics Data System (ADS)

    Khazan, Albert

    2011-05-01

    The scientists working on the problems of the Periodic Table of Elements regularly attempt to create models of the elements on the basis of the laws of Quantum Mechanics. One even attempted to use the calculation of the dependency ``atomic mass - element's number'' on this basis, in order to extend the Table by introducing two new Periods containing 50 elements each. The hyperbolic law we have found in the Periodic Table allows to find, first, the atomic mass of the last (heaviest stable) element (411.66), then - the number of the protons in it (155). Two functions were compared: the IUPAC 2007 function (elements 80-118) and another one created according the other data (elements 80-224). Both functions have a large deviation of data in No.104-118. Commencing in Period 8, there are three ``shifts'' of atomic mass for 17, 20, and 25 AMU. Also, our analysis manifests that there in all the aforementioned data is a single point with atomic mass 412 and number 155, where the parameters meet each other. This fact verifies our theory (Khazan A. Upper Limit in Mendeleev's Periodic Table - Element No.155. 2nd ed., Svenska fysikarkivet, Stockholm, 2010).

  16. The (impossible?) formation of acetaldehyde on the grain surfaces: insights from quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Enrique-Romero, J.; Rimola, A.; Ceccarelli, C.; Balucani, N.

    2016-06-01

    Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesized by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.

  17. Full dimension Rb2He ground triplet potential energy surface and quantum scattering calculations.

    PubMed

    Guillon, Grégoire; Viel, Alexandra; Launay, Jean-Michel

    2012-05-01

    We have developed a three-dimensional potential energy surface for the lowest triplet state of the Rb(2)He complex. A global analytic fit is provided as in the supplementary material [see supplementary material at http://dx.doi.org/10.1063/1.4709433 for the corresponding Fortran code]. This surface is used to perform quantum scattering calculations of (4)He and (3)He colliding with (87)Rb(2) in the partial wave J = 0 at low and ultralow energies. For the heavier helium isotope, the computed vibrational relaxation probabilities show a broad and strong shape resonance for a collisional energy of 0.15 K and a narrow Feshbach resonance at about 17 K for all initial Rb(2) vibrational states studied. The broad resonance corresponds to an efficient relaxation mechanism that does not occur when (3)He is the colliding partner. The Feshbach resonance observed at higher collisional energy is robust with respect to the isotopic substitution. However, its effect on the vibrational relaxation mechanism is faint for both isotopes. PMID:22583230

  18. Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table.

    PubMed

    Aquilante, Francesco; Autschbach, Jochen; Carlson, Rebecca K; Chibotaru, Liviu F; Delcey, Mickaël G; De Vico, Luca; Fdez Galván, Ignacio; Ferré, Nicolas; Frutos, Luis Manuel; Gagliardi, Laura; Garavelli, Marco; Giussani, Angelo; Hoyer, Chad E; Li Manni, Giovanni; Lischka, Hans; Ma, Dongxia; Malmqvist, Per Åke; Müller, Thomas; Nenov, Artur; Olivucci, Massimo; Pedersen, Thomas Bondo; Peng, Daoling; Plasser, Felix; Pritchard, Ben; Reiher, Markus; Rivalta, Ivan; Schapiro, Igor; Segarra-Martí, Javier; Stenrup, Michael; Truhlar, Donald G; Ungur, Liviu; Valentini, Alessio; Vancoillie, Steven; Veryazov, Valera; Vysotskiy, Victor P; Weingart, Oliver; Zapata, Felipe; Lindh, Roland

    2016-02-15

    In this report, we summarize and describe the recent unique updates and additions to the Molcas quantum chemistry program suite as contained in release version 8. These updates include natural and spin orbitals for studies of magnetic properties, local and linear scaling methods for the Douglas-Kroll-Hess transformation, the generalized active space concept in MCSCF methods, a combination of multiconfigurational wave functions with density functional theory in the MC-PDFT method, additional methods for computation of magnetic properties, methods for diabatization, analytical gradients of state average complete active space SCF in association with density fitting, methods for constrained fragment optimization, large-scale parallel multireference configuration interaction including analytic gradients via the interface to the Columbus package, and approximations of the CASPT2 method to be used for computations of large systems. In addition, the report includes the description of a computational machinery for nonlinear optical spectroscopy through an interface to the QM/MM package Cobramm. Further, a module to run molecular dynamics simulations is added, two surface hopping algorithms are included to enable nonadiabatic calculations, and the DQ method for diabatization is added. Finally, we report on the subject of improvements with respects to alternative file options and parallelization. PMID:26561362

  19. AFNMR: automated fragmentation quantum mechanical calculation of NMR chemical shifts for biomolecules.

    PubMed

    Swails, Jason; Zhu, Tong; He, Xiao; Case, David A

    2015-10-01

    We evaluate the performance of the automated fragmentation quantum mechanics/molecular mechanics approach (AF-QM/MM) on the calculation of protein and nucleic acid NMR chemical shifts. The AF-QM/MM approach models solvent effects implicitly through a set of surface charges computed using the Poisson-Boltzmann equation, and it can also be combined with an explicit solvent model through the placement of water molecules in the first solvation shell around the solute; the latter substantially improves the accuracy of chemical shift prediction of protons involved in hydrogen bonding with solvent. We also compare the performance of AF-QM/MM on proteins and nucleic acids with two leading empirical chemical shift prediction programs SHIFTS and SHIFTX2. Although the empirical programs outperform AF-QM/MM in predicting chemical shifts, the differences are in some cases small, and the latter can be applied to chemical shifts on biomolecules which are outside the training set employed by the empirical programs, such as structures containing ligands, metal centers, and non-standard residues. The AF-QM/MM described here is implemented in version 5 of the SHIFTS software, and is fully automated, so that only a structure in PDB format is required as input. PMID:26232926

  20. Quantum statistical modified entropic gravity as a theoretical basis for MOND

    NASA Astrophysics Data System (ADS)

    Pazy, Ehoud

    2013-04-01

    Considering the quantum statistics of the degrees of freedom on the holographic screen, it is shown that the ratio of the number of excited bulk degrees of freedom to the number of excited surface degrees of freedom is given by the modified Newtonian dynamics (MOND) interpolating function μ˜. This relationship is shown to hold also in aquadratic Lagrangian theory and in the extension of MOND to de Sitter space. Based on the relationship between the entropy and the number of degrees of freedom on the holographic screen, a simple expression, relating the MOND interpolating function to the ratio of the two-dimensional entropy to Bekenstein-Hawking entropy, is obtained. In terms of this expression MOND can be viewed as a modification of gravity arising due to a bound on the maximum entropy for the holographic screen.

  1. Nanowire terahertz quantum cascade lasers

    SciTech Connect

    Grange, Thomas

    2014-10-06

    Quantum cascade lasers made of nanowire axial heterostructures are proposed. The dissipative quantum dynamics of their carriers is theoretically investigated using non-equilibrium Green functions. Their transport and gain properties are calculated for varying nanowire thickness, from the classical-wire regime to the quantum-wire regime. Our calculation shows that the lateral quantum confinement provided by the nanowires allows an increase of the maximum operation temperature and a strong reduction of the current density threshold compared to conventional terahertz quantum cascade lasers.

  2. Studies on the s-cis-trans isomerism for some furan derivatives through IR and NMR spectroscopies and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Rittner, Roberto; Ducati, Lucas C.; Tormena, Cláudio F.; Cormanich, Rodrigo A.; Fiorin, Barbara C.; Braga, Carolyne B.; Abraham, Raymond J.

    2013-02-01

    The s-cis-trans isomerism of two furan derivatives [2-acetyl- (AF) and 2-acetyl-5-methylfuran, (AMF)] was analyzed, using data from the deconvolution of their carbonyl absorption band in two solvents (CH2Cl2 and CH3CN). These infrared data showed that the O,O-trans conformers predominate in the less polar solvent (CH2Cl2), but these equilibria change in a more polar solvent (CH3CN) leading to a slight predominance of the O,O-cis conformers, in agreement with the theoretical calculations. The later results were obtained using B3LYP-IEFPCM/6-31++g(3df,3p) level of theory, which taking into account the solvent effects at IEFPCM (Integral Equation Formalism Polarizable Continuum Model). Low temperature 13C NMR spectra in CD2Cl2 (ca. -75 °C) showed pairs of signals for each carbon, due to the known high energy barrier for the cis-trans interconversion leading to a large predominance of the trans isomers, which decreases in acetone-d6. This was confirmed by their 1H NMR spectra at the same temperatures. Moreover, despite the larger hyperconjugative interactions for the O,O-cis isomers, obtained from NBO data, these isomers are destabilized by the their Lewis energy.

  3. Coagulation Behavior of Graphene Oxide on Nanocrystallined Mg/Al Layered Double Hydroxides: Batch Experimental and Theoretical Calculation Study.

    PubMed

    Zou, Yidong; Wang, Xiangxue; Ai, Yuejie; Liu, Yunhai; Li, Jiaxing; Ji, Yongfei; Wang, Xiangke

    2016-04-01

    Graphene oxide (GO) has attracted considerable attention because of its remarkable enhanced adsorption and multifunctional properties. However, the toxic properties of GO nanosheets released into the environment could lead to the instability of biological system. In aqueous phase, GO may interact with fine mineral particles, such as chloridion intercalated nanocrystallined Mg/Al layered double hydroxides (LDH-Cl) and nanocrystallined Mg/Al LDHs (LDH-CO3), which are considered as coagulant molecules for the coagulation and removal of GO from aqueous solutions. Herein the coagulation of GO on LDHs were studied as a function of solution pH, ionic strength, contact time, temperature and coagulant concentration. The presence of LDH-Cl and LDH-CO3 improved the coagulation of GO in solution efficiently, which was mainly attributed to the surface oxygen-containing functional groups of LDH-Cl and LDH-CO3 occupying the binding sites of GO. The coagulation of GO by LDH-Cl and LDH-CO3 was strongly dependent on pH and ionic strength. Results of theoretical DFT calculations indicated that the coagulation of GO on LDHs was energetically favored by electrostatic interactions and hydrogen bonds, which was further evidenced by FTIR and XPS analysis. By integrating the experimental results, it was clear that LDH-Cl could be potentially used as a cost-effective coagulant for the elimination of GO from aqueous solutions, which could efficiently decrease the potential toxicity of GO in the natural environment. PMID:26978487

  4. Theoretical Investigation of Calculating Temperatures in the Combining Zone of Cu/Fe Composite Plate Jointed by Explosive Welding

    NASA Astrophysics Data System (ADS)

    Qu, Y. D.; Zhang, W. J.; Kong, X. Q.; Zhao, X.

    2016-03-01

    The heat-transfer behavior of the interface of Flyer plate (or Base Plate) has great influence on the microcosmic structures, stress distributions, and interface distortion of the welded interface of composite plates by explosive welding. In this paper, the temperature distributions in the combing zone are studied for the case of Cu/Fe composite plate jointed by explosive welding near the lower limit of explosive welding. The results show that Flyer plate (Cu plate) and Base Plate (Fe plate) firstly almost have the same melting rate in the explosive welding process. Then, the melting rate of Cu plate becomes higher than that of Fe plate. Finally, the melt thicknesses of Cu plate and Fe plate trend to be different constants, respectively. Meanwhile, the melting layer of Cu plate is thicker than that of Fe plate. The research could supply some theoretical foundations for calculating the temperature distribution and optimizing the explosive welding parameters of Cu/Fe composite plate to some extent.

  5. Adsorption configuration of sodium 2-quinoxalinecarboxylate on iron substrate: Investigation by in situ SERS, XPS and theoretical calculation.

    PubMed

    Huo, Sheng-Juan; He, Jin-Mei; Chen, Li-Hong; Fang, Jian-Hui

    2016-03-01

    The adsorption geometry of sodium 2-quinoxalinecarboxylate (2-QC) on iron surface was investigated by in situ surface-enhanced Raman scattering spectroscopy (SERS) and X-ray photoelectron spectroscopy (XPS) measurements. The density functional theory (DFT) calculations predicted that 2-QC ion was a highly efficient inhibitor and N as well as O atoms were the possible adsorption centers, and theoretically offered the Raman-active band position and intensity. Potential-dependent SERS results suggested that the 2-QC strongly bonded to the iron surface via the lone pair electrons of the two O atoms of the carboxylate group in a bidentate configuration with a vertical orientation at more positive potentials; However, at -1.0V, only one O atom of the carboxylate and the neighboring N(1) atom (or very close to surface) adsorbed on the iron surface forming an unidentate configuration with a titled orientation. The ions did not remain on the iron surface at more negative potentials. PMID:26655073

  6. An accurate, efficient algorithm for calculation of quantum transport in extended structures

    SciTech Connect

    Godin, T.J.; Haydock, R.

    1994-05-01

    In device structures with dimensions comparable to carrier inelastic scattering lengths, the quantum nature of carriers will cause interference effects that cannot be modeled by conventional techniques. The basic equations that govern these ``quantum`` circuit elements present significant numerical challenges. The authors describe the block recursion method, an accurate, efficient method for solving the quantum circuit problem. They demonstrate this method by modeling dirty inversion layers.

  7. Line Coupling Effects in the Isotropic Raman Spectra of N2: A Quantum Calculation at Room Temperature

    NASA Technical Reports Server (NTRS)

    Thibault, Franck; Boulet, Christian; Ma, Qiancheng

    2014-01-01

    We present quantum calculations of the relaxation matrix for the Q branch of N2 at room temperature using a recently proposed N2-N2 rigid rotor potential. Close coupling calculations were complemented by coupled states studies at high energies and provide about 10200 two-body state-to state cross sections from which the needed one-body cross-sections may be obtained. For such temperatures, convergence has to be thoroughly analyzed since such conditions are close to the limit of current computational feasibility. This has been done using complementary calculations based on the energy corrected sudden formalism. Agreement of these quantum predictions with experimental data is good, but the main goal of this work is to provide a benchmark relaxation matrix for testing more approximate methods which remain of a great utility for complex molecular systems at room (and higher) temperatures.

  8. Experimental and theoretical quantum chemical investigations of 8-hydroxy-5-nitroquinoline.

    PubMed

    Arjunan, V; Balamourougane, P S; Kalaivani, M; Raj, Arushma; Mohan, S

    2012-10-01

    The FT-IR and FT-Raman spectra of 8-hydroxy-5-nitroquinoline have been recorded in the regions 4000-400 and 4000-100 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The normal coordinate analysis was carried out to confirm the precision of the assignments. The structure of the compound was optimised and the structural characteristics were determined by density functional theory (DFT) using B3LYP method with 6-31G(**), 6-311++G(**) and cc-pVDZ basis sets. The vibrational frequencies were calculated in all these methods and were compared with the experimental frequencies which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. (1)H and (13)C NMR spectra were recorded and (1)H and (13)C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-Visible spectrum of the compound was recorded and the electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. The influences of the nitro and hydroxy groups on the skeletal modes and on the proton chemical shifts have been investigated. PMID:22728969

  9. Direct calculation of the reactive transition matrix by L-squared quantum mechanical variational methods with complex boundary conditions

    NASA Technical Reports Server (NTRS)

    Sun, Yan; Yu, Chin-Hui; Kouri, Donald J.; Schwenke, David W.; Halvick, Philippe

    1989-01-01

    A new formalism of the generalized Newton variational principle for the calculation of quantum mechanical state-to-state reaction probabilities is presented. The reformulation involves solving directly for the transition matrix rather than the reactance mtrix so that calculations may be carried out for individual columns of the transition matrix without obtaining solutions for all possible initial channels. The convergence of calculations with real and complex boundary conditions are compared for H + H2 - H2 + H, O + H2 - OH + H, and O + HD - OH + D and OD + H.

  10. Quantum dynamics calculations on atom-diatom collisions: bosons versus fermions

    NASA Astrophysics Data System (ADS)

    Hutson, Jeremy M.

    2006-05-01

    We have obtained new potential energy surfaces and carried out full quantum dynamics calculations for spin-polarized Li + Li2 [1] and K + K2 [2] collisions for both bosonic and fermionic isotopes. These are ``reactive'' scattering collisions because they include all possible arrangement channels. They are carried out in hyperspherical coordinates [3], which allow the full boson or fermion symmetry to be imposed. The potential energy surfaces are highly non-additive [4]. Our calculations give very high quenching rates for alkali dimers in excited vibrational states. For the low vibrationally excited states that we can handle at present, we do not see any suppression of inelastic scattering for fermionic atoms, even when the scattering length is large and positive. The low-temperature inelastic rate coefficients are typically above 10-10 cm^3 s-1. We conclude that Pauli blocking occurs only for molecules formed in the highest vibrational state in the potential well. Our results have important implications for experiments aimed at transferring molecules to lower vibrational states. We expect that it will be necessary to transfer them directly to the ground vibrational state for them to be long-lived. Molecules produced in any intermediate vibrational state are likely to be ejected from the trap very quickly. We have also carried out calculations for mixed-isotope collisions involving alkali dimers [5]. For ^7Li colliding with either ^6Li2 or ^6Li^7Li, reactive scattering is possible even when the molecule is in its lowest rovibrational state because of the change in zero-point energy. For ^7Li + ^6Li^7Li, there is only one reactive channel and the reactive scattering rate is suppressed by a factor of 50 compares to the vibrational relaxation rates. [1] M. T. Cvitas et al., PRL 94, 033201 (2005). [2] G. Qu'em'ener et al., PRA 71, 032722 (2005). [3] P. Sold'an et al., PRL 89, 153201 (2002). [4] P. Sold'an et al., PRA. 67, 054702 (2003). [5] M. T. Cvitas et al., PRL 94, 200402 (2005).

  11. Protonation/deprotonation process of Emodin in aqueous solution and pKa determination: UV/Visible spectrophotometric titration and quantum/molecular mechanics calculations

    NASA Astrophysics Data System (ADS)

    da Cunha, Antonio R.; Duarte, Evandro L.; Lamy, M. Teresa; Coutinho, Kaline

    2014-08-01

    We combined theoretical and experimental studies to elucidate the important deprotonation process of Emodin in water. We used the UV/Visible spectrophotometric titration curves to obtain its pKa values, pKa1 = 8.0 ± 0.1 and pKa2 = 10.9 ± 0.2. Additionally, we obtained the pKa values of Emodin in the water-methanol mixture (1:3v/v). We give a new interpretation of the experimental data, obtaining apparent pKa1 = 6.2 ± 0.1, pKa2 = 8.3 ± 0.1 and pKa3 > 12.7. Performing quantum mechanics calculations for all possible deprotonation sites and tautomeric isomers of Emodin in vacuum and in water, we identified the sites of the first and second deprotonation. We calculated the standard deprotonation free energy of Emodin in water and the pKa1, using an explicit model of the solvent, with Free Energy Perturbation theory in Monte Carlo simulations obtaining, ΔGaq = 12.1 ± 1.4 kcal/mol and pKa1 = 8.7 ± 0.9. With the polarizable continuum model for the solvent, we obtained ΔGaq = 11.6 ± 1.0 kcal/mol and pKa1 = 8.3 ± 0.7. Both solvent models gave theoretical results in very good agreement with the experimental values.

  12. Comparison of quantum Monte Carlo with time-dependent and static density-functional theory calculations of diamondoid excitation energies and Stokes shifts

    NASA Astrophysics Data System (ADS)

    Marsusi, F.; Sabbaghzadeh, J.; Drummond, N. D.

    2011-12-01

    We compute the absorption and emission energies and hence Stokes shifts of small diamondoids as a function of size using different theoretical approaches, including density-functional theory (DFT) and quantum Monte Carlo (QMC) calculations. The absorption spectra of these molecules are also investigated by time-dependent DFT and compared with experiment. We analyze the structural distortion and formation of a self-trapped exciton in the excited state, and we study the effects of these on the Stokes shift as a function of size. Compared to recent experiments, QMC overestimates the excitation energies by about 0.8(1) eV on average. Benefiting from a cancellation of errors, the optical gaps obtained in DFT calculations with the B3LYP functional are in better agreement with experiment. It is also shown that time-dependent B3LYP calculations can reproduce most of the features found in the experimental spectra. According to our calculations, the structures of diamondoids in the excited state show a distortion which is hardly noticeable compared to that found for methane. As the number of diamond cages is increased, the distortion mechanism abruptly changes character. We have shown that the Stokes shift is size dependent and decreases with the number of diamond cages. If we neglect orbital symmetry effects on the optical excitations, the rate of decrease in the Stokes shift is, on average, 0.1 eV per cage for small diamondoids.

  13. Segmented crystalline scintillators: empirical and theoretical investigation of a high quantum efficiency EPID based on an initial engineering prototype CsI(TI) detector.

    PubMed

    Sawant, Amit; Antonuk, Larry E; El-Mohri, Youcef; Zhao, Qihua; Wang, Yi; Li, Yixin; Du, Hong; Perna, Louis

    2006-04-01

    Modern-day radiotherapy relies on highly sophisticated forms of image guidance in order to implement increasingly conformal treatment plans and achieve precise dose delivery. One of the most important goals of such image guidance is to delineate the clinical target volume from surrounding normal tissue during patient setup and dose delivery, thereby avoiding dependence on surrogates such as bony landmarks. In order to achieve this goal, it is necessary to integrate highly efficient imaging technology, capable of resolving soft-tissue contrast at very low doses, within the treatment setup. In this paper we report on the development of one such modality, which comprises a nonoptimized, prototype electronic portal imaging device (EPID) based on a 40 mm thick, segmented crystalline CsI(Tl) detector incorporated into an indirect-detection active matrix flat panel imager (AMFPI). The segmented detector consists of a matrix of 160 x 160 optically isolated, crystalline CsI(Tl) elements spaced at 1016 microm pitch. The detector was coupled to an indirect detection-based active matrix array having a pixel pitch of 508 microm, with each detector element registered to 2 x 2 array pixels. The performance of the prototype imager was evaluated under very low-dose radiotherapy conditions and compared to that of a conventional megavoltage AMFPI based on a Lanex Fast-B phosphor screen. Detailed quantitative measurements were performed in order to determine the x-ray sensitivity, modulation transfer function, noise power spectrum, and detective quantum efficiency (DQE). In addition, images of a contrast-detail phantom and an anthropomorphic head phantom were also acquired. The prototype imager exhibited approximately 22 times higher zero-frequency DQE (approximately 22%) compared to that of the conventional AMFPI (approximately 1%). The measured zero-frequency DQE was found to be lower than theoretical upper limits (approximately 27%) calculated from Monte Carlo simulations, which were based solely on the x-ray energy absorbed in the detector-indicating the presence of optical Swank noise. Moreover, due to the nonoptimized nature of this prototype, the spatial resolution was observed to be significantly lower than theoretical expectations. Nevertheless, due to its high quantum efficiency (approximately 55%), the prototype imager exhibited significantly higher DQE than that of the conventional AMFPI across all spatial frequencies. In addition, the frequency-dependent DQE was observed to be relatively invariant with respect to the amount of incident radiation, indicating x-ray quantum limited behavior. Images of the contrast-detail phantom and the head phantom obtained using the prototype system exhibit good visualization of relatively large, low-contrast features, and appear significantly less noisy compared to similar images from a conventional AMFPI. Finally, Monte Carlo-based theoretical calculations indicate that, with proper optimization, further, significant improvements in the DQE performance of such imagers could be achieved. It is strongly anticipated that the realization of optimized versions of such very high-DQE EPIDs would enable megavoltage projection imaging at very low doses, and tomographic imaging from a "beam's eye view" at clinically acceptable doses. PMID:16696482

  14. Segmented crystalline scintillators: Empirical and theoretical investigation of a high quantum efficiency EPID based on an initial engineering prototype CsI(Tl) detector

    SciTech Connect

    Sawant, Amit; Antonuk, Larry E.; El-Mohri, Youcef; Zhao Qihua; Wang Yi; Li Yixin; Du Hong; Perna, Louis

    2006-04-15

    Modern-day radiotherapy relies on highly sophisticated forms of image guidance in order to implement increasingly conformal treatment plans and achieve precise dose delivery. One of the most important goals of such image guidance is to delineate the clinical target volume from surrounding normal tissue during patient setup and dose delivery, thereby avoiding dependence on surrogates such as bony landmarks. In order to achieve this goal, it is necessary to integrate highly efficient imaging technology, capable of resolving soft-tissue contrast at very low doses, within the treatment setup. In this paper we report on the development of one such modality, which comprises a nonoptimized, prototype electronic portal imaging device (EPID) based on a 40 mm thick, segmented crystalline CsI(Tl) detector incorporated into an indirect-detection active matrix flat panel imager (AMFPI). The segmented detector consists of a matrix of 160x160 optically isolated, crystalline CsI(Tl) elements spaced at 1016 {mu}m pitch. The detector was coupled to an indirect detection-based active matrix array having a pixel pitch of 508 {mu}m, with each detector element registered to 2x2 array pixels. The performance of the prototype imager was evaluated under very low-dose radiotherapy conditions and compared to that of a conventional megavoltage AMFPI based on a Lanex Fast-B phosphor screen. Detailed quantitative measurements were performed in order to determine the x-ray sensitivity, modulation transfer function, noise power spectrum, and detective quantum efficiency (DQE). In addition, images of a contrast-detail phantom and an anthropomorphic head phantom were also acquired. The prototype imager exhibited approximately 22 times higher zero-frequency DQE ({approx}22%) compared to that of the conventional AMFPI ({approx}1%). The measured zero-frequency DQE was found to be lower than theoretical upper limits ({approx}27%) calculated from Monte Carlo simulations, which were based solely on the x-ray energy absorbed in the detector--indicating the presence of optical Swank noise. Moreover, due to the nonoptimized nature of this prototype, the spatial resolution was observed to be significantly lower than theoretical expectations. Nevertheless, due to its high quantum efficiency ({approx}55%), the prototype imager exhibited significantly higher DQE than that of the conventional AMFPI across all spatial frequencies. In addition, the frequency-dependent DQE was observed to be relatively invariant with respect to the amount of incident radiation, indicating x-ray quantum limited behavior. Images of the contrast-detail phantom and the head phantom obtained using the prototype system exhibit good visualization of relatively large, low-contrast features, and appear significantly less noisy compared to similar images from a conventional AMFPI. Finally, Monte Carlo-based theoretical calculations indicate that, with proper optimization, further, significant improvements in the DQE performance of such imagers could be achieved. It is strongly anticipated that the realization of optimized versions of such very high-DQE EPIDs would enable megavoltage projection imaging at very low doses, and tomographic imaging from a 'beam's eye view' at clinically acceptable doses.

  15. FeynDyn: A MATLAB program for fast numerical Feynman integral calculations for open quantum system dynamics on GPUs

    NASA Astrophysics Data System (ADS)

    Dattani, Nikesh S.

    2013-12-01

    This MATLAB program calculates the dynamics of the reduced density matrix of an open quantum system modeled either by the Feynman-Vernon model or the Caldeira-Leggett model. The user gives the program a Hamiltonian matrix that describes the open quantum system as if it were in isolation, a matrix of the same size that describes how that system couples to its environment, and a spectral distribution function and temperature describing the environment’s influence on it, in addition to the open quantum system’s initial density matrix and a grid of times. With this, the program returns the reduced density matrix of the open quantum system at all moments specified by that grid of times (or just the last moment specified by the grid of times if the user makes this choice). This overall calculation can be divided into two stages: the setup of the Feynman integral, and the actual calculation of the Feynman integral for time propagation of the density matrix. When this program calculates this propagation on a multi-core CPU, it is this propagation that is usually the rate-limiting step of the calculation, but when it is calculated on a GPU, the propagation is calculated so quickly that the setup of the Feynman integral can actually become the rate-limiting step. The overhead of transferring information from the CPU to the GPU and back seems to have a negligible effect on the overall runtime of the program. When the required information cannot fit on the GPU, the user can choose to run the entire program on a CPU. Catalogue identifier: AEPX_v1_0. Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEPX_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.: 703. No. of bytes in distributed program, including test data, etc.: 11026. Distribution format: tar.gz. Programming language: MATLAB R2012a. Computer: See “Operating system”. Operating system: Any operating system that can run MATLAB R2007a or above. Classification: 4.4. Nature of problem: Calculating the dynamics of the reduced density operator of an open quantum system. Solution method: Numerical Feynman integral. Running time: Depends on the input parameters. See the main text for examples.

  16. Calculation of linear and nonlinear intersubband refractive-index changes in an asymmetrical semiparabolic quantum well with applied electric field

    NASA Astrophysics Data System (ADS)

    Zhang, Li; Shi, Jun-Jie

    2005-04-01

    By using the displacement harmonic variant method and the compact density matrix approach, the linear and nonlinear intersubband refractive-index changes (RICs) in a semiparabolic quantum well (QW) with an applied electric field have been investigated in detail. Simple analytical formulae for the linear and nonlinear RICs in the system were also deduced. The effect of the band nonparabolicity has been taken into account. Numerical calculations of typical GaAs semiparabolic QWs were performed. The dependence of the linear and nonlinear RICs on the incident optical intensity, the frequency of the confined potential of the semiparabolic quantum well, and the strength of the applied electric field were discussed under both conditions of considering and ignoring the band nonparabolicity. Results reveal that the RICs in the semiparabolic quantum-well system sensitively depend on these factors.

  17. Theoretical Prediction of Hydrogen-Bond Basicity pKBHX Using Quantum Chemical Topology Descriptors

    PubMed Central

    2014-01-01

    Hydrogen bonding plays an important role in the interaction of biological molecules and their local environment. Hydrogen-bond strengths have been described in terms of basicities by several different scales. The pKBHX scale has been developed with the interests of medicinal chemists in mind. The scale uses equilibrium constants of acid···base complexes to describe basicity and is therefore linked to Gibbs free energy. Site specific data for polyfunctional bases are also available. The pKBHX scale applies to all hydrogen-bond donors (HBDs) where the HBD functional group is either OH, NH, or NH+. It has been found that pKBHX can be described in terms of a descriptor defined by quantum chemical topology, ΔE(H), which is the change in atomic energy of the hydrogen atom upon complexation. Essentially the computed energy of the HBD hydrogen atom correlates with a set of 41 HBAs for five common HBDs, water (r2 = 0.96), methanol (r2 = 0.95), 4-fluorophenol (r2 = 0.91), serine (r2 = 0.93), and methylamine (r2 = 0.97). The connection between experiment and computation was strengthened with the finding that there is no relationship between ΔE(H) and pKBHX when hydrogen fluoride was used as the HBD. Using the methanol model, pKBHX predictions were made for an external set of bases yielding r2 = 0.90. Furthermore, the basicities of polyfunctional bases correlate with ΔE(H), giving r2 = 0.93. This model is promising for the future of computation in fragment-based drug design. Not only has a model been established that links computation to experiment, but the model may also be extrapolated to predict external experimental pKBHX values. PMID:24460383

  18. Nuclear Quantum Effects in Ice Phases and Water from First Principles Calculations

    NASA Astrophysics Data System (ADS)

    Pamuk, Betul

    Despite the simplicity of the molecule, condensed phases of water show many physical anomalies, some of which are still unexplained to date. This thesis focuses on one striking anomaly that has been largely neglected and never explained. When hydrogen (1H) is replaced by deuterium (2 D), zero point fluctuations of the heavy isotope causes ice to expand, whereas in normal isotope effect, heavy isotope causes volume contraction. Furthermore, in a normal isotope effect, the shift in volume should decrease with increasing temperature, while, in ice, the volume shift increases with increasing temperature and persists up to the melting temperature and also exists in liquid water. In this dissertation, nuclear quantum effects on structural and cohesive properties of different ice polymorphs are investigated. We show that the anomalous isotope effect is well described by first principles density functional theory with van der Waals (vdW-DF) functionals within the quasi-harmonic approximation. Our theoretical modeling explains how the competition between the intra- and inter-molecular bonding of ice leads to an anomalous isotope effect in the volume and bulk modulus of ice. In addition, we predict a normal isotope effect when 16O is replaced by 18O, which is experimentally confirmed. Furthermore, the transition from proton disordered hexagonal phase, ice Ih to proton ordered hexagonal phase, ice XI occurs with a temperature difference between 1H and 2D of 6K, in good agreement with experimental value of 4K. We explain, for first time for that this temperature difference is entirely due to the zero point energy. In the second half of this thesis, we expand our study to the other ice phases: ice Ic, ice IX, ice II, ice VIII, clathrate hydrates, and low and high density amorphous ices. We employ the methodology that we have developed to investigate the isotope effect in structures with different configurations. We show that there is a transition from anomalous isotope effect to normal isotope effect in these structures as the density increases. We analyse the bonding mechanism of these structures and make links to the most important anomalies of liquid water.

  19. Theoretical study of quantum molecular reaction dynamics and of the effects of intense laser radiation on a diatomic molecule

    SciTech Connect

    Dardi, P.S.

    1984-11-01

    Within the very broad field of molecular dynamics, we have concentrated on two simple yet important systems. The systems are simple enough so that they are adequately described with a single Born-Oppenheimer potential energy surface and that the dynamics can be calculated accurately. They are important because they give insight into solving more complicated systems. First we discuss H + H/sub 2/ reactive scattering. We present an exact formalism for atom-diatom reactive scattering which avoids the problem of finding a coordinate system appropriate for both reactants and products. We present computational results for collinear H + H/sub 2/ reactive scattering which agree very well with previous calculations. We also present a coupled channel distorted wave Born approximation for atom-diatom reactive scattering which we show is a first order approximation to our exact formalism. We present coupled channel DWBA results for three dimensional H + H/sub 2/ reactive scattering. The second system is an isolated HF molecule in an intense laser field. Using classical trajectories and quantum dynamics, we look at energy absorbed and transition probabilities as a function of the laser pulse time and also averaged over the pulse time. Calculations are performed for both rotating and nonrotating HF. We examine one and two photon absorption about the fundamental frequency, multiphoton absorption, and overtone absorption. 127 references, 31 figures, 12 tables.

  20. Theoretical foundation for real-time prostate localization using an inductively coupled transmitter and a superconducting quantum interference device (SQUID) magnetometer system.

    PubMed

    McGary, John E

    2004-01-01

    Real-time, 3D localization of the prostate for intensity-modulated radiotherapy can be accomplished with passively charged radio frequency transmitters and superconducting quantum interference device (SQUID) magnetometers. The overall system design consists of an external dipole antenna as a power source for charging a microchip implant transmitter and SQUID magnetometers for signal detection. An external dipole antenna charges an on-chip capacitor through inductive coupling in the near field region through a small implant inductor. The charge and discharge sequence between the external antenna and the implant circuit can be defined by half duplex, full duplex, or sequential operations. The resulting implant discharge current creates an alternating magnetic field through the inductor. The field is detected by the surrounding magnetometers, and the location of the implant transmitter can be calculated. Problems associated with this system design are interrelated with the signal strength at the detectors, detector sensitivity, and charge time of the implant capacitor. The physical parameters required for optimizing the system for real-time applications are the operating frequency, implant inductance and capacitance, the external dipole current and loop radius, the detector distance, and mutual inductance. Consequently, the sequential operating mode is the best choice for real-time localization for constraints requiring positioning within 1 s due to the mutual inductance and detector sensitivity. We present the theoretical foundation for designing a real-time, 3D prostate localization system including the associated physical parameters and demonstrate the feasibility and physical limitations for such a system. PMID:15738919

  1. Vibrational analysis and quantum chemical calculations of 2,2‧-bipyridine Zinc(II) halide complexes

    NASA Astrophysics Data System (ADS)

    Ozel, Aysen E.; Kecel, Serda; Akyuz, Sevim

    2007-05-01

    In this study the molecular structure and vibrational spectra of Zn(2,2'-bipyridine)X 2 (X = Cl and Br) complexes were studied in their ground states by computational vibrational study and scaled quantum mechanical (SQM) analysis. The geometry optimization, vibrational wavenumber and intensity calculations of free and coordinated 2,2'-bipyridine were carried out with the Gaussian03 program package by using Hartree-Fock (HF) and Density Functional Theory (DFT) with B3LYP functional and 6-31G (d,p) basis set. The total energy distributions (TED) of the vibrational modes were calculated by using Scaled Quantum Mechanical (SQM) analysis. Fundamentals were characterised by their total energy distributions. Coordination sensitive modes of 2,2'-bipyridine were determined.

  2. Predicted phototoxicities of carbon nano-material by quantum mechanical calculations.

    EPA Science Inventory

    The basis of this research is obtaining the best quantum mechanical structure of carbon nanomaterials and is fundamental in determining their other properties. Therefore, their predictive phototoxicity is directly related to the materials structure. The results of this project w...

  3. Predicted phototoxicities of carbon nano-material by quantum mechanical calculations.

    EPA Science Inventory

    The basis of this research is obtaining the best quantum mechanical structure of carbon nanomaterials and is fundamental in determining their other properties. Therefore, their predictive phototoxicity is directly related to the materials’ structure. The results of this project w...

  4. Speeding Up and Quantifying Approximation Error in Continuum Quantum Monte Carlo Solid-State Calculations

    NASA Astrophysics Data System (ADS)

    Parker, William David

    Quantum theory has successfully explained the mechanics of much of the microscopic world. However, Schrodinger's equations are difficult to solve for many-particle systems. Mean-field theories such as Hartree-Fock and density functional theory account for much of the total energy of electronic systems but fail on the crucial correlation energy that predicts solid cohesion and material properties. Monte Carlo methods solve differential and integral equations with error independent of the number of dimensions in the problem. Variational Monte Carlo (VMC) applies the variational principle to optimize the wave function used in the Monte Carlo integration of Schrodinger's time-independent equation. Diffusion Monte Carlo (DMC) represents the wave function by electron configurations diffusing stochastically in imaginary time to the ground state. Approximations in VMC and DMC make the problem tractable but introduce error in parameter-controlled and uncontrolled ways. The many-electron wave function consists of single-particle orbitals. The orbitals are combined in a functional form to account for electron exchange and correlation. Plane waves are a convenient basis for the orbitals. However, plane-wave orbitals grow in evaluation cost with basis-set completeness and system size. To speed up the calculation, polynomials approximate the plane-wave sum. Four polynomial methods tested are: Lagrange interpolation, pp-spline interpolation, B-spline interpolation and B-spline approximation. The polynomials all increase speed by an order of the number of particles. B-spline approximation most consistently maintains accuracy in the seven systems tested. However, polynomials increase the memory needed by a factor of two to eight. B-spline approximation with a separate approximation for the Laplacian of the orbitals increases the memory by a factor of four over plane waves. Polynomial-based orbitals enable larger calculations and careful examination of error introduced by approximations in VMC and DMC. In silicon bulk and interstitial defects, tens of variational parameters in the wave function converge the VMC energy. A basis set cutoff ≈1000 eV converges the VMC energy to within 10 meV. Controlling the population of electron configurations representing the DMC wave function does not bias the energy above 24 configurations. An imaginary time step for the configurations of 10-2 hartree-1 introduces no error above the 10 meV level. Finite-size correction methods on the 16-atom cell size with difference up to 2 eV error and 1 eV discrepancy between 16- and 64-atom cells indicate finite-size error is still significant. Pseudopotentials constructed with and without scalar relativistic correction agree in DMC energy differences at the 100 meV level, and mean-field calculations with and without pseudopotentials suggest a correction of 50--100 meV. Using the VMC wave function to evaluate the nonlocal portion of the pseudopotential introduces an error on the 1 meV level. DMC energies using orbitals produced with varying mean-field approximations produce a 1 eV range in the defect formation energies while applying a backflow transformation to the electron coordinates reduces Monte Carlo fluctuations. The backflow-transformed average also permits an extrapolation to zero fluctuation. The extrapolated value estimates the formation energy unbiased by the starting wave function to be 4.5--5 eV.

  5. Comparison of Oxygen Gauche Effects in Poly(Oxyethylene) and Poly(ethylene terephtylene) Based on Quantum Chemistry Calculations

    NASA Technical Reports Server (NTRS)

    Jaffe, Richard; Han, Jie; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)

    1997-01-01

    The so-called oxygen gauche effect in poly(oxyethylene) (POE) and its model molecules such as 1,2-dimethoxyethane (DME) and diglyme (CH3OC2H4OC2H4OCH3) is manifested in the preference for gauche C-C bond conformations over trans. This has also been observed for poly(ethylene terephthalate) (PET). Our previous quantum chemistry calculations demonstrated that the large C-C gauche population in DME is due, in part, to a low-lying tg +/- g+ conformer that exhibits a substantial 1,5 CH ... O attraction. New calculations will be described that demonstrate the accuracy of the original quantum chemistry calculations. In addition, an extension of this work to model molecules for PET will be presented. It is seen that the C-C gauche preference is much stronger in 1,2 diacetoxyethane than in DME. In addition, there exist low-lying tg +/- g+/- and g+/-g+/-g+/- conformers that exhibit 1,5 CH ... O attractions involving the carbonyl oxygens. It is expected that the -O-C-C-O- torsional properties will be quite different in these two polymers. The quantum chemistry results are used to parameterize rotational isomeric states models (RIS) and force fields for molecular dynamics simulations of these polymers.

  6. Effect of hydroxyl group position on adsorption behavior and corrosion inhibition of hydroxybenzaldehyde Schiff bases: Electrochemical and quantum calculations

    NASA Astrophysics Data System (ADS)

    Danaee, I.; Ghasemi, O.; Rashed, G. R.; Rashvand Avei, M.; Maddahy, M. H.

    2013-03-01

    The corrosion inhibition and adsorption of N,N'-bis(n-hydroxybenzaldehyde)-1,3-propandiimine (n-HBP) Schiff bases has been investigated on steel electrode in 1 M HCl by using electrochemical techniques. The experimental results suggest that the highest inhibition efficiency was obtained for 3-HBP. Polarization curves reveal that all studied inhibitors are mixed type. Density functional theory (DFT) at the B3LYP/6-31G(d,p) and B3LYP/3-21G basis set levels and ab initio calculations using HF/6-31G(d,p) and HF/3-21G methods were performed on three Schiff bases. By studying the effects of hydroxyl groups in ortho-, meta-, para- positions, the best one as inhibitor was found to be meta-position of OH in Schiff base (i.e., 3-HBP). The order of inhibition efficiency obtained was corresponded with the order of most of the calculated quantum chemical parameters. Quantitative structure activity relationship (QSAR) approach has been used and a correlation of the composite index of some of the quantum chemical parameters was performed to characterize the inhibition performance of the Schiff bases studied. The results showed that %IE of the Schiff bases was closely related to some of the quantum chemical parameters but with varying degrees/order. The calculated %IE of the Schiff base studied was found to be close to their experimental corrosion inhibition efficiencies.

  7. First-principles theoretical analysis of transition-metal doping of ZnSe quantum dots

    NASA Astrophysics Data System (ADS)

    Singh, Tejinder; Mountziaris, T. J.; Maroudas, Dimitrios

    2012-07-01

    We present a systematic analysis of the underlying mechanism of transition-metal doping in ZnSe nanocrystals, using first-principles density functional theory calculations. Our analysis focuses on the adsorption and surface segregation of Mn dopants on ZnSe nanocrystal surface facets. We find that the chemical potentials of the growth precursor species determine the surface structure and morphology of the nanocrystals. We report binding energies for Mn adsorption onto ZnSe surfaces and find that all the anion-rich surfaces contribute toward dopant adsorption onto ZnSe nanocrystal surface facets. Beyond a critical value of dopant surface coverage, these adsorbed dopants may induce structural transitions in low-Miller-index surface facets, resulting in morphological transitions of the ZnSe nanocrystals. In addition, the dopant binding-energy dependence on the dopant surface concentration explains the doping difficulties during nanocrystal growth. Finally, we report surface segregation energy profiles for Mn dopant segregation on low-Miller-index ZnSe nanocrystal surface facets. We find that, under conditions that render ZnSe(001)-(2 × 1) as the dominant dopable surface of ZnSe nanocrystals, Mn dopants do not have a tendency to segregate on this surface; this guarantees that the dopants remain incorporated into the core regions of the nanocrystal instead of escaping to the surface.

  8. Effects of strain and quantum confinement in optically pumped nuclear magnetic resonance in GaAs: Interpretation guided by spin-dependent band structure calculations

    NASA Astrophysics Data System (ADS)

    Wood, R. M.; Saha, D.; McCarthy, L. A.; Tokarski, J. T.; Sanders, G. D.; Kuhns, P. L.; McGill, S. A.; Reyes, A. P.; Reno, J. L.; Stanton, C. J.; Bowers, C. R.

    2014-10-01

    A combined experimental-theoretical study of optically pumped nuclear magnetic resonance (OPNMR) has been performed in a GaAs /A l0.1G a0.9As quantum well film epoxy bonded to a Si substrate with thermally induced biaxial strain. The photon energy dependence of the Ga OPNMR signal was recorded at magnetic fields of 4.9 and 9.4 T at a temperature of 4.8-5.4 K. The data were compared to the nuclear spin polarization calculated from the electronic structure and differential absorption to spin-up and spin-down states of the electron conduction band using a modified k .p model based on the Pidgeon-Brown model. Comparison of theory with experiment facilitated the assignment of features in the OPNMR energy dependence to specific interband Landau level transitions. The results provide insight into how effects of strain and quantum confinement are manifested in optical nuclear polarization in semiconductors.

  9. ``Additive'' cooperativity of hydrogen bonds in complexes of catechol with proton acceptors in the gas phase: FTIR spectroscopy and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Varfolomeev, Mikhail A.; Klimovitskii, Alexander E.; Abaidullina, Dilyara I.; Madzhidov, Timur I.; Solomonov, Boris N.

    2012-06-01

    Experimental study of hydrogen bond cooperativity in hetero-complexes in the gas phase was carried out by IR-spectroscopy method. Stretching vibration frequencies of Osbnd H groups in phenol and catechol molecules as well as of their complexes with nitriles and ethers were determined in the gas phase using a specially designed cell. Osbnd H groups experimental frequency shifts in the complexes of catechol induced by the formation of intermolecular hydrogen bonds are significantly higher than in the complexes of phenol due to the hydrogen bond cooperativity. It was shown that the cooperativity factors of hydrogen bonds in the complexes of catechol with nitriles and ethers in the gas phase are approximately the same. Quantum chemical calculations of the studied systems have been performed using density functional theory (DFT) methods. It was shown, that theoretically obtained cooperativity factors of hydrogen bonds in the complexes of catechol with proton acceptors are in good agreement with experimental values. Cooperative effects lead to a strengthening of intermolecular hydrogen bonds in the complexes of catechol on about 30%, despite the significant difference in the proton acceptor ability of the bases. The analysis within quantum theory of atoms in molecules was carried out for the explanation of this fact.

  10. Quantum chemical calculations of the Cl- + CH3I --> CH3Cl + I- potential energy surface.

    PubMed

    Zhang, Jiaxu; Lourderaj, Upakarasamy; Addepalli, Srirangam V; de Jong, Wibe A; Hase, William L

    2009-03-12

    Electronic structure theory calculations, using MP2 theory and the DFT functionals OPBE, OLYP, HCTH407, BhandH, and B97-1, were performed to characterize the structures, vibrational frequencies, and energies for stationary points on the Cl(-) + CH(3)I --> ClCH(3) + I(-) potential energy surface. The aug-cc-pVDZ and aug-cc-pVTZ basis sets, with an effective core potential (ECP) for iodine, were employed. Single-point CCSD(T) calculations were performed to obtain the complete basis set (CBS) limit for the reaction energies. DFT was found to give significantly longer halide ion/carbon atom bond lengths for the ion-dipole complexes and central barrier transition state than MP2. BhandH, with either the aug-cc-pVDZ or aug-cc-pVTZ basis sets, gives good agreement with the experimental structures for both CH(3)I and CH(3)Cl. The frequencies of CH(3)I and CH(3)Cl, obtained with the different levels of theory and basis sets, are in excellent agreement with experiment. The major difference between the MP2 and DFT frequencies is for the imaginary frequency of the central barrier. Using the aug-cc-pVTZ basis the MP2 value for this frequency ranges from 1.26 to 1.59 times larger than those for the DFT functionals. Thus, the MP2 and DFT theories have different PES shapes in the vicinity of the [Cl--CH(3)--I](-) central barrier. The CCSD(T)/CBS energies are in good agreement with experiments for the complexation energies and reaction exothermicity, with a small 1 kcal/mol difference for the latter. The CCSD(T)/CBS central barrier height is lower than values deduced by using statistical theoretical models to fit the Cl(-) + CH(3)I --> ClCH(3) + I(-) experimental rate constant, which is consistent with the expected nonstatistical dynamics for the reaction. The BhandH energies are in overall best agreement with the CCSD(T) values, with a largest difference of only 0.7 kcal/mol. PMID:19115824

  11. Quantum Monte Carlo Calculation for the Equation of State of MgSiO3 perovskite at high pressures

    NASA Astrophysics Data System (ADS)

    Lin, Yangzheng; Cohen, R. E.; Driver, Kevin P.; Militzer, Burkhard; Shulenburger, Luke; Kim, Jeongnim

    2014-03-01

    Magnesium silicate (MgSiO3) is among the most abundant minerals in the Earth's mantle. Its phase behavior under high pressure has important implications for the physical properties of deep Earth and the core-mantle boundary. A number of experiments and density functional theory calculations have studied perovskite and its transition to the post-perovskite phase. Here, we present our initial work on the equation of state of perovskite at pressures up to 200 GPa using quantum Monte Carlo (QMC), a benchmark ab initio method. Our QMC calculations optimize electron correlation by using a Slater-Jastrow type wave function with a single determinant comprised of single-particle orbitals extracted from fully converged DFT calculations. The equation of state obtained from QMC calculations agrees with experimental data. E-mail: rcohen@carnegiescience.edu; This work is supported by NSF.

  12. Quantum mechanical calculations on cis-2,6-bis(2-chlorophenyl)-3,3-dimethylpiperidin-4-one

    NASA Astrophysics Data System (ADS)

    Öner, Nazmiye; Tamer, Ömer; Avci, Davut; Atalay, Yusuf

    2016-03-01

    Quantum mechanical calculations on cis-2, 6-bis (2-chlorophenyl)-3, 3-dimethylpiperidin-4-one were performed by using HSEH1PBE level of density functional theory (DFT) with 6-311++G (d, p) basis set. Geometric parameters of the title molecule in the ground state were found to be in good agreement with experimental data. The frontier molecular orbitals (HOMO and LUMO) were simulated by the same level. Small energy gap between the HOMO and LUMO is an indicator molecular charge transfer within the title molecule. The electronegativity, chemical hardness and softness were also calculated by using HOMO and LUMO energies. Dipole moment, polarizability and hyperpolarizability parameters were also calculated by using HSEH1PBE level. All calculations were carried out with the GAUSSIAN 09 package program.

  13. The influence of interfaces and intra-band transitions on the band gap of CdS/HgS and GaN/X (X=InN, In0.33Ga0.67N) core/shell/shell quantum dot quantum well - A theoretical study

    NASA Astrophysics Data System (ADS)

    Ganesan, P.; Senthilkumar, L.

    2015-11-01

    A theoretical model is presented to calculate the 1s-1s transition energy of an exciton in spherically layered semiconductor quantum-dot quantum-well (QDQW), based on the LCAO variational method using effective mass approximation. The confinement energies of electron and hole and the Coulombic interaction energy between them are calculated for CdS/HgS/CdS, GaN/X/GaN (X=InN, In0.33Ga0.67N) (QDQW) with core/shell/shell structures. The results of the proposed model effectively accommodates the polarization effects at the interfaces of different semiconductor materials in a core/shell/shell structure and elucidates the significant influence of interfaces on the band gap with consistency among previous theoretical and experimental results. The wave function of exciton studied shows significant differences with other theory. The change in the band gap of QDQW is attributed to the exciton excitations by thermal occupation of the lowest dark exciton states at different temperatures. In addition, based on Quantum Confined Stark Effect (QCSE) the effect of high electric field on the charge carriers and the corresponding changes in the band gap has been investigated. The applied electric field provides strong overlap between the electron and hole wave functions as well as increases the binding energy of the exciton, which eventually decreases the band gap.

  14. On the inclusion of prime factors to calculate the theoretical lower bounds in multiplierless single constant multiplications

    NASA Astrophysics Data System (ADS)

    Troncoso Romero, David E.; Meyer-Baese, Uwe; Dolecek, Gordana Jovanovic

    2014-12-01

    This paper presents an extension to the theoretical lower bounds for the number of adders and for the adder depth in multiplierless single constant multiplications (SCM). It is shown that the number of prime factors of the constants is key information to extend the current lower bounds in certain cases that have not yet been exposed. Additionally, the hidden theoretical lower bound for the number of adders required to preserve the minimum adder depth is revealed.

  15. Research on the chelation between luteolin and Cr(III) ion through infrared spectroscopy, UV-vis spectrum and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Gao, Li-Guo; Wang, Hua; Song, Xiao-Li; Cao, Wei

    2013-02-01

    The chelation between luteolin and Cr(III) ion is studied using the theoretical methods. Many different potential complexes, formed with natural and deprotonated luteolin chelating bare and hydrated Cr(III) ion, respectively, are studied by using Density Functional Theory method. Both total and binding energies are calculated. The results from the studies indicate that Cr(III) ion is affine in forming a complex with luteolin at the 5-hydroxy-4-keto site and that deprotonated luteolin has stronger chelating power than natural luteolin. The reactivity differences between luteolin and luteolin-Cr(III) complexes are observed through comparison of their Conceptual DFT reactivity indices. Apart from the theoretical studies, the experiments are performed to modify the theoretical conclusions. Meanwhile, luteolin-Cr(III) complex has been synthesized, and the chelation site is analyzed using IR spectroscopy and UV/vis spectrum. The experimental results are found to have the same conclusions as those by theoretical studies.

  16. Localization of firearm projectiles in the human body using a superconducting quantum interference device magnetometer: A theoretical study

    NASA Astrophysics Data System (ADS)

    Hall Barbosa, C.

    2004-06-01

    A technique had been previously developed, based on magnetic field measurements using a superconducting quantum interference device sensor, to localize in three dimensions steel needles lost in the human body. In all six cases that were treated until now, the technique allowed easy surgical localization of the needles with high accuracy. The technique decreases, by a large factor, the surgery time for foreign body extraction, and also reduces the generally high odds of failure. The method is accurate, noninvasive, and innocuous, and with clear clinical importance. Despite the importance of needle localization, the most prevalent foreign body in the modern society is the firearm projectile (bullet), generally composed of lead, a paramagnetic material, thus not presenting a remanent magnetic field as steel needles do. On the other hand, since lead is a good conductor, eddy current detection techniques can be employed, by applying an alternating magnetic field with the aid of excitation coils. The primary field induces eddy currents on the lead, which in turn generate a secondary magnetic field that can be detected by a magnetometer, and give information about position and volume of the conducting foreign body. In this article we present a theoretical study for the development of a localization technique for lead bullets inside the human body. Initially, we present a model for the secondary magnetic field generated by the bullet, given a known applied field. After that, we study possible excitation systems, and propose a localization algorithm based on the detected magnetic field.

  17. Mixed quantum classical calculation of proton transfer reaction rates: From deep tunneling to over the barrier regimes

    SciTech Connect

    Xie, Weiwei; Xu, Yang; Zhu, Lili; Shi, Qiang

    2014-05-07

    We present mixed quantum classical calculations of the proton transfer (PT) reaction rates represented by a double well system coupled to a dissipative bath. The rate constants are calculated within the so called nontraditional view of the PT reaction, where the proton motion is quantized and the solvent polarization is used as the reaction coordinate. Quantization of the proton degree of freedom results in a problem of non-adiabatic dynamics. By employing the reactive flux formulation of the rate constant, the initial sampling starts from the transition state defined using the collective reaction coordinate. Dynamics of the collective reaction coordinate is treated classically as over damped diffusive motion, for which the equation of motion can be derived using the path integral, or the mixed quantum classical Liouville equation methods. The calculated mixed quantum classical rate constants agree well with the results from the numerically exact hierarchical equation of motion approach for a broad range of model parameters. Moreover, we are able to obtain contributions from each vibrational state to the total reaction rate, which helps to understand the reaction mechanism from the deep tunneling to over the barrier regimes. The numerical results are also compared with those from existing approximate theories based on calculations of the non-adiabatic transmission coefficients. It is found that the two-surface Landau-Zener formula works well in calculating the transmission coefficients in the deep tunneling regime, where the crossing point between the two lowest vibrational states dominates the total reaction rate. When multiple vibrational levels are involved, including additional crossing points on the free energy surfaces is important to obtain the correct reaction rate using the Landau-Zener formula.

  18. Effect of boundary conditions on the energy spectra of semiconductor quantum dots calculated in the effective mass approximation

    NASA Astrophysics Data System (ADS)

    Vorobiev, Y. V.; Gorley, P. M.; Vieira, V. R.; Horley, P. P.; González-Hernández, J.; Torchynska, T. V.; Diaz Cano, A.

    2010-07-01

    We consider semiconductor quantum dots shaped as a rectangular prism and a sphere, in the framework of the effective mass approximation. The Schrödinger equation was solved assuming a specular reflection of a particle from the boundary of the quantum dot, which will set the equivalent values for the particle wave function for an arbitrary original point inside the quantum dot and its image in the quantum dot wall. It is shown that the results obtained in this approximation for some classical problems coincide with those based on traditional approaches using “impenetrable walls” or periodic Born-von Karman boundary conditions. Additionally, several problems that are difficult to treat using the traditional approaches could be easily resolved with the suggested mirror-type boundary conditions. It is also shown that this “mirror walls” approach is favorable for effective mass approximation. The comparison of the calculated energy spectra with existing experimental data shows reasonable agreement between the theory and the experiment.

  19. Quantum mechanical calculation of electric fields and vibrational Stark shifts at active site of human aldose reductase

    NASA Astrophysics Data System (ADS)

    Wang, Xianwei; Zhang, John Z. H.; He, Xiao

    2015-11-01

    Recent advance in biophysics has made it possible to directly measure site-specific electric field at internal sites of proteins using molecular probes with C = O or C≡N groups in the context of vibrational Stark effect. These measurements directly probe changes of electric field at specific protein sites due to, e.g., mutation and are very useful in protein design. Computational simulation of the Stark effect based on force fields such as AMBER and OPLS, while providing good insight, shows large errors in comparison to experimental measurement due to inherent difficulties associated with point charge based representation of force fields. In this study, quantum mechanical calculation of protein's internal electrostatic properties and vibrational Stark shifts was carried out by using electrostatically embedded generalized molecular fractionation with conjugate caps method. Quantum calculated change of mutation-induced electric field and vibrational Stark shift is reported at the internal probing site of enzyme human aldose reductase. The quantum result is in much better agreement with experimental data than those predicted by force fields, underscoring the deficiency of traditional point charge models describing intra-protein electrostatic properties.

  20. Quantum mechanical calculation of electric fields and vibrational Stark shifts at active site of human aldose reductase.

    PubMed

    Wang, Xianwei; Zhang, John Z H; He, Xiao

    2015-11-14

    Recent advance in biophysics has made it possible to directly measure site-specific electric field at internal sites of proteins using molecular probes with C = O or C≡N groups in the context of vibrational Stark effect. These measurements directly probe changes of electric field at specific protein sites due to, e.g., mutation and are very useful in protein design. Computational simulation of the Stark effect based on force fields such as AMBER and OPLS, while providing good insight, shows large errors in comparison to experimental measurement due to inherent difficulties associated with point charge based representation of force fields. In this study, quantum mechanical calculation of protein's internal electrostatic properties and vibrational Stark shifts was carried out by using electrostatically embedded generalized molecular fractionation with conjugate caps method. Quantum calculated change of mutation-induced electric field and vibrational Stark shift is reported at the internal probing site of enzyme human aldose reductase. The quantum result is in much better agreement with experimental data than those predicted by force fields, underscoring the deficiency of traditional point charge models describing intra-protein electrostatic properties. PMID:26567650

  1. How Iron-Containing Proteins Control Dioxygen Chemistry: A Detailed Atomic Level Description Via Accurate Quantum Chemical and Mixed Quantum Mechanics/Molecular Mechanics Calculations.

    SciTech Connect

    Friesner, Richard A.; Baik, Mu-Hyun; Gherman, Benjamin F.; Guallar, Victor; Wirstam, Maria E.; Murphy, Robert B.; Lippard, Stephen J.

    2003-03-01

    Over the past several years, rapid advances in computational hardware, quantum chemical methods, and mixed quantum mechanics/molecular mechanics (QM/MM) techniques have made it possible to model accurately the interaction of ligands with metal-containing proteins at an atomic level of detail. In this paper, we describe the application of our computational methodology, based on density functional (DFT) quantum chemical methods, to two diiron-containing proteins that interact with dioxygen: methane monooxygenase (MMO) and hemerythrin (Hr). Although the active sites are structurally related, the biological function differs substantially. MMO is an enzyme found in methanotrophic bacteria and hydroxylates aliphatic C-H bonds, whereas Hr is a carrier protein for dioxygen used by a number of marine invertebrates. Quantitative descriptions of the structures and energetics of key intermediates and transition states involved in the reaction with dioxygen are provided, allowing their mechanisms to be compared and contrasted in detail. An in-depth understanding of how the chemical identity of the first ligand coordination shell, structural features, electrostatic and van der Waals interactions of more distant shells control ligand binding and reactive chemistry is provided, affording a systematic analysis of how iron-containing proteins process dioxygen. Extensive contact with experiment is made in both systems, and a remarkable degree of accuracy and robustness of the calculations is obtained from both a qualitative and quantitative perspective.

  2. Quantum chemical calculations predict biological function: The case of T cell receptor interaction with a peptide/MHC class I

    NASA Astrophysics Data System (ADS)

    Antipas, Georgios S. E.; Germenis, Anastasios

    2015-02-01

    A combination of atomic correlation statistics and quantum chemical calculations are shown to predict biological function. In the present study, various antigenic peptide-Major Histocompatibility Complex (pMHC) ligands with near-identical stereochemistries, in complexation with the same T cell receptor (TCR), were found to consistently induce distinctly different quantum chemical behavior, directly dependent on the peptide’s electron spin density and intrinsically expressed by the protonation state of the peptide’s N-terminus. Furthermore, the cumulative coordination difference of any variant in respect to the native peptide was found to accurately reflect peptide biological function and immerges as the physical observable which is directly related to the immunological end-effect of pMHC-TCR interaction.

  3. Comprehensive comparison and experimental validation of band-structure calculation methods in III-V semiconductor quantum wells

    NASA Astrophysics Data System (ADS)

    Zerveas, George; Caruso, Enrico; Baccarani, Giorgio; Czornomaz, Lukas; Daix, Nicolas; Esseni, David; Gnani, Elena; Gnudi, Antonio; Grassi, Roberto; Luisier, Mathieu; Markussen, Troels; Osgnach, Patrik; Palestri, Pierpaolo; Schenk, Andreas; Selmi, Luca; Sousa, Marilyne; Stokbro, Kurt; Visciarelli, Michele

    2016-01-01

    We present and thoroughly compare band-structures computed with density functional theory, tight-binding, k · p and non-parabolic effective mass models. Parameter sets for the non-parabolic Γ, the L and X valleys and intervalley bandgaps are extracted for bulk InAs, GaAs and InGaAs. We then consider quantum-wells with thickness ranging from 3 nm to 10 nm and the bandgap dependence on film thickness is compared with experiments for In0.53Ga0.47 As quantum-wells. The impact of the band-structure on the drain current of nanoscale MOSFETs is simulated with ballistic transport models, the results provide a rigorous assessment of III-V semiconductor band structure calculation methods and calibrated band parameters for device simulations.

  4. Structure analysis and spectroscopic characterization of 2-Fluoro-3-Methylpyridine-5-Boronic Acid with experimental (FT-IR, Raman, NMR and XRD) techniques and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Alver, Özgür; Dikmen, Gökhan

    2016-03-01

    Possible stable conformers, geometrical molecular structures, vibrational properties as well as band assignments, nuclear magnetic shielding tensors of 2-Fluoro-3-Methylpyridine-5-Boronic Acid (2F3MP5BA) were studied experimentally and theoretically using FT-IR, Raman, (CP/MAS) NMR and XRD spectroscopic methods. FT-IR and Raman spectra were evaluated in the region of 3500-400 cm-1, and 3200-400 cm-1, respectively. The optimized geometric structures, vibrational wavenumbers and nuclear magnetic shielding tensors were examined using Becke-3-Lee-Yang-Parr (B3LYP) hybrid density functional theory method with 6-311++G(d, p) basis set. 1H, 13C NMR chemical shifts were calculated using the gauge invariant atomic orbital (GIAO) method. 1H, 13C, APT and HETCOR NMR experiments of title molecule were carried out in DMSO solution. 13C CP/MAS NMR measurement was done with 4 mm zirconium rotor and glycine was used as an external standard. Single crystal of 2F3MP5BA was also prepared for XRD measurements. Assignments of vibrational wavenumbers were also strengthened by calculating the total energy distribution (TED) values using scaled quantum mechanical (SQM) method.

  5. Studies on the Conformational Landscape of Tert-Butyl Acetate Using Microwave Spectroscopy and Quantum Chemical Calculations

    NASA Astrophysics Data System (ADS)

    Zhao, YueYue; Mouhib, Halima; Li, Guohua; Stahl, Wolfgang; Kleiner, Isabelle

    2014-06-01

    The tert-Butyl acetate molecule was studied using a combination of quantum chemical calculations and molecular beam Fourier transform microwave spectroscopy in the 9 to 14 GHz range. Due to its rather rigid frame, the molecule possesses only two different conformers: one of Cs and one of C1 symmetry. According to ab initio calculations, the Cs conformer is 46 kJ/mol lower in energy and is the one observed in the supersonic jet. We report on the structure and dynamics of the most abundant conformer of tert-butyl acetate, with accurate rotational and centrifugal distortion constants. Additionally, the barrier to internal rotation of the acetyl methyl group was determined. Splittings due to the internal rotation of the methyl group of up to 1.3 GHz were observed in the spectrum. Using the programs XIAM and BELGI-Cs, we determine the barrier height to be about 113 cm-1 and compare the molecular parameters obtained from these two codes. Additionally, the experimental rotational constants were used to validate numerous quantum chemical calculations. This study is part of a larger project which aims at determining the lowest energy conformers of organic esters and ketones which are of interest for flavor or perfume synthetic applications Project partly supported by the PHC PROCOPE 25059YB.

  6. Molecular structure, spectroscopic characterization of (S)-2-Oxopyrrolidin-1-yl Butanamide and ab initio, DFT based quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Ramya, T.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-10-01

    The experimental and theoretical spectra of (S)-2-Oxopyrrolidin-1-yl Butanamide (S2OPB) were studied. FT-IR and FT-Raman spectra of S2OPB in the solid phase were recorded and analyzed in the range 4000-450 and 5000-50 cm-1 respectively. The structural and spectroscopic analyses of S2OPB were calculated using ab initio Hartree Fock (HF) and density functional theory calculations (B3PW91, B3LYP) with 6-31G(d,p) basis set. A complete vibrational interpretation has been made on the basis of the calculated Potential Energy Distribution (PED). The HF, B3LYP and B3PW91 methods based NMR calculation has been used to assign the 1H NMR and 13C NMR chemical shift of S2OPB. Comparative study on UV-Vis spectral analysis between the experimental and theoretical (B3PW91, B3LYP) methods and the global chemical parameters and local descriptor of reactivity through the Fukui function were performed. Finally the thermodynamic properties of S2OPB were calculated at different temperatures and the corresponding relations between the properties and temperature were also studied.

  7. Theoretical vibrational spectra of OH(-)(H2O)2: the effect of quantum distribution and vibrational coupling.

    PubMed

    Ogata, Yudai; Kawashima, Yukio; Takahashi, Kaito; Tachikawa, Masanori

    2015-10-14

    We performed ab initio path integral molecular dynamics simulations for the hydroxide-water cluster, OH(-)(H2O)2, at 50 K, 100 K, and 150 K to investigate its flexible structure. From our simulations, we found that nuclear quantum effects enhance hydroxide hydrogen atom inversion and the conformational change between isomers occurs by simultaneous rotation of the free hydrogen atom. We propose the importance of including the transition state conformer with C2 symmetry, for the description of this system at temperatures realized in predissociation experiments. Temperature dependence of relative populations of each conformer along with multidimensional vibrational calculations were used to simulate the vibrational spectra and compare with the experimental spectra of Johnson and coworkers. We assign the doublet peaks seen in the experiment at 2500 to 3000 cm(-1), as the mixture of the ionic hydrogen bonded OH stretching overtone, ionic hydrogen bonded OH bending overtone, and the combination band of the ionic hydrogen bonded OH stretch and bend, which are modulated by the van der Waals OO vibrations. We concluded that for OH(-)(H2O)2, the vibrational couplings between the ionic hydrogen bonded motion and floppy modes contribute to the broadening of peaks observed in the 2500 to 3000 cm(-1) region. PMID:26365920

  8. Development of a True Transition State Force Field from Quantum Mechanical Calculations.

    PubMed

    Madarász, Ádám; Berta, Dénes; Paton, Robert S

    2016-04-12

    Transition state force fields (TSFF) treated the TS structure as an artificial minimum on the potential energy surface in the past decades. The necessary parameters were developed either manually or by the Quantum-to-molecular mechanics method (Q2MM). In contrast with these approaches, here we propose to model the TS structures as genuine saddle points at the molecular mechanics level. Different methods were tested on small model systems of general chemical reactions such as protonation, nucleophilic attack, and substitution, and the new procedure led to more accurate models than the Q2MM-type parametrization. To demonstrate the practicality of our approach, transferrable parameters have been developed for Mo-catalyzed olefin metathesis using quantum mechanical properties as reference data. Based on the proposed strategy, any force field can be extended with true transition state force field (TTSFF) parameters, and they can be readily applied in several molecular mechanics programs as well. PMID:26925858

  9. Variational calculations of subbands in a quantum well with uniform electric field - Gram-Schmidt orthogonalization approach

    NASA Technical Reports Server (NTRS)

    Ahn, Doyeol; Chuang, S. L.

    1986-01-01

    Variational calculations of subband eigenstates in an infinite quantum well with an applied electric field using Gram-Schmidt orthogonalized trial wave functions are presented. The results agree very well with the exact numerical solutions even up to 1200 kV/cm. It is also shown that, for increasing electric fields, the energy of the ground state decreases, while that of higher subband states increases slightly up to 1000 kV/cm and then decreases for a well size of 100 A.

  10. The quantum Hall effect in quantum dot systems

    NASA Astrophysics Data System (ADS)

    Beltukov, Y. M.; Greshnov, A. A.

    2014-12-01

    It is proposed to use quantum dots in order to increase the temperatures suitable for observation of the integer quantum Hall effect. A simple estimation using Fock-Darwin spectrum of a quantum dot shows that good part of carriers localized in quantum dots generate the intervals of plateaus robust against elevated temperatures. Numerical calculations employing local trigonometric basis and highly efficient kernel polynomial method adopted for computing the Hall conductivity reveal that quantum dots may enhance peak temperature for the effect by an order of magnitude, possibly above 77 K. Requirements to potentials, quality and arrangement of the quantum dots essential for practical realization of such enhancement are indicated. Comparison of our theoretical results with the quantum Hall measurements in InAs quantum dot systems from two experimental groups is also given.

  11. Mechanism for quantum speedup in open quantum systems

    NASA Astrophysics Data System (ADS)

    Liu, Hai-Bin; Yang, W. L.; An, Jun-Hong; Xu, Zhen-Yu

    2016-02-01

    The quantum speed limit (QSL) time for open system characterizes the most efficient response of the system to the environmental influences. Previous results showed that the non-Markovianity governs the quantum speedup. Via studying the dynamics of a dissipative two-level system, we reveal that the non-Markovian effect is only the dynamical way of the quantum speedup, while the formation of the system-environment bound states is the essential reason for the quantum speedup. Our attribution of the quantum speedup to the energy-spectrum character can supply another vital path for experiments when the quantum speedup shows up without any dynamical calculations. The potential experimental observation of our quantum speedup mechanism in the circuit QED system is discussed. Our results may be of both theoretical and experimental interest in exploring the ultimate QSL in realistic environments, and may open new perspectives for devising active quantum speedup devices.

  12. Theoretical optimization of multi-layer InAs/GaAs quantum dots subject to post-growth thermal annealing for tailoring the photoluminescence emission beyond 1.3 ?m

    NASA Astrophysics Data System (ADS)

    Ghosh, K.; Naresh, Y.; Srichakradhar Reddy, N.

    2012-07-01

    In this paper, we present theoretical analysis and computation for tuning the ground state (GS) photoluminescence (PL) emission of InAs/GaAs quantum dots (QDs) at telecommunication window of 1.3-1.55 ?m by optimizing its height and base dimensions through quantum mechanical concepts. For this purpose, numerical modelling is carried out to calculate the quantized energy states of finite dimensional QDs so as to obtain the GS PL emission at or beyond 1.3 ?m. Here, we also explored strain field altering the QD size distribution in multilayer heterostructure along with the changes in the PL spectra, simulation on post growth thermal annealing process which blueshifts the operating wavelength away from the vicinity of 1.3 ?m and improvement of optical properties by varying the thickness of GaAs spacing. The results are discussed in detail which will serve as an important information tool for device scientist fabricating high quality semiconductor quantum structures with reduced defects at telecommunication wavelengths.

  13. Experimental Ft-Ir Dispersive Raman and Theoretical DFT Calculations on Cu(ii) Chloride Complex of P-Toluidine

    NASA Astrophysics Data System (ADS)

    Bardakci, Tayyibe; Kumru, Mustafa

    2013-06-01

    In this study Cu(p-tol)2Cl2 (p-tol: p-toluidine) is prepared and characterized by elemental analysis, FT-IR, FT-FIR, and dispersive Raman spectral analysis. The molecular geometry and vibrational modes of p-tol and Cu(p-tol)2Cl2 are calculated using DFT- BVP86 and DFT-B3LYP methods with 6-311G+(d,p) basis set. The optimized geometries and calculated vibrational frequencies have been evaluated via comparison with experimental values, and the normal modes were assigned on the basis of the percent potential energy distribution (PED). The coordination effects on vibrational frequencies of p-tol are discussed by comparing the spectra of free p-tol and its Cu (II) chloride complex. A good agreement between calculated and experimental data is observed. Keywords: IR and Raman spectra; DFT; p-toluidine; Copper (II) chloride complex

  14. Theoretical calculation of the optical properties of Y{sub 3}Fe{sub 5}O{sub 12}

    SciTech Connect

    Ching, W. Y.; Gu, Zong-quan; Xu, Yong-Nian

    2001-06-01

    The electronic structure and the optical properties of Y{sub 3}Fe{sub 5}O{sub 12} crystal are calculated using the local spin density approximation+U approach. The intra-atomic correlation effect of the Fe 3d electrons is shown to be important in describing the insulating nature of the crystal. With a choice of the parameters U=3.5eV and J=0.8eV in the model Hamiltonian, a gap of 2.66 eV is obtained and a significant lowering of the occupied potion of the Fe 3d states is observed. The calculated optical absorption in the range 3{endash}6 eV is from the bulk O 2p to the Fe 3d band states. The calculated spin magnetic moments are in good agreement with experiment. {copyright} 2001 American Institute of Physics.

  15. Theoretical study on flueggenines A and B: A comparison of calculated spectroscopic properties with IR, UV and ECD experimental data

    NASA Astrophysics Data System (ADS)

    Zhou, Chang-Xin; Mo, Jian-Xia; Wang, Xue-Yao; Zhang, Jian; Gan, Li-She

    2011-03-01

    Using DFT at the B3LYP/6-31+G (d) level, DFT-D at the wb97xd/tzvpp level and TD-DFT at the B3LYP/aug-cc-pVDZ level, computational analysis of the first examples of naturally occurring dimeric indolizidine alkaloids, flueggenines A and B, accomplished the simulation and interpretation of their IR, UV and ECD spectra. Compared with the experimental ones, the calculated IR and UV spectra allowed the reinforcement of the carbon skeletons and functional groups. Calculation of the ECD spectra assured the formerly assigned absolute configurations for flueggenines A and B.

  16. Structural and theoretical investigations of short hydrogen bonds: neutron diffraction and plane-wave DFT calculations of urea phosphoric acid

    NASA Astrophysics Data System (ADS)

    Wilson, Chick C.; Morrison, Carole A.

    2002-08-01

    Low temperature neutron diffraction and high level computational methods have been applied to investigate the short hydrogen bond in urea-phosphoric acid. It is found that isolated molecule calculations predict a `normal' O-H⋯O hydrogen bond, in strong disagreement with the very short, 3 c-4 e hydrogen bond found from the neutron diffraction. Extending these calculations into a periodic environment using plane-wave DFT methods give much improved agreement with experiment, with a much shorter, stronger hydrogen bond, and significant elongation of the O-H `covalent' bond.

  17. Quantum-chemical calculations of bonding energy and the unit-cell parameters of crystalline magnesium difluoride

    SciTech Connect

    Iomin, L.M.; Buznik, V.M.

    1988-11-01

    Quantum-chemical calculations of the bonding energy of the crystal lattice, the unit-cell parameters, and the coordinates of the anions in crystalline magnesium difluoride have been performed in the framework of the Loewdin model. An expression for the energy of the three-particle interactions in rutile-like crystals has been obtained. The calculations were carried out in three successive approximations. A comparison with the experimental data shows that the best description of the interatomic interactions in rutile-like magnesium fluoride (in the framework of the Loewdin model) is achieved in an approximation which takes into account the non-Madelung interactions only in the first coordination sphere. Consideration of the short-range interactions with more distant ions worsens the agreement between theory and experiment.

  18. Theoretical study of transition state structure and reaction enthalpy of the F + H2-->HF + H reaction by a diffusion quantum Monte Carlo approach.

    PubMed

    Lu, Shih-I

    2005-05-15

    Ab initio calculations of transition state structure and reaction enthalpy of the F + H2-->HF + H reaction has been carried out by the fixed-node diffusion quantum Monte Carlo method in this study. The Monte Carlo sampling is based on the Ornstein-Uhlenbeck random walks guided by a trial wave function constructed from the floating spherical Gaussian orbitals and spherical Gaussian geminals. The Monte Carlo calculated barrier height of 1.09(16) kcal/mol is consistent with the experimental values, 0.86(10)/1.18(10) kcal/mol, and the calculated value from the multireference-type coupled-cluster (MRCC) calculation with the aug-cc-pVQZ(F)/cc-pVQZ(H) basis set, 1.11 kcal/mol. The Monte Carlo-based calculation also gives a similar value of the reaction enthalpy, -32.00(4) kcal/mol, compared with the experimental value, -32.06(17) kcal/mol, and the calculated value from a MRCC/aug-cc-pVQZ(F)/cc-pVQZ(H) calculation, -31.94 kcal/mol. This study clearly indicates a further application of the random-walk-based approach in the field of quantum chemical calculation. PMID:16161589

  19. Calculation of rotational--vibrational preionization in H/sub 2/ by multichannel quantum defect theory

    SciTech Connect

    Jungen, C.; Dill, D.

    1980-10-01

    Multichannel quantum defect theory is adapted to treat simultaneous rotational and vibrational preionization in H/sub 2/. The strongly preionized spectrum between the N/sup +/=0 and N/sup +/=2 rotational thresholds of photoionization of H/sub 2/X/sup 1/..sigma../sub g//sup +/(J''=0, v''=0) to produce H/sub 2//sup +/X/sup 2/..sigma../sub g//sup +/(N/sup +/, v/sup +/=0) is computed as example and good agreement is obtained with the photoionization data of Dehmer and Chupka.

  20. Classical Electrodynamics Coupled to Quantum Mechanics for Calculation of Molecular Optical Properties: a RT-TDDFT/FDTD Approach

    SciTech Connect

    Chen, Hanning; McMahon, J. M.; Ratner, Mark A.; Schatz, George C.

    2010-09-02

    A new multiscale computational methodology was developed to effectively incorporate the scattered electric field of a plasmonic nanoparticle into a quantum mechanical (QM) optical property calculation for a nearby dye molecule. For a given location of the dye molecule with respect to the nanoparticle, a frequency-dependent scattering response function was first determined by the classical electrodynamics (ED) finite-difference time-domain (FDTD) approach. Subsequently, the time-dependent scattered electric field at the dye molecule was calculated using the FDTD scattering response function through a multidimensional Fourier transform to reflect the effect of polarization of the nanoparticle on the local field at the molecule. Finally, a real-time time-dependent density function theory (RT-TDDFT) approach was employed to obtain a desired optical property (such as absorption cross section) of the dye molecule in the presence of the nanoparticle’s scattered electric field. Our hybrid QM/ED methodology was demonstrated by investigating the absorption spectrum of the N3 dye molecule and the Raman spectrum of pyridine, both of which were shown to be significantly enhanced by a 20 nm diameter silver sphere. In contrast to traditional quantum mechanical optical calculations in which the field at the molecule is entirely determined by intensity and polarization direction of the incident light, in this work we show that the light propagation direction as well as polarization and intensity are important to nanoparticle-bound dye molecule response. At no additional computation cost compared to conventional ED and QM calculations, this method provides a reliable way to couple the response of the dye molecule’s individual electrons to the collective dielectric response of the nanoparticle.