Science.gov

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; Sansn, 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 ?,?-unsaturated reactant (R) to the ?,?-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. Topics in theoretical and computational nanoscience: From controlling light at the nanoscale to calculating quantum effects with classical electrodynamics

    NASA Astrophysics Data System (ADS)

    McMahon, Jeffrey Michael

    Interest in structures with nanometer-length features has significantly increased as experimental techniques for their fabrication have become possible. The study of phenomena in this area is termed nanoscience, and is a research focus of chemists, pure and applied physicists, electrical engineers, and others. The reason for such focus is the wide range of novel effects that exist at this scale, both of fundamental and practical interest, which often arise from the interaction between metallic nanostructures and light, and range from large electromagnetic field enhancements to extraordinary optical transmission of light through arrays of subwavelength holes. For the theoretician and computational scientist, this area has been, and continues to be rich with interesting problems to explore and phenomena to explain. For the most part, the phenomena can be explained using classical electrodynamics. However, recent experimental techniques allow individual nanostructures to be studied, questioning the accuracy of such methods at this most detailed level. Moreover, for structures with dimensions of just a few nanometers, the applicability of such methods at all needs to be questioned. Even if a system contains many hundreds of atoms or more so that a continuum level of description is adequate, the optical (and other) properties can be difficult to correctly calculate due to the importance of quantum effects. Thus, the theoretician is in trouble, and the accurate descriptions of such structures remain largely unknown. This dissertation is aimed at addressing some of the most fundamental and outstanding questions in nanoscience from a theoretical and computational perspective, specifically: (i) At the single nanoparticle level, how well do experiment and classical electrodynamics agree? (ii) What is the detailed relationship between optical response and nanoparticle morphology, composition, and environment? (iii) Does an optimal nanostructure exist for generating large electromagnetic field enhancements, and is there a fundamental limit to this? (iv) Can nanostructures be used to control light, such as confining it, or causing fundamentally different scattering phenomena to interact, such as electromagnetic surface modes and diffraction effects? (v) Is it possible to calculate quantum effects using classical electrodynamics, and if so, how do they affect optical properties?

  3. 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.

  4. 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.

  5. 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)

  6. 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

  7. 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.

  8. Theoretical studies of quantum dynamics

    NASA Astrophysics Data System (ADS)

    Sim, Eunji

    1997-12-01

    Quantum mechanical methods have been developed for the study of dynamical processes in polyatomic systems and condensed matter. First, we developed an exact scheme for wavefunction propagation with a few degrees of freedom based on time-dependent discrete variable representations (TD-DVR) of the evolution operator. The TD-DVR evolves under appropriate reference Hamiltonians and leads to an efficient scheme for studying intramolecular or collision dynamics, allowing significant reduction of grid size and large time steps while requiring numerical effort that scales almost linearly with the total number of grid points. The method is readily applicable to systems described by time-dependent Hamiltonians. The filtered propagator functional (FPF) method, based on Feynman's path integral formulation of time-dependent quantum mechanics, has been introduced to propagate the reduced density matrix of a one-dimensional quantum mechanical system coupled to a harmonic dissipative environment. An adiabatic reference is employed to obtain accurate propagators and the harmonic bath is replaced by an influence functional which is discretized by optimal discrete variable representations. A functional of statistically important path segments selected by a Monte Carlo procedure is propagated forward in time via multiplication with a propagator functional which included finite-length nonlocal interaction arising from the dissipative bath. High efficiency and dramatic reduction of the required storage are achieved with the aid of sorting and filtering criteria, allowing iterative evaluation of the path integral over long time periods even for processes involving long-memory kernels characteristic of low-frequency solvents. Using the FPF method, we have carried out accurate path integral simulations of the primary charge separation in bacterial photosynthesis. The process is modeled in terms of three coupled electronic states corresponding to the photoexcited special pair, the reduced accessory bacteriochlorophyll and the reduced bacteriopheophytin of the L branch which interact with a dissipative medium of protein and solvent degrees of freedom. We found that a free energy of the reduced bacteriochlorophyll state about 400 cm-1 lower than that of the excited special pair, which is associated with a two-step electron transfer mechanism, yields state populations in agreement with experimental results on wild-type and modified reaction centers including the observed temperature dependence. The results are found to be rather stable with respect to reasonable changes of the medium spectral density and the specifics of the nonequilibrium configuration of the photoexcited donor state.

  9. 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.

  10. 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.

  11. Quantum turbulence: Theoretical and numerical problems

    NASA Astrophysics Data System (ADS)

    Nemirovskii, Sergey K.

    2013-03-01

    The term quantum turbulence (QT) unifies the wide class of phenomena where the chaotic set of one dimensional quantized vortex filaments (vortex tangles) appear in quantum fluids and greatly influence various physical features. Quantum turbulence displays itself differently depending on the physical situation, and ranges from quasi-classical turbulence in flowing fluids to a near equilibrium set of loops in phase transition. The statistical configurations of the vortex tangles are certainly different in, say, the cases of counterflowing helium and a rotating bulk, but in all the physical situations very similar theoretical and numerical problems arise. Furthermore, quite similar situations appear in other fields of physics, where a chaotic set of one dimensional topological defects, such as cosmic strings, or linear defects in solids, or lines of darkness in nonlinear light fields, appear in the system. There is an interpenetration of ideas and methods between these scientific topics which are far apart in other respects. The main purpose of this review is to bring together some of the most commonly discussed results on quantum turbulence, focusing on analytic and numerical studies. We set out a series of results on the general theory of quantum turbulence which aim to describe the properties of the chaotic vortex configuration, starting from vortex dynamics. In addition we insert a series of particular questions which are important both for the whole theory and for the various applications. We complete the article with a discussion of the hot topic, which is undoubtedly mainstream in this field, and which deals with the quasi-classical properties of quantum turbulence. We discuss this problem from the point of view of the theoretical results stated in the previous sections. We also included section, which is devoted to the experimental and numerical suggestions based on the discussed theoretical models.

  12. Theoretical studies of graphene nanoribbon quantum dot qubits

    NASA Astrophysics Data System (ADS)

    Chen, Chih-Chieh; Chang, Yia-Chung

    2015-12-01

    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.

  13. 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.

  14. 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

  15. Multi-million atom electronic structure calculations for quantum dots

    NASA Astrophysics Data System (ADS)

    Usman, Muhammad

    Quantum dots grown by self-assembly process are typically constructed by 50,000 to 5,000,000 structural atoms which confine a small, countable number of extra electrons or holes in a space that is comparable in size to the electron wavelength. Under such conditions quantum dots can be interpreted as artificial atoms with the potential to be custom tailored to new functionality. In the past decade or so, these nanostructures have attracted significant experimental and theoretical attention in the field of nanoscience. The new and tunable optical and electrical properties of these artificial atoms have been proposed in a variety of different fields, for example in communication and computing systems, medical and quantum computing applications. Predictive and quantitative modeling and simulation of these structures can help to narrow down the vast design space to a range that is experimentally affordable and move this part of nanoscience to nano-Technology. Modeling of such quantum dots pose a formidable challenge to theoretical physicists because: (1) Strain originating from the lattice mismatch of the materials penetrates deep inside the buffer surrounding the quantum dots and require large scale (multi-million atom) simulations to correctly capture its effect on the electronic structure, (2) The interface roughness, the alloy randomness, and the atomistic granularity require the calculation of electronic structure at the atomistic scale. Most of the current or past theoretical calculations are based on continuum approach such as effective mass approximation or k.p modeling capturing either no or one of the above mentioned effects, thus missing some of the essential physics. The Objectives of this thesis are: (1) to model and simulate the experimental quantum dot topologies at the atomistic scale; (2) to theoretically explore the essential physics i.e. long range strain, linear and quadratic piezoelectricity, interband optical transition strengths, quantum confined stark shift, coherent coupling of electronic states in a quantum dot molecule etc.; (3) to assess the potential use of the quantum dots in real device implementation and to provide physical insight to the experimentalists. Full three dimensional strain and electronic structure simulations of quantum dot structures containing multi-million atoms are done using NEMO 3-D. Both single and vertically stacked quantum dot structures are analyzed in detail. The results show that the strain and the piezoelectricity significantly impact the electronic structure of these devices. This work shows that the InAs quantum dots when placed in the InGaAs quantum well red shifts the emission wavelength. Such InAs/GaAs-based optical devices can be used for optical-fiber based communication systems at longer wavelengths (1.3um -- 1.5um). Our atomistic simulations of InAs/InGaAs/GaAs quantum dots quantitatively match with the experiment and give the critical insight of the physics involved in these structures. A single quantum dot molecule is studied for coherent quantum coupling of electronic states under the influence of static electric field applied in the growth direction. Such nanostructures can be used in the implementation of quantum information technologies. A close quantitative match with the experimental optical measurements allowed us to get a physical insight into the complex physics of quantum tunnel couplings of electronic states as the device operation switches between atomic and molecular regimes. Another important aspect is to design the quantum dots for a desired isotropic polarization of the optical emissions. Both single and coupled quantum dots are studied for TE/TM ratio engineering. The atomistic study provides a detailed physical analysis of these computationally expensive large nanostructures and serves as a guide for the experimentalists for the design of the polarization independent devices for the optical communication systems.

  16. A quantum theoretical study of polyimides

    NASA Technical Reports Server (NTRS)

    Burke, Luke A.

    1987-01-01

    One of the most important contributions of theoretical chemistry is the correct prediction of properties of materials before any costly experimental work begins. This is especially true in the field of electrically conducting polymers. Development of the Valence Effective Hamiltonian (VEH) technique for the calculation of the band structure of polymers was initiated. The necessary VEH potentials were developed for the sulfur and oxygen atoms within the particular molecular environments and the explanation explored for the success of this approximate method in predicting the optical properties of conducting polymers.

  17. 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.

  18. Quantum Theoretical Study of KCl and LiCl Clusters

    NASA Astrophysics Data System (ADS)

    Koetter, Ted; Hira, Ajit; Salazar, Justin; Jaramillo, Danelle

    2014-03-01

    This research focuses on the theoretical study of molecular clusters to examine the chemical properties of small KnClnandLinCln clusters (n = 2 - 20). The potentially important role of these molecular species in biochemical and medicinal processes is well known. This work applies the hybrid ab initio methods of quantum chemistry to derive the different alkali-halide (MnHn) geometries. Of particular interest is the competition between hexagonal ring geometries and rock salt structures. Electronic energies, rotational constants, dipole moments, and vibrational frequencies for these geometries are calculated. Magic numbers for cluster stability are identified and are related to the property of cluster compactness. Mapping of the singlet, triplet, and quintet, potential energy surfaces is performed. Calculations were performed to examine the interactions of these clusters with some atoms and molecules of biological interest, including O, O2, and Fe. Potential design of new medicinal drugs is explored.

  19. Quantum Monte Carlo calculations of light nuclei.

    SciTech Connect

    Pieper, S. C.

    1998-08-25

    Quantum Monte Carlo calculations using realistic two- and three-nucleon interactions are presented for nuclei with up to eight nucleons. We have computed the ground and a few excited states of all such nuclei with Greens function Monte Carlo (GFMC) and all of the experimentally known excited states using variational Monte Carlo (VMC). The GFMC calculations show that for a given Hamiltonian, the VMC calculations of excitation spectra are reliable, but the VMC ground-state energies are significantly above the exact values. We find that the Hamiltonian we are using (which was developed based on {sup 3}H, {sup 4}He, and nuclear matter calculations) underpredicts the binding energy of p-shell nuclei. However our results for excitation spectra are very good and one can see both shell-model and collective spectra resulting from fundamental many-nucleon calculations. Possible improvements in the three-nucleon potential are also be discussed.

  20. Quantum Monte Carlo calculations for light nuclei

    SciTech Connect

    Wiringa, R.B.

    1997-10-01

    Quantum Monte Carlo calculations of ground and low-lying excited states for nuclei with A {le} 8 have been made using a realistic Hamiltonian that fits NN scattering data. Results for more than two dozen different (J{sup {pi}}, T) p-shell states, not counting isobaric analogs, have been obtained. The known excitation spectra of all the nuclei are reproduced reasonably well. Density and momentum distributions and various electromagnetic moments and form factors have also been computed. These are the first microscopic calculations that directly produce nuclear shell structure from realistic NN interactions.

  1. 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.

  2. Information-theoretic differential geometry of quantum phase transitions.

    PubMed

    Zanardi, Paolo; Giorda, Paolo; Cozzini, Marco

    2007-09-01

    The manifold of coupling constants parametrizing a quantum Hamiltonian is equipped with a natural Riemannian metric with an operational distinguishability content. We argue that the singularities of this metric are in correspondence with the quantum phase transitions featured by the corresponding system. This approach provides a universal conceptual framework to study quantum critical phenomena which is differential geometric and information theoretic at the same time. PMID:17930382

  3. On kaonic hydrogen. Quantum field theoretic and relativistic covariant approach

    NASA Astrophysics Data System (ADS)

    Ivanov, A. N.; Cargnelli, M.; Faber, M.; Marton, J.; Troitskaya, N. I.; Zmeskal, J.

    2004-07-01

    We study kaonic hydrogen, the bound K - p state A K p . Within a quantum field theoretic and relativistic covariant approach we derive the energy level displacement of the ground state of kaonic hydrogen in terms of the amplitude of K - p scattering for arbitrary relative momenta. The amplitude of low-energy K - p scattering near threshold is defined by the contributions of three resonances ?(1405), ?(1800) and ?^0(1750) and a smooth elastic background. The amplitudes of inelastic channels of low-energy K - p scattering fit experimental data on the near-threshold behaviour of the cross-sections and the experimental data by the DEAR Collaboration. We use the soft-pion technique (leading order in Chiral Perturbation Theory) for the calculation of the partial width of the radiative decay of pionic hydrogen A_{? p} to n + ? and the Panofsky ratio. The theoretical prediction for the Panofsky ratio agrees well with experimental data. We apply the soft-kaon technique (leading order in Chiral Perturbation Theory) to the calculation of the partial widths of radiative decays of kaonic hydrogen A_{Kp} to ?^0 + ? and A_{K p} to ?^0 + ?. We show that the contribution of these decays to the width of the energy level of the ground state of kaonic hydrogen is less than 1%.

  4. A theoretical study on the molecular structure of biphenylene in its first excited singlet and triplet states: quantum chemical calculations on the structural changes of an antiaromatic molecule upon excitation

    NASA Astrophysics Data System (ADS)

    Zimmermann, Ralf

    1996-03-01

    The structural changes accompanying the electronic excitation of the antiaromatic biphenylene molecule were studied by semiempirical quantum chemical calculations, using the AM1 hamiltonian with configuration interaction (S 1, S 2, T 1, T 2, X + states). The largest bond length differences of the molecular states investigated were observed within the central four-membered ring. Potential curves of the CC bonds which connect the two benzene rings have been calculated for all molecular states investigated. For the S 0 and S 1 states, potential hypersurfaces, using the two different bond lengths of the central four-membered "cyclobutadiene" subsystem as variables, were presented. Furthermore, the geometry of 1,3-cyclobutadiene in different states (S 0, S 1, T 1, X + states) was investigated with the AM1-CI hamiltonian and compared with recent 6-31G ? MC-SCF ab initio results.

  5. 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.

  6. Ligand Affinities Estimated by Quantum Chemical Calculations.

    PubMed

    Sderhjelm, Pr; Kongsted, Jacob; Ryde, Ulf

    2010-05-11

    We present quantum chemical estimates of ligand-binding affinities performed, for the first time, at a level of theory for which there is a hope that dispersion and polarization effects are properly accounted for (MP2/cc-pVTZ) and at the same time effects of solvation, entropy, and sampling are included. We have studied the binding of seven biotin analogues to the avidin tetramer. The calculations have been performed by the recently developed PMISP approach (polarizable multipole interactions with supermolecular pairs), which treats electrostatic interactions by multipoles up to quadrupoles, induction by anisotropic polarizabilities, and nonclassical interactions (dispersion, exchange repulsion, etc.) by explicit quantum chemical calculations, using a fragmentation approach, except for long-range interactions that are treated by standard molecular-mechanics Lennard-Jones terms. In order to include effects of sampling, 10 snapshots from a molecular dynamics simulation are studied for each biotin analogue. Solvation energies are estimated by the polarized continuum model (PCM), coupled to the multipole-polarizability model. Entropy effects are estimated from vibrational frequencies, calculated at the molecular mechanics level. We encounter several problems, not previously discussed, illustrating that we are first to apply such a method. For example, the PCM model is, in the present implementation, questionable for large molecules, owing to the use of a surface definition that gives numerous small cavities in a protein. PMID:26615702

  7. 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.

  8. 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.

  9. 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.

  10. Theoretical study of excitons in semiconductor quantum wires and related systems

    NASA Astrophysics Data System (ADS)

    Sidor, Yosyp

    The main goal of this thesis is a theoretical study of the excitonic properties in semiconductor quantum wires. Excitons dominate the optical properties of these one-dimensional structures, producing broad or sharp absorption and photoluminescence lines. The confinement of the electron and the hole is responsible for the properties of the exciton in a quantum wire. Confinement of the particles can be controlled through the size and shape of the quantum wire as well as through the selection of structure and barrier materials to produce various band offsets. The application of a magnetic field can give important information about the exciton confinement. Therefore, theoretical investigations of excitons in quantum wires is a strong theoretical tool to provide valuable information about quantum wire characteristics, as size uniformity, dimensions and photoluminescence spectrum. In the present thesis self-assembled InAs/InP and GaAs/AlGaAs V-shaped quantum wires are considered. The calculated photoluminescence transition energies in these structures are compared with available experimental data in order to deduce the dimensions of the wires. Both wires are investigated theoretically in the presence of an external magnetic field applied along different directions of the quantum wires. The computed exciton diamagnetic shift for both V-shaped and self-assembled quantum wires are reported and a detailed comparison is obtained with available magneto-photoluminescence experimental data. Since strain is important for the formation of the self-assembled quantum wires, results on the influence of strain on the electron and hole confinement will also be presented. Further, exciton coupling in self-assembled InAs/InP coupled quantum wires is considered. The charge confinement in InAs/InP based quantum wells and self-assembled quantum wires is examined, where for the narrow quantum well a local circular width fluctuation is included in order to describe the localization of the exciton along the quantum well. Lastly the formation of negatively and positively charged excitons in self-assembled InAs/InP and GaAs/AIGaAs V-shaped quantum wires is discussed. Additionally, the magnetic field dependence of the excitonic states in unstrained GaAs/AlGaAs quantum dot is studied. Where possible a comparison is made with experimental data.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  16. Theoretical Method of Calculating Solvent Nonequilibrium Effect on Solute Movement

    NASA Astrophysics Data System (ADS)

    Hara, Ryohei; Yoshimori, Akira

    2015-12-01

    We formulate a theoretical method for studying the solvent particle dynamics around a moving solute, using time-dependent density functional theory. The theoretical method is applied to the insertion process of a large sphere into a cylindrical vessel immersed in solvent particles. For various velocities of the large sphere, we calculate the nonequilibrium spatial distribution of number density of solvent particles. We find a nonequilibrium effect on the distribution, which is characterized by the total number of solvent particles inside of the vessel. The number is 32.5% larger for a velocity of DS/2dS than for the equilibrium state, where, dS and DS are the diameter and diffusion coefficient of a solvent particle, respectively.

  17. 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.

  18. 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

  19. Calculating the social cost of illegal drugs: a theoretical approach.

    PubMed

    Diomidous, Marianna; Zimeras, Stelios; Mechili, Aggelos

    2013-01-01

    The use of illegal drugs generates a wide range of social harms depending on various ways, according to the policy definition of the problem. The challenge is the way to model the impact of illegal drugs use during a long time period considering the factors that affects the process. Based on these models, estimation could be measured and prediction could be achieved. The illegal drugs use might affect the economic and social structure of the public system leading to direct and effective decisions to overcome the problematic. For that reason, calculation of social cost related to the use of illegal could be introduced over time (t) as a proposed social measure to define the variability of social indicator on society. In this work, a theoretical approach for the calculation of social cost of illegal drugs is proposed and models over time are defined. PMID:23823436

  20. Using the Chebychev expansion in quantum transport calculations

    NASA Astrophysics Data System (ADS)

    Popescu, Bogdan; Rahman, Hasan; Kleinekathfer, Ulrich

    2015-04-01

    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.

  1. Using the Chebychev expansion in quantum transport calculations.

    PubMed

    Popescu, Bogdan; Rahman, Hasan; Kleinekathfer, 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. PMID:25903862

  2. 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.

  3. Theoretical investigation on the inclusion of TCDD with ?-cyclodextrin by performing QM calculations and MD simulations.

    PubMed

    Pan, Wenxiao; Zhang, Dongju; Zhan, Jinhua

    2011-09-15

    The rapid enrichment and detection of trace polychlorinated dibenzo-p-dioxins (PCDDs) and polychlorinated dibenzofurans (PCDFs) are currently challenging issues in the field of environmental science. In this paper, by performing quantum chemistry (QM) calculations and molecular dynamics (MD) simulations, we studied the inclusion complexation of 2,3,7,8-tetrachlorodibenzo-p-dioxin (TCDD), a representative PCDD molecule, with ?-cyclodextrin (?-CD), one of the widely used compounds in supramolecular chemistry. The calculated results reveal that the stable inclusion complex can be formed in both the gas phase and solvent, which proposes that ?-CD may serve as a potential substrate enriching TCDD. The calculated vibrational spectra indicate that the infrared (IR) and Raman spectroscopy may be suitable for the detection of ?-CD-modified TCDD. The present theoretical results may be informative to environmental scientists who are devoting themselves to developing effective methods for detection and treatment of POPs. PMID:21794979

  4. 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)

  5. Quantum mechanical calculation of the carbine valent zone

    NASA Astrophysics Data System (ADS)

    Baitinger, E. M.; Gagarin, S. G.

    1989-07-01

    Results of a quantum mechanical calculation of the valent states of carbine are presented. A comparison is performed with data from spectroscopic experiments studying the valent states of this modification of solid carbon.

  6. 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.

  7. 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 ? equal to a projector (every member of the ensemble is assigned the same projector, ?i=| ?i> < ?i|= ?i2, or the same wave function ? 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, ?>? 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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

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

    PubMed

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

    2015-02-25

    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. PMID:25305611

  15. 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.

  16. Quantum mechanical cluster calculations of critical scintillationprocesses

    SciTech Connect

    Derenzo, Stephen E.; Klintenberg, Mattias K.; Weber, Marvin J.

    2000-02-22

    This paper describes the use of commercial quantum chemistrycodes to simu-late several critical scintillation processes. The crystalis modeled as a cluster of typically 50 atoms embedded in an array oftypically 5,000 point charges designed to reproduce the electrostaticfield of the infinite crystal. The Schrodinger equation is solved for theground, ionized, and excited states of the system to determine the energyand electron wavefunction. Computational methods for the followingcritical processes are described: (1) the formation and diffusion ofrelaxed holes, (2) the formation of excitons, (3) the trapping ofelectrons and holes by activator atoms, (4) the excitation of activatoratoms, and (5) thermal quenching. Examples include hole diffusion in CsI,the exciton in CsI, the excited state of CsI:Tl, the energy barrier forthe diffusion of relaxed holes in CaF2 and PbF2, and prompt hole trappingby activator atoms in CaF2:Eu and CdS:Te leading to an ultra-fast (<50ps) scintillation risetime.

  17. 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.

  18. 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.

  19. 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.

  20. 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

  1. 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.

  2. Quantum photoelectrochemistry: Theoretical studies of organic adsorbates on metal oxide surfaces

    NASA Astrophysics Data System (ADS)

    Persson, Nils Petter

    Interactions between organic molecules and transition metal oxide surfaces have been investigated by means of quantum chemical calculations. The studies have been aimed at understanding electrode-adsorbate interactions in photoelectrochemical devices, such as dye-sensitized solar cells. Structural properties of the interface between metal oxide surfaces and organic adsorbates have been investigated for formic acid on a ZnO surface, and for bi-isonicotinic acid on TiO2 surfaces. Questions of surface-adsorbate binding, adsorbate- adsorbate interactions, surface relaxations, and sensitizer strain have been considered. Relevant to the solar cells is the finding that strong sensitizer- anchoring via carboxyl groups is compatible with moderate sensitizer deformations. Electronic effects have been studied for aromatic molecules adsorbed on TiO2 surfaces and nanocrystals. Electronic coupling strengths, substrate- induced changes to the adsorbate electronic structure, and mechanisms of electron injection are discussed. The calculations have been made with semiempirical, periodic Hartree-Fock, and density functional methods. Semiempirical parameters are presented for systems containing both organic molecules and transition metal oxide surfaces. Much of the theoretical work has been successfully combined with data from XPS and XAS experiments. More generally, this thesis demonstrates the capability of quantum chemical calculations to address important questions regarding molecular properties of sensitized metal oxide electrodes, and the prospects of such quantum photoelectrochemistry is discussed.

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

    PubMed

    Karandashev, Konstantin; Van?ek, Ji?

    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 ?H? + H?H? ? H?H? + ? H? 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

  4. Accelerating quantum instanton calculations of the kinetic isotope effects

    NASA Astrophysics Data System (ADS)

    Karandashev, Konstantin; Van?ek, Ji?

    2015-11-01

    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 ?H? + H?H? ? H?H? + ? H? reaction as an example, we apply the proposed method to obtain several kinetic isotope effects on CH4 + ? H ? ? CH3 + H2 forward and backward reactions.

  5. Spatially resolved photoluminescence in quantum wells with interface roughness: a theoretical description

    NASA Astrophysics Data System (ADS)

    Martino, G.; Pistone, G.; Savasta, S.; Di Stefano, O.; Girlanda, R.

    2006-03-01

    We present a microscopic theoretical description of spatially resolved photoluminescence in GaAs quantum wells with interface roughness. The theory derives the kinetic equations using the excitonic wavefunctions obtained by solving numerically the effective Schrdinger equation for the excitonic centre of mass motion in the presence of disorder. The kinetic equations describe acoustic phonon scattering, radiative decay, and inhomogeneous sample excitation and/or light detection. The influence of disorder, temperature, and spatial resolution on the image formation is analysed with emphasis on the role of different interface textures. In particular, we consider two samples characterized by effective disorder potentials with different correlation lengths. Numerically calculated two-dimensional images agree with images from spatially resolved photoluminescence experiments and put forward the potential of the method for the understanding of near-field light emission from semiconductor quantum structures.

  6. 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 Schrdinger 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).

  7. 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.

  8. 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)(?) distribution and PL decay of QD Au@SiO2-5 nm, additional blinking traces and g(2)(?) 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

  9. 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 Bttiker 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

  10. Knitting algorithm for calculating Green functions in quantum systems

    NASA Astrophysics Data System (ADS)

    Kazymyrenko, K.; Waintal, X.

    2008-03-01

    We propose a fast and versatile algorithm to calculate local and transport properties such as conductance, shot noise, local density of state, and local currents in mesoscopic quantum systems. Within the nonequilibrium Green function formalism, we generalize the recursive Green function technique to tackle multiterminal devices with arbitrary geometries. We apply our method to analyze two recent experiments: an electronic Mach Zehnder interferometer in a two-dimensional gas and a Hall bar made of graphene nanoribbons in a quantum Hall regime. In the latter case, we find that the Landau edge state pinned to the Dirac point gets diluted upon increasing carrier density.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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 ?* transition, and the stronger absorption in the E belt of benzene electronic transition from ? to ?*. There are blue shift for DOP end absorption belt from n to ?* transition and red shift for DOP E absorption belt from ? to ?* transition relative to that of DBP. This calculation results are better in accord with the spectral data measured by UNICO ultraviolet and visible spectrophotometer.

  17. 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

  18. On kaonic hydrogen. Phenomenological quantum field theoretic model revisited

    NASA Astrophysics Data System (ADS)

    Ivanov, A. N.; Cargnelli, M.; Faber, M.; Fuhrmann, H.; Ivanova, V. A.; Marton, J.; Troitskaya, N. I.; Zmeskal, J.

    2005-09-01

    We argue that due to isospin and U-spin invariance of strong low-energy interactions the S-wave scattering lengths a 0 0 and a 1 0 of N scattering with isospin I = 0 and I = 1 satisfy the low-energy theorem a 0 0 +3a 1 0 = 0 valid to leading order in chiral expansion. In the model of strong low-energy N interactions at threshold (Eur. Phys. J. A 21, 11 (2004)) we revisit the contribution of the ?(1750) resonance, which does not saturate the low-energy theorem a 0 0 +3a 1 0 = 0, and replace it by the baryon background with properties of an SU(3) octet. We calculate the S-wave scattering amplitudes of K-N and K-d scattering at threshold. We calculate the energy level displacements of the ground states of kaonic hydrogen and deuterium. The result obtained for kaonic hydrogen agrees well with recent experimental data by the DEAR Collaboration. We analyse the cross-sections for elastic and inelastic K-p scattering for laboratory momenta 70MeV/c < p K < 150MeV/c of the incident K--meson. The theoretical results agree with the available experimental data within two standard deviations.

  19. The numerical calculation of quantum field theory in hadron spectroscopy

    NASA Astrophysics Data System (ADS)

    Sun, M. Z.; Cao, Y.; Hu, B. T.; Zhang, Y.; Chen, X. R.

    2014-04-01

    In this paper, we introduced QFT++, a C++ toolkit for numerical calculation of quantum field theory. By comparing the result from QFT++ with the traditional calculation result of the Feynman amplitude p\\bar {p} -> m? , the validity of QFT++ was demonstrated. Furthermore, the toolkit was optimized in a fixed convention, in which a significant improvement of performance was found. The optimized version will be used in the partial wave analysis (PWA) of hadron spectroscopy, where the computation speed is a crucial bottleneck in most cases.

  20. 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

  1. Theoretical calculation of zero field splitting parameters of Cr3+ doped ammonium oxalate monohydrate

    NASA Astrophysics Data System (ADS)

    Kripal, Ram; Yadav, Awadhesh Kumar

    2015-06-01

    Zero field splitting parameters (ZFSPs) D and E of Cr3+ ion doped ammonium oxalate monohydrate (AOM) are calculated with formula using the superposition model. The theoretically calculated ZFSPs for Cr3+ in AOM crystal are compared with the experimental value obtained by electron paramagnetic resonance (EPR). Theoretical ZFSPs are in good agreement with the experimental ones. The energy band positions of optical absorption spectra of Cr3+ in AOM crystal calculated with CFA package are in good match with the experimental values.

  2. 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

  3. 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…

  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. Calculation of hyperfine interaction in spherical quantum dot

    NASA Astrophysics Data System (ADS)

    Yakar, Yusuf; ak?r, Bekir; zmen, Ayhan

    2015-10-01

    In this study, we have calculated the unperturbed wavefunctions and energy eigenvalues of the ground and excited states of a spherical quantum dot, GaAs/AlxGa1-xAs, by using quantum genetic algorithm and Hartree-Fock Roothaan method. Hyperfine coupling constant and hyperfine energy of 1s, 2p, 3d and 4f levels are carried out as a function of dot radius. The results show that the hyperfine constant and hyperfine energy varies rapidly in the strong and medium confining regions as dot radius decreases. It is worth pointing out that dot radius, impurity charge and angular momentum have a strong influence on the hyperfine energy. It is also found that hyperfine energy and hyperfine splitting vary with aluminium concentration ratio x.

  6. Calculation of the partition function using quantum genetic algorithms

    NASA Astrophysics Data System (ADS)

    Grigorenko, I.; Garcia, M. E.

    2002-10-01

    We present a new method based on genetic algorithms which permits to determine efficiently the partition function and the excitation spectrum of few-body quantum systems. In our approach, we use a variational formulation for the partition function Z of the system as a functional of its eigenfunctions. Z is obtained by applying the procedure of survival of the fittest, starting from initial random population. During the evolution the best representative converges to a set of eigenfunctions for a given Hamiltonian, while the partition function attains its global extremum (maximum) for a given temperature. We calculate the spectrum and the partition function in the case of few interacting particles in one-dimensional infinite potential well. We investigate formation of the Wigner crystal and study its melting induced by termal and quantum fluctuations.

  7. 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.

  8. Ab initio quantum transport calculations using plane waves

    NASA Astrophysics Data System (ADS)

    Garcia-Lekue, A.; Vergniory, M. G.; Jiang, X. W.; Wang, L. W.

    2015-08-01

    We present an ab initio method to calculate elastic quantum transport at the nanoscale. The method is based on a combination of density functional theory using plane wave nonlocal pseudopotentials and the use of auxiliary periodic boundary conditions to obtain the scattering states. The method can be applied to any applied bias voltage and the charge density and potential profile can either be calculated self-consistently, or using an approximated self-consistent field (SCF) approach. Based on the scattering states one can straightforwardly calculate the transmission coefficients and the corresponding electronic current. The overall scheme allows us to obtain accurate and numerically stable solutions for the elastic transport, with a computational time similar to that of a ground state calculation. This method is particularly suitable for calculations of tunneling currents through vacuum, that some of the nonequilibrium Greens function (NEGF) approaches based on atomic basis sets might have difficulty to deal with. Several examples are provided using this method from electron tunneling, to molecular electronics, to electronic devices: (i) On a Au nanojunction, the tunneling current dependence on the electrode-electrode distance is investigated. (ii) The tunneling through field emission resonances (FERs) is studied via an accurate description of the surface vacuum states. (iii) Based on quantum transport calculations, we have designed a molecular conformational switch, which can turn on and off a molecular junction by applying a perpendicular electric field. (iv) Finally, we have used the method to simulate tunnel field-effect transistors (TFETs) based on two-dimensional transition-metal dichalcogenides (TMDCs), where we have studied the performance and scaling limits of such nanodevices and proposed atomic doping to enhance the transistor performance.

  9. 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?. 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.

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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

  15. 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.

  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. Theoretical description of quantum effects in multi-chromophoric aggregates.

    PubMed

    Zimanyi, Eric N; Silbey, Robert J

    2012-08-13

    Recent experiments on light-harvesting complexes have shown clear indication of coherent transport of excitations in these aggregates. We discuss the theoretical models that have been used to study energy transfer in molecular aggregates, beginning with the early models of Frster and Davydov and ending with the theoretical models of the present day. PMID:22753817

  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. Biological applications of hybrid quantum mechanics/molecular mechanics calculation.

    PubMed

    Kang, Jiyoung; Hagiwara, Yohsuke; Tateno, Masaru

    2012-01-01

    Since in most cases biological macromolecular systems including solvent water molecules are remarkably large, the computational costs of performing ab initio calculations for the entire structures are prohibitive. Accordingly, QM calculations that are jointed with MM calculations are crucial to evaluate the long-range electrostatic interactions, which significantly affect the electronic structures of biological macromolecules. A UNIX-shell-based interface program connecting the quantum mechanics (QMs) and molecular mechanics (MMs) calculation engines, GAMESS and AMBER, was developed in our lab. The system was applied to a metalloenzyme, azurin, and PU.1-DNA complex; thereby, the significance of the environmental effects on the electronic structures of the site of interest was elucidated. Subsequently, hybrid QM/MM molecular dynamics (MD) simulation using the calculation system was employed for investigation of mechanisms of hydrolysis (editing reaction) in leucyl-tRNA synthetase complexed with the misaminoacylated tRNA(Leu), and a novel mechanism of the enzymatic reaction was revealed. Thus, our interface program can play a critical role as a powerful tool for state-of-the-art sophisticated hybrid ab initio QM/MM MD simulations of large systems, such as biological macromolecules. PMID:22536015

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

    SciTech Connect

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

    2010-03-15

    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 a 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.

  1. 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

  2. Quantum states of confined hydrogen plasma species: Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Micca Longo, G.; Longo, S.; Giordano, D.

    2015-12-01

    The diffusion Monte Carlo method with symmetry-based state selection is used to calculate the quantum energy states of \\text{H}2+ confined into potential barriers of atomic dimensions (a model for these ions in solids). Special solutions are employed, permitting one to obtain satisfactory results with rather simple native code. As a test case, {{}2}{{\\Pi}u} and {{}2}{{\\Pi}g} states of \\text{H}2+ ions under spherical confinement are considered. The results are interpreted using the correlation of \\text{H}2+ states to atomic orbitals of H atoms lying on the confining surface and perturbation calculations. The method is straightforwardly applied to cavities of any shape and different hydrogen plasma species (at least one-electron ones, including H) for future studies with real crystal symmetries.

  3. 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.

  4. Theoretical discussion for quantum computation in biological systems

    NASA Astrophysics Data System (ADS)

    Baer, Wolfgang

    2010-04-01

    Analysis of the brain as a physical system, that has the capacity of generating a display of every day observed experiences and contains some knowledge of the physical reality which stimulates those experiences, suggests the brain executes a self-measurement process described by quantum theory. Assuming physical reality is a universe of interacting self-measurement loops, we present a model of space as a field of cells executing such self-measurement activities. Empty space is the observable associated with the measurement of this field when the mass and charge density defining the material aspect of the cells satisfy the least action principle. Content is the observable associated with the measurement of the quantum wave function ? interpreted as mass-charge displacements. The illusion of space and its content incorporated into cognitive biological systems is evidence of self-measurement activity that can be associated with quantum operations.

  5. 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

  6. 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.

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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...

  12. 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

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

    PubMed Central

    Strmpfer, 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 PHIs 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

  14. Linkages between the calculable and the incalculable in quantum theory

    SciTech Connect

    Madjid, F.H.; Myers, J.M. )

    1993-02-01

    Seemingly disparate phenomena-e.g., the optimal reception of light signals, experimental designs to rule out hidden-parameter theories, and the triggering that is essential to the demonstration of wave-particle duality-involve a common but previously overlooked thread. The common thread is a quantum field that defines several measurement steps, leading to several spatio-temporally distinct outcomes. In the case of light reception, this operator field has values at later spacetime points influenced by incalculable outcomes at earlier spacetime points; these outcomes are outcomes of measurement steps defined by values of the field itself at earlier spacetime points. This field, called a linkage field, is defined carefully to show the coupling between random, incalculable outcomes, on the one hand, and the propagation of calculable field values on the other. We inquire into the necessity of this field for optimal measurements. Assumptions implicit in quantum decision theory are stated, pertaining to: (1) the expression of possibilities by random variables, and (2) the locating of outcomes of measurements. A proposition is stated and proved that such a randomly influenced linkage field is necessary to the optimal measurement of binary coherent light signals. Other examples of linkage fields and their applications are discussed briefly.

  15. 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.

  16. Exact Quantum Dynamics Calculations Using Phase Space Wavelets

    NASA Astrophysics Data System (ADS)

    Halverson, Thomas; Poirier, Bill

    2013-06-01

    In a series of earlier papers, the authors introduced the first exact quantum dynamics method that defeats the exponential scaling of CPU effort with system dimensionality. The method used a ``weylet'' basis set (orthogonalized Weyl-Heisenberg wavelets), combined with a phase space truncation scheme first proposed by M. Davis and E. Heller. Here, we use a related, but much simpler, wavelet basis consisting of momentum-symmetrized phase space Gaussians. Despite being non-orthogonal, symmetrized Gaussians exhibit collective locality, allowing for effective phase space truncation and the defeat of exponential scaling. A ``universal'' and remarkably simple code has been written, which is dimensionally independent, and which also exploits massively parallel algorithms. The codes have been used to calculate the vibrational spectra of several molecules of varying dimensionality.

  17. QTAIM Analysis in the Context of Quasirelativistic Quantum Calculations.

    PubMed

    Pilm, Julien; Renault, Eric; Bassal, Fadel; Amaouch, Mohamed; Montavon, Gilles; Galland, Nicolas

    2014-11-11

    Computational chemistry currently lacks ad hoc tools for probing the nature of chemical bonds in heavy and superheavy-atom systems where the consideration of spin-orbit coupling (SOC) effects is mandatory. We report an implementation of the Quantum Theory of Atoms-In-Molecules in the framework of two-component relativistic calculations. Used in conjunction with the topological analysis of the Electron Localization Function, we show for astatine (At) species that SOC significantly lowers At electronegativity and boosts its propensity to make charge-shift bonds. Relativistic spin-dependent effects are furthermore able to change some bonds from mainly covalent to charge-shift type. The implication of the disclosed features regarding the rationalization of the labeling protocols used in nuclear medicine for (211)At radioisotope nicely illustrates the potential of the introduced methodology for investigating the chemistry of (super)heavy elements. PMID:26584370

  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. 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.

  20. 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.

  1. [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

  2. 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.

  3. 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.

  4. 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.

  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. Quantum Monte Carlo calculations of nuclei with A<=7

    NASA Astrophysics Data System (ADS)

    Pudliner, B. S.; Pandharipande, V. R.; Carlson, J.; Pieper, Steven C.; Wiringa, R. B.

    1997-10-01

    We report quantum Monte Carlo calculations of ground and low-lying excited states for nuclei with A<=7 using a realistic Hamiltonian containing the Argonne v18 two-nucleon and Urbana IX three-nucleon potentials. A detailed description of the Green's-function Monte Carlo algorithm for systems with state-dependent potentials is given and a number of tests of its convergence and accuracy are performed. We find that the Hamiltonian being used results in ground states of both 6Li and 7Li that are stable against breakup into subclusters, but somewhat underbound compared to experiment. We also have results for 6He, 7He, and their isobaric analogs. The known excitation spectra of all these nuclei are reproduced reasonably well and we predict a number of excited states in 6He and 7He. We also present spin-polarized one-body and several different two-body density distributions. These are the first microscopic calculations that directly produce nuclear shell structure from realistic interactions that fit NN scattering data.

  9. Efficient entanglement channel construction schemes for a theoretical quantum network model with d-level system

    NASA Astrophysics Data System (ADS)

    Wang, Ming-Ming; Chen, Xiu-Bo; Luo, Shou-Shan; Yang, Yi-Xian

    2012-12-01

    Quantum entanglement plays an essential role in the field of quantum information and quantum computation. In quantum network, a general assumption for many quantum tasks is that the quantum entanglement has been prior shared among participants. Actually, the distribution of entanglement becomes complex in the network environment. We present a theoretical quantum network model with good scalability. Then, three efficient and perfect schemes for the entanglement channel construction are proposed. Some general results for d-level system are also given. Any two communication sites can construct an entanglement channel via Bell states with the assistance of the intermediate sites on their quantum chain. By using the established entanglement channel, n sites can efficiently and perfectly construct an entanglement channel via an n-qudit cat state. More importantly, an entanglement channel via an arbitrary n-qudit state can also be constructed among any n sites, or even among any t sites where 1 ? t ? n. The constructed multiparticle entanglement channels have many useful applications in quantum network environment.

  10. 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.

  11. Theoretical calculations of the 2B 1- 2A 1 subband of NO 2

    NASA Astrophysics Data System (ADS)

    Zhao, X. Z.; Lu, T. X.; Cui, Z. F.

    1989-06-01

    The vibronic levels of the 2B 1( K' = 0) state of NO 2 and the fluorescence intensity distribution from these levels is calculated in this Letter using the Rennet-Teller theory. The vibronic quantum number of the upper level of the 454.5 nm subband is found to be ?' 2 = 17, and the band origin and the fluorescence distribution agree with experimental data.

  12. 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.

  13. Microcomputer Calculation of Theoretical Pre-Exponential Factors for Bimolecular Reactions.

    ERIC Educational Resources Information Center

    Venugopalan, Mundiyath

    1991-01-01

    Described is the application of microcomputers to predict reaction rates based on theoretical atomic and molecular properties taught in undergraduate physical chemistry. Listed is the BASIC program which computes the partition functions for any specific bimolecular reactants. These functions are then used to calculate the pre-exponential factor of

  14. 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...

  15. NMR quantum computing: applying theoretical methods to designing enhanced systems.

    PubMed

    Mawhinney, Robert C; Schreckenbach, Georg

    2004-10-01

    Density functional theory results for chemical shifts and spin-spin coupling constants are presented for compounds currently used in NMR quantum computing experiments. Specific design criteria were examined and numerical guidelines were assessed. Using a field strength of 7.0 T, protons require a coupling constant of 4 Hz with a chemical shift separation of 0.3 ppm, whereas carbon needs a coupling constant of 25 Hz for a chemical shift difference of 10 ppm, based on the minimal coupling approximation. Using these guidelines, it was determined that 2,3-dibromothiophene is limited to only two qubits; the three qubit system bromotrifluoroethene could be expanded to five qubits and the three qubit system 2,3-dibromopropanoic acid could also be used as a six qubit system. An examination of substituent effects showed that judiciously choosing specific groups could increase the number of available qubits by removing rotational degeneracies in addition to introducing specific conformational preferences that could increase (or decrease) the magnitude of the couplings. The introduction of one site of unsaturation can lead to a marked improvement in spectroscopic properties, even increasing the number of active nuclei. PMID:15366045

  16. 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.

  17. 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.

  18. 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).

  19. 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 Mller-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 Mller-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.

  20. Quantum Monte Carlo Calculations of Excitations in Hydrogenated Germanium Clusters

    NASA Astrophysics Data System (ADS)

    Vincent, Jordan; Kim, Jeongnim; Martin, Richard

    2006-03-01

    Quantum Monte Carlo (QMC) calculations are presented for energies of ground and excited states of Ge atom and hydrogen passivated closed-shell molecules and clusters: GeH4, Ge2H6, Ge5H12, Ge10H16 and Ge29H36. We compare the results for excitations with previous QMC and time-dependant Density Functional Theory (TD- DFT) done for the corresponding Silicon clusters [1,2]; in particular; we find that preliminary results for lowest excitation enregy of Ge29H36 5.08[29]eV is lower than the gap 5.4eV reported for Si[2]. Core-valence partitioning for Ge is implemented by replacing the core-states with a Hartree-Fock pseudopotential plus a Core Polarization Potential (CPP)[3]. Core-valence correlation treated by the CPP is shown to be essential for accurate atomic energies and significant for the molecules, but smaller in the clusters. [1] Porter et. al., PRB 64, 035320 (2001). [2] Williamson et. al., PRL 89, 196803 (2002). [3] Shirley and Martin, PRB 47, 15413 (1993)

  1. 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.

  2. 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.

  3. 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.

  4. Superhalogen properties of BS2(-) and BSO(-): photoelectron spectroscopy and theoretical calculations.

    PubMed

    Zhao, Li-Juan; Xu, Hong-Guang; Feng, Gang; Wang, Peng; Xu, Xi-Ling; Zheng, Wei-Jun

    2016-02-17

    We investigate BS2(-) and BSO(-) clusters using photoelectron spectroscopy and theoretical calculations. The electron affinities of BS2 and BSO are measured to be 3.80 0.03 and 3.88 0.03 eV, respectively, higher than those of halogen atoms. Thus, BS2 and BSO can be considered as superhalogens. The comparison of experimental and theoretical results confirmed that the ground state structures of BS2(-), BSO(-), and their neutrals are all linear. Analyses of natural bond orbitals suggest that both BS2(-) and BSO(-) have dual 3c-4e ? hyperbonds. PMID:26847710

  5. The calculation of theoretical chromospheric models and predicted OSO 1 spectra

    NASA Technical Reports Server (NTRS)

    Avrett, E. H.

    1975-01-01

    Theoretical solar chromospheric and photospheric models are computed for use in analyzing OSO 8 spectra. The Vernazza, Avrett, and Loeser (1976) solar model is updated and self-consistent non-LTE number densities for H I, He I, He II, C I, Mg I, Al I, Si I, and H(-) are produced. These number densities are used in the calculation of a theoretical solar spectrum from 90 to 250 nm, including approximately 7000 lines in non-LTE. More than 60,000 lines of other elements are treated with approximate source functions.

  6. Rotational isomerism of some chloroacetamides: Theoretical and experimental studies through calculations, infrared and NMR

    NASA Astrophysics Data System (ADS)

    Santos, Marcela F.; Braga, Carolyne B.; Rozada, Thiago C.; Basso, Ernani A.; Fiorin, Barbara C.

    2014-08-01

    The geometries involved in the conformational equilibria of 2,2-dichloro-N-cyclohexyl-N-methyl-acetamide (DCCMA) and 2-chloro-N,N-dicyclohexylacetamide (CDCA) were investigated. Theoretical calculations at the B3LYP/cc-pVDZ level of theory showed that gauche forms (Clsbnd Csbnd Cdbnd O) are the most stable and the predominant conformers in isolated phase. Both compounds had the conformational behavior in solvents of different polarities estimated from theoretical calculations with the PCM (Polarizable Continuum Model), at the same level of theory, using infrared data from deconvolution of the carbonyl absorption bands and 13C NMR spectra. Their IR spectra showed two carbonyl absorptions and that the conformer with the highest dipole moment had its population increased when the most polar solvents were used, in accordance with the theoretical calculation in solution. 1JCH coupling constants were obtained from their NMR spectra, and revealed that there was population variation of conformers with solvent exchange. Experimental data (NMR and IR) as well as calculations including the solvent effects followed the same trend.

  7. 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.

  8. Energy from CO2 using capacitive electrodes--theoretical outline and calculation of open circuit voltage.

    PubMed

    Paz-Garcia, J M; Schaetzle, O; Biesheuvel, P M; Hamelers, H V M

    2014-03-15

    Recently, a new technology has been proposed for the utilization of energy from CO2 emissions (Hamelers et al., 2014). The principle consists of controlling the dilution process of CO2-concentrated gas (e.g., exhaust gas) into CO2-dilute gas (e.g., air) thereby extracting a fraction of the released mixing energy. In this paper, we describe the theoretical fundamentals of this technology when using a pair of charge-selective capacitive electrodes. We focus on the behavior of the chemical system consisting of CO2 gas dissolved in water or monoethanolamine solution. The maximum voltage given for the capacitive cell is theoretically calculated, based on the membrane potential. The different aspects that affect this theoretical maximum value are discussed. PMID:24461836

  9. 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

  10. 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.

  11. 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.; Wry, 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.

  12. 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.

  13. 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.

  14. 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.

  15. An analysis of states in the phase space: a possible approach to calculate the energy of quantum systems

    NASA Astrophysics Data System (ADS)

    Tosto, Sebastiano

    1997-04-01

    The presentation aims to show the basic features of an "ab initio" approach to calculate the energy levels of quantum systems. The purpose of the model is not to furtherly increase the accuracy of some already existing computational method or to develop a new mathematical algorithm but rather to examine the consequences of introducing since the beginning the quantum uncertainty in the energy equations of atoms and molecules. Without any hypothesis on the state of motion of the electrons but merely concerning the number of states allowed in the phase space as a function of momentum and space uncertainty ranges, one obtains simple formulae enabling to calculate the enegy levels of multielectron atoms in a good agreement with the experimental data. The same theoretical approach has been also utilized to describe the diatomic molecules in terms of anharmonic oscillators. Also in this case, simple formulae enable to correlate dissociation energy, vibrational frequency and bond length in a good agreement with the experimental data

  16. 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.

  17. 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

  18. Quantum scattering calculations on the NH3+OH --> NH2+H2O reaction

    NASA Astrophysics Data System (ADS)

    Nyman, Gunnar

    1996-04-01

    Quantum scattering calculations on the NH3+OH?NH2+H2O reaction have been performed at energies up to 0.8 eV. The rotating bond approximation is used, treating NH2 as a pseudoatom. The OH rotation and a reactive N-H stretch of NH3 are treated explicitly as well as the bending motion and one OH local stretch vibration of H2O. A reduced dimensionality potential energy surface is developed. It has accurate reactant and product rovibrational energy levels for the modes explicitly treated in the scattering calculations and incorporates the zero point energy of the other modes. Quantized transition states gating the flux are found and mode selectivity is observed. Reactants in their ground rovibrational states produce mainly ground state H2O and vibrationally excited NH3 produces mainly vibrationally excited H2O. Rate constants are obtained using an adiabatic approach to account for all degrees of freedom not explicitly treated in the scattering calculations. Tunneling makes a dominant contribution to the rate constants, which are in reasonable agreement with previous theoretical and experimental work.

  19. Quantum scattering calculations on the CH4+OH --> CH3+H2O reaction

    NASA Astrophysics Data System (ADS)

    Nyman, Gunnar; Clary, David C.

    1994-10-01

    Quantum scattering calculations on the CH4+OH?CH3+H2O reaction have been performed at thermal energies. The rotating bond approximation is used, treating CH3 as a pseudoatom. The OH rotation and a reactive C-H stretch of CH4 are treated explicitly as well as the bending motion and one OH local stretch vibration of H2O. Two potential energy surfaces are used. Both have accurate reactant and product rovibrational energy levels for the modes explicitly treated in the scattering calculations and incorporate the zero point energy of the other modes. They have correct bond dissociation energies and transition state geometries in reasonable accord with ab initio data. Mode selectivity is found: reactants in the ground rovibrational states produce ground state H2O, and vibrationally excited CH4 produces vibrationally excited H2O. Reactant OH rotational excitation decreases the reaction cross sections. Rate constants are obtained using an adiabatic approach to account for all degrees of freedom not explicitly treated in the scattering calculations. Large contributions due to tunneling are observed. The rate constants are in quite good agreement with previous theoretical and experimental work.

  20. 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 HCO 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 HCO collisions in astrophysical models.

  1. 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.

  2. 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.

  3. 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

  4. 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 DPA2H 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.

  5. 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

  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.

    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.

  7. 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.

  8. 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.

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

    NASA Astrophysics Data System (ADS)

    Aly, Abou El-Maaty M.; Nasr, A.

    2014-03-01

    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 Schrdinger 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.

  10. 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.

  11. 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.

  12. 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

  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. 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

  15. 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.

  16. 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+1? 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 ?e, 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.

  17. A perspective on quantum mechanics calculations in ADMET predictions.

    PubMed

    Bowen, J Phillip; Gner, Osman F

    2013-01-01

    Understanding the molecular basis of drug action has been an important objective for pharmaceutical scientists. With the increasing speed of computers and the implementation of quantum chemistry methodologies, pharmacodynamic and pharmacokinetic problems have become more computationally tractable. Historically the former has been the focus of drug design, but within the last two decades efforts to understand the latter have increased. It takes about fifteen years and over $1 billion dollars for a drug to go from laboratory hit, through lead optimization, to final approval by the U.S. Food and Drug Administration. While the costs have increased substantially, the overall clinical success rate for a compound to emerge from clinical trials is approximately 10%. Most of the attrition rate can be traced to ADMET (absorption, distribution, metabolism, excretion, and toxicity) problems, which is a powerful impetus to study these issues at an earlier stage in drug discovery. Quantum mechanics offers pharmaceutical scientists the opportunity to investigate pharmacokinetic problems at the molecular level prior to laboratory preparation and testing. This review will provide a perspective on the use of quantum mechanics or a combination of quantum mechanics coupled with other classical methods in the pharmacokinetic phase of drug discovery. A brief overview of the essential features of theory will be discussed, and a few carefully selected examples will be given to highlight the computational methods. PMID:23675934

  18. 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

  19. 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

  20. 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.

  1. Conformational analysis of morpholine studied using Raman spectroscopy and density functional theoretical calculations

    NASA Astrophysics Data System (ADS)

    SenGupta, Sumana; Maiti, Nandita; Chadha, Ridhima; Kapoor, Sudhir

    2015-10-01

    Morpholine is a very interesting cyclic compound which is an ether as well as a secondary amine. The relative distribution of different conformations of morpholine depends on the medium. Using Raman spectroscopy and theoretical calculations, we found that, equatorial chair conformer is predominant in the pure liquid, but in aqueous solution, contribution from the axial conformer increases. The surface-enhanced Raman scattering (SERS) studies in presence of silver nanoparticles showed change in relative intensities of different vibrational modes of morpholine. It was found that the axial chair conformer is preferentially adsorbed vertically through the Nsbnd Ag bond on the nanoparticle surface.

  2. The dynamics simulation and quantum calculation investigation about luminescence mechanism of coelenteramide.

    PubMed

    Li, Zuo-Sheng; Zhao, Xi; Zou, Lu-Yi; Ren, Ai-Min

    2013-01-01

    The dynamics simulation and quantum chemical calculation are employed to investigate spectrum properties of deprotonation process of coelenteramide and two final states neutral state and phenolate anion. According to the calculation results, theoretical evidence supporting the luminescence mechanism hypothesis is proposed in a significant bioluminescence process. In vivo of marine bioluminescent organisms, if the protein motion provides the conditions for the deprotonation of coelenteramide in some protein molecules, the phenolate anion is completely deprotonated coelenteramide as an emitter in these protein molecules and emits fluorescence assigned to the lower energy peak. And in another emitter in which the condition of deprotonation is not met, the fluorescence is produced by the neutral state of coelenteramide and assigned to the higher energy peak. The energy difference decreases gradually when the proton of coelenteramide gradually approaches to His22. For phenolate anion and neutral state, electronic cloud distributions between their each frontier molecular orbitals HOMO and LUMO have high overlapping volume. The molecular electrostatic potential indicates that for phenolate anion, the oxygen atom after deprotonation has greater electron density, which is good for formation hydrogen bonds with amino acids in the environment. PMID:23495829

  3. 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.

  4. Epithermal effects in muon-catalyzed [ital dt] fusion: Comparison of experimental data with theoretical calculations

    SciTech Connect

    Jeitler, M.; Breunlich, W.H.; Cargnelli, M.; Kammel, P.; Marton, J.; Naegele, N.; Pawlek, P.; Scrinzi, A.; Werner, J.; Zmeskal, J. ); Bossy, H.; Daniel, H.; Hartmann, F.J.; Schmidt, G.; von Egidy, T. ); Petitjean, C. ); Bistirlich, J.; Crowe, K.M.; Justice, M.; Kurck, J. ); Sherman, R.H. ); Neumann, W. ); Faifman, M.P. )

    1995-04-01

    Epithermal effects in muonic molecular formation were observed during experiments in a low-density deuterium-tritium gas target carried out at the Paul Scherrer Institute. The high molecular formation rate of epithermal'' (not yet thermalized) muonic tritium atoms was reflected by a strong fast component in the fusion neutron time spectra followed by a smaller steady-state'' component where molecular formation occurs mostly from thermalized ( cold'') [ital t][mu] atoms. Further experimental evidence for high epithermal [ital dt][mu] molecular formation rates has been derived from measurements in triple H-D-T mixtures. First, theoretical calculations predicted strong resonances at high [ital t][mu] kinetic energies and showed qualitative agreement with the observed experimental data, but yielded molecular formation rates that differed substantially from the observed values. At present, refined calculations are being carried out which may improve the agreement with experiment. Further experiments are being planned to clarify open questions.

  5. 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

  6. 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.

  7. 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.

  8. Theoretical Calculations of Structure and Exchange Coupling of a Room-Temperature Molecular Magnet

    NASA Astrophysics Data System (ADS)

    Cimpoesu, Fanica; Frecu?, Bogdan; Oprea, Corneliu I.; Gr?u, Minai A.

    2010-01-01

    We report here quantum chemical calculations advancing structural hypotheses and corresponding methodological concerns devoted to the elucidation of magneto-structural features of the V[TCNE]2 molecular magnet (TCNE = tetracyanoethylene). V[TCNE]xy(CH2Cl2) is the first room-temperature molecular magnet discovered and the only one with an active organic component. Despite previous detailed magnetic, spectroscopic and conductivity studies, the mechanism for the strong exchange coupling in the family M[TCNE]xy(solvent) has remained an open question, the difficulty being related to the absence of structural data for these amorphous compounds. Starting from a structural model that we propose, we report the results of Density Functional Theory (DFT) calculations providing the optimized geometry of a periodic lattice. The DFT methods retrieve the long range magnetic ordering of the system, but overestimate the absolute values of exchange constants. We analyze the DFT results assessing the intrinsic limitations in the systematic account of the Broken Symmetry regime and long range effects. In this respect, Gaussian-type and Plane Wave calculations were corroborated, finding comparable results. We suggest and preliminarily checked improved treatments realized by multi-configuration ab initio methods, providing better estimates of the exchange constants.

  9. 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.

  10. 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.

  11. 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 ?g/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.

  12. 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.

  13. 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.

  14. Quantum noise in the mirror-field system: A field theoretic approach

    SciTech Connect

    Hsiang, Jen-Tsung; Wu, Tai-Hung; Lee, Da-Shin; King, Sun-Kun; Wu, Chun-Hsien

    2013-02-15

    We revisit the quantum noise problem in the mirror-field system by a field-theoretic approach. Here a perfectly reflecting mirror is illuminated by a single-mode coherent state of the massless scalar field. The associated radiation pressure is described by a surface integral of the stress-tensor of the field. The read-out field is measured by a monopole detector, from which the effective distance between the detector and mirror can be obtained. In the slow-motion limit of the mirror, this field-theoretic approach allows to identify various sources of quantum noise that all in all leads to uncertainty of the read-out measurement. In addition to well-known sources from shot noise and radiation pressure fluctuations, a new source of noise is found from field fluctuations modified by the mirror's displacement. Correlation between different sources of noise can be established in the read-out measurement as the consequence of interference between the incident field and the field reflected off the mirror. In the case of negative correlation, we found that the uncertainty can be lowered than the value predicted by the standard quantum limit. Since the particle-number approach is often used in quantum optics, we compared results obtained by both approaches and examine its validity. We also derive a Langevin equation that describes the stochastic dynamics of the mirror. The underlying fluctuation-dissipation relation is briefly mentioned. Finally we discuss the backreaction induced by the radiation pressure. It will alter the mean displacement of the mirror, but we argue this backreaction can be ignored for a slowly moving mirror. - Highlights: Black-Right-Pointing-Pointer The quantum noise problem in the mirror-field system is re-visited by a field-theoretic approach. Black-Right-Pointing-Pointer Other than the shot noise and radiation pressure noise, we show there are new sources of noise and correlation between them. Black-Right-Pointing-Pointer The noise correlations can be used to suppress the overall quantum noise on the mirror. Black-Right-Pointing-Pointer The equation of motion of the mirror is derived and the backreaction of the radiation field is discussed.

  15. 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.

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

    PubMed

    Garca-Granados, A; Melguizo, E; Parra, A; Sime, 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

  17. 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

  18. Conformations of silica-bound (pentafluorophenyl)propyl groups determined by solid-state NMR spectroscopy and theoretical calculations.

    PubMed

    Mao, Kanmi; Kobayashi, Takeshi; Wiench, Jerzy W; Chen, Hung-Ting; Tsai, Chih-Hsiang; Lin, Victor S-Y; Pruski, Marek

    2010-09-01

    The conformations of (pentafluorophenyl)propyl groups (-CH(2)-CH(2)-CH(2)-C(6)F(5), abbreviated as PFP), covalently bound to the surface of mesoporous silica nanoparticles (MSNs), were determined by solid-state NMR spectroscopy and further refined by theoretical modeling. Two types of PFP groups were described, including molecules in the prone position with the perfluorinated aromatic rings located above the siloxane bridges (PFP-p) and the PFP groups denoted as upright (PFP-u), whose aromatic rings do not interact with the silica surface. Two-dimensional (2D) (13)C-(1)H, (13)C-(19)F and (19)F-(29)Si heteronuclear correlation (HETCOR) spectra were obtained with high sensitivity on natural abundance samples using fast magic angle spinning (MAS), indirect detection of low-gamma nuclei and signal enhancement by Carr-Purcell-Meiboom-Gill (CPMG) spin-echo sequence. 2D double-quantum (DQ) (19)F MAS NMR spectra and spin-echo measurements provided additional information about the structure and mobility of the pentafluorophenyl rings. Optimization of the PFP geometry, as well as calculations of the interaction energies and (19)F chemical shifts, proved very useful in refining the structural features of PFP-p and PFP-u functional groups on the silica surface. The prospects of using the PFP-functionalized surface to modify its properties (e.g., the interaction with solvents, especially water) and design new types of the heterogeneous catalytic system are discussed. PMID:20707348

  19. 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.

  20. The implementation of ab initio quantum chemistry calculations on transporters.

    PubMed

    Cooper, M D; Hillier, I H

    1991-06-01

    The RHF and geometry optimization sections of the ab initio quantum chemistry code, GAMESS, have been optimized for a network of parallel microprocessors, Inmos T800-20 transputers, using both indirect and direct SCF techniques. The results indicate great scope for implementation of such codes on small parallel computer systems, very high efficiencies having been achieved, particularly in the cases of direct SCF and geometry optimization with large basis sets. The work, although performed upon one particular parallel system, the Meiko Computing Surface, is applicable to a wide range of parallel systems with both shared and distributed memory. PMID:1919615

  1. 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.

  2. 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.

  3. Black hole state counting in loop quantum gravity: a number-theoretical approach.

    PubMed

    Agull, Ivn; Barbero G, J Fernando; Daz-Polo, Jacobo; Fernndez-Borja, Enrique; Villaseor, Eduardo J S

    2008-05-30

    We give an efficient method, combining number-theoretic and combinatorial ideas, to exactly compute black hole entropy in the framework of loop quantum gravity. Along the way we provide a complete characterization of the relevant sector of the spectrum of the area operator, including degeneracies, and explicitly determine the number of solutions to the projection constraint. We use a computer implementation of the proposed algorithm to confirm and extend previous results on the detailed structure of the black hole degeneracy spectrum. PMID:18518596

  4. Theoretical calculations of a compound formed by Fe(+3) and tris(catechol).

    PubMed

    Kara, ?zzet; Kara, Ye?im; ztrk Kiraz, Asl?; Mammadov, Ramazan

    2015-10-01

    Phenolic compounds generally have special smell, easily soluble in water, organic solvents (alcohols, esters, chloroform, ethyl acetate), in aqueous solutions of bases, colorless or colorful, crystalline and amorphous materials. Phenols form colorful complexes when they form compounds with heavy metals. In this study, the structural properties of a compound formed by catechol and Fe(+3) are investigated theoretically. The electronic and thermodynamic properties of the complex were also investigated in gas phase and organic solvents at B3LYP/6-31+G(d,p) and B3LYP/6-311++G(d,p) basis set. The formation of Fe-tris(catechol) complex compound is exothermic, and it is difficult to obtain the complex as the temperature increases. The observed and calculated FT-IR and geometric parameters spectra are in good agreement with empirical. PMID:25983060

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. A 3-D Theoretical Model for Calculating Plasma Effects in Germanium Detectors

    NASA Astrophysics Data System (ADS)

    Wei, Wenzhao; Liu, Jing; Mei, Dongming; Cubed Collaboration

    2015-04-01

    In the detection of WIMP-induced nuclear recoil with Ge detectors, the main background source is the electron recoil produced by natural radioactivity. The capability of discriminating nuclear recoil (n) from electron recoil (?) is crucial to WIMP searches. Digital pulse shape analysis is an encouraging approach to the discrimination of nuclear recoil from electron recoil since nucleus is much heavier than electron and heavier particle generates ionization more densely along its path, which forms a plasma-like cloud of charge that shields the interior from the influence of the electric field. The time needed for total disintegration of this plasma region is called plasma time. The plasma time depends on the initial density and radius of the plasma-like cloud, diffusion constant for charge carriers, and the strength of electric field. In this work, we developed a 3-D theoretical model for calculating the plasma time in Ge detectors. Using this model, we calculated the plasma time for both nuclear recoils and electron recoils to study the possibility for Ge detectors to realize n/ ? discrimination and improve detector sensitivity in detecting low-mass WIMPs. This work is supported by NSF in part by the NSF PHY-0758120, DOE Grant DE-FG02-10ER46709, and the State of South Dakota.

  10. Vibrationally resolved photoelectron imaging of Cu2H- and AgCuH- and theoretical calculations.

    PubMed

    Xie, Hua; Li, Xiaoyi; Zhao, Lijuan; Liu, Zhiling; Qin, Zhengbo; Wu, Xia; Tang, Zichao; Xing, Xiaopeng

    2013-02-28

    Vibrationally resolved photoelectron spectra have been obtained for Cu(2)H(-) and AgCuH(-) using photoelectron imaging at 355 nm. Two transition bands X and A are observed for each spectrum. The X bands in both spectra show the vibration progressions of the Cu-H stretching mode and the broad peaks of these progressions indicate significant structural changes from Cu(2)H(-) and AgCuH(-) to their neutral ground states. The A bands in the spectra of Cu(2)H(-) and CuAgH(-) show stretching progressions of Cu-Cu and Ag-Cu, respectively. The contours of these two progressions are pretty narrow, indicating relatively small structural changes from Cu(2)H(-) and AgCuH(-) to their neutral excited states. Calculations based on density functional theory indicate that the ground states of Cu(2)H(-) and AgCuH(-) and the first excited states of their neutrals are linear, whereas their neutral ground states are bent. The photoelectron detachment energies and vibrational frequencies from these calculations are in good agreement with the experimental observations. Especially, the theoretical predication of linear structures for the anions and the neutral excited states are supported by the spectral features of A bands, in which the bending modes are inactive. Comparisons among the vertical detachment energies of Cu(2)H(-), AgCuH(-), and their analogs help to elucidate electronic characteristics of coinage metal elements and hydrogen in small clusters. PMID:23388039

  11. 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.

  12. a Constructive Quantum Field Theoretic Approach to Chern-Simons Theory

    NASA Astrophysics Data System (ADS)

    Nill, Florian

    Chern-Simons theory is formulated quantum field theoretically in terms of string operators, which are localized on finite non-selfintersecting paths in the zero-time plane R2. It is shown how the Weyl algebra approach to the abelian Chern-Simons theory leads to a bundle theoretic construction of these Chern-Simons string operators. To proceed to the non-abelian case topological Chern-Simons theory is considered as a specific model of a more general theory describing the quantum kinematics of coloured framed Plek ton s in R2. This theory allows the construction of string operators as pair-creation operators, mapping n-Plekton states into (n+2)-Plekton states. Link invariants are obtained as vacuum correlation functions of string operators and obey a natural version of reflection positivity. The vacuum sector of such a purely kinematical Plekton theory may be recovered from the link invariants by Osterwalder-Schrader reconstruction. To make the theory work one needs the structures of a ribbon graph category, for which the representations of a quasi-triangular quasi-Hopf algebra may serve as a specific realization.

  13. 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.

  14. 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

  15. Machine Learning of Parameters for Accurate Semiempirical Quantum Chemical Calculations

    PubMed Central

    2015-01-01

    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. PMID:26146493

  16. 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.

  17. 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)

  18. 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.

  19. 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.

  20. Accuracy of theoretical calculations of the main parameters of the F2-layer of the daytime ionosphere

    NASA Astrophysics Data System (ADS)

    Pavlov, A. V.; Sitnov, Iu. S.

    1985-10-01

    Pavlov's (1984) method is used to determine the relative errors (due to errors in measuring the input parameters of the model) in theoretical calculations of the main parameters of the daytime F2-layer under quiet conditions. The parameters calculated are the height of the F2-layer maximum and the electron density.

  1. Quantum Monte Carlo calculations of the thermal conductivity of neutron star crusts

    NASA Astrophysics Data System (ADS)

    Abbar, Sajad; Carlson, Joseph; Duan, Huaiyu; Reddy, Sanjay

    2015-10-01

    We use quantum Monte Carlo (QMC) techniques to calculate the static structure function S (q ) of a one-component ion lattice and use it to calculate the thermal conductivity ? of high-density solid matter expected in the neutron star crust. By making detailed comparisons with the results for the thermal conductivity obtained using standard techniques based on the one-phonon approximation (OPA) valid at low temperatures and the multiphonon harmonic approximation expected to be valid over a wide range of temperatures, we assess the temperature regime where S (q ) from the QMC can be used directly to calculate ? . We also compare the QMC results to those obtained using the classical Monte Carlo to quantitatively assess the magnitude of the quantum corrections. We found that quantum effects became relevant for the calculation of ? at a temperature of T ?0.3 ?P , where ?P is the ion plasma frequency. At T ?0.1 ?P the quantum effects suppress ? by about 30%. The comparison with the results of the OPA indicates that dynamical information beyond the static structure is needed when T ?0.1 ?P . These quantitative comparisons help to establish QMC as a viable technique to calculate ? at moderate temperatures in the range of T =0.1 -1 ?P of relevance to the study of accreting neutron stars. This finding is especially important because QMC is the only viable technique so far for calculating ? in multicomponent systems at low temperatures.

  2. 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

  3. Quantum Monte Carlo Calculations of A <=6 Nuclei

    NASA Astrophysics Data System (ADS)

    Pudliner, B. S.; Pandharipande, V. R.; Carlson, J.; Wiringa, R. B.

    1995-05-01

    The energies of 3H, 3He, and 4He ground states, the 32- and 12- scattering states of 5He, the ground states of 6He, 6Li, and 6Be, and the 3+ and 0+ excited states of 6Li have been accurately calculated with the Green's function Monte Carlo method using realistic models of two- and three-nucleon interactions. The splitting of the A = 3 isospin T = 12 and A = 6 isospin T = 1, J? = 0+ multiplets is also studied. The observed energies and radii are generally well reproduced, however, some definite differences between theory and experiment can be identified.

  4. 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.

  5. Linearized Tensor Renormalization Group Algorithm for the Calculation of Thermodynamic Properties of Quantum Lattice Models

    NASA Astrophysics Data System (ADS)

    Li, Wei; Ran, Shi-Ju; Gong, Shou-Shu; Zhao, Yang; Xi, Bin; Ye, Fei; Su, Gang

    2011-03-01

    A linearized tensor renormalization group algorithm is developed to calculate the thermodynamic properties of low-dimensional quantum lattice models. This new approach employs the infinite time-evolving block decimation technique, and allows for treating directly the transfer-matrix tensor network that makes it more scalable. To illustrate the performance, the thermodynamic quantities of the quantum XY spin chain as well as the Heisenberg antiferromagnet on a honeycomb lattice are calculated by the linearized tensor renormalization group method, showing the pronounced precision and high efficiency.

  6. 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

  7. LETTER TO THE EDITOR: Mn2+ impurities in fluoroperovskites: a test for theoretical calculations

    NASA Astrophysics Data System (ADS)

    Barriuso, M. T.; Aramburu, J. A.; Moreno, M.

    1999-12-01

    The equilibrium impurity-ligand distance, Re, in six fluoroperovskites of the AMF3 series (A: K, Rb, Cs; M: Mg, Zn, Cd, Ca) doped with Mn2+ has been explored through density functional calculations for MnF6A8M616+ clusters where the effects of the electrostatic potential due to the rest of the lattice are included. The Re-values obtained coincide, within the experimental uncertainties, with those derived from the analysis of the experimental isotropic superhyperfine constant, As, and the 10Dq-parameter and also with available extended x-ray absorption fine-structure results. This important result is shown to be practically independent of the quality of the basis set employed. From the analysis of recent electron paramagnetic resonance data for AlF3:Mn2+ it is concluded that, for this system, Reicons/Journals/Common/approx" ALT="approx" ALIGN="TOP"/>197 pm which is 7% smaller than the average distance for pure compounds involving MnF64- complexes. The latter figure is shown to be consistent with the substitution of Mn2+ for a trivalent cation in AlF3:Mn2+. The present theoretical scheme has also been applied to Tl+ impurities in NaI. First results indicate an outwards relaxation of ligands which is equal to, at least, 5% and thus is much higher than the figure (1%) calculated by Aguado et al (Aguado A, Ayuela A, Lopez J M and Alonso J A 1998 Phys. Rev. B 58 11 964).

  8. Theoretical study of ignition reactions of linear symmetrical monoethers as potential diesel fuel additives: DFT calculations

    NASA Astrophysics Data System (ADS)

    Marrouni, Karim El; Abou-Rachid, Hakima; Kaliaguine, Serge

    This work investigates the chemical reactivity of four linear symmetrical monoethers with molecular oxygen. Such oxygenated compounds may be considered as potential diesel fuel additives in order to reduce the ignition delay in diesel fuel engines. For this purpose, a kinetic study is proposed to clarify the relation between the molecular structure of the fuel molecule and its ignition properties. To this end, DFT calculations were performed for these reactions using B3LYP/6-311G(d,p) and BH&HLYP/6-311G(d,p) to determine structures, energies, and vibrational frequencies of stationary points as well as activated complexes involved in each gas-phase combustion initiation reaction of the monoethers CH3OCH3, C2H5OC2H5, C3H7OC3H7, or C4H9OC4H9 with molecular oxygen. This theoretical kinetic study was carried out using electronic structure results and the transition state theory, to assess the rate constants for all studied combustion reactions. As it has been shown in our previous work [Abou-Rachid et al., J Mol Struct (Theochem) 2003, 621, 293], the cetane number (CN) of a pure organic molecule depends on the initiation rate of its homogeneous gas-phase reaction with molecular oxygen. Indeed, the calculated initiation rate constants of the H-abstraction process of linear monoethers with O2 show a very good correlation with experimental CN data of these pure compounds at T D 1,000 K. This temperature is representative of the operating conditions of a diesel fuel engine.0

  9. Bioactive Polycyclic Tetramate Macrolactams from Lysobacter enzymogenes and Their Absolute Configurations by Theoretical ECD Calculations.

    PubMed

    Xu, Liangxiong; Wu, Ping; Wright, Stephen J; Du, Liangcheng; Wei, Xiaoyi

    2015-08-28

    Two new polycyclic tetramate macrolactams, lysobacteramides A (1) and B (2), together with HSAF (heat-stable antifungal factor, 3), 3-dehydroxy HSAF (4), and alteramide A (5) were isolated from a culture of Lysobacter enzymogenes C3 in nutrient yeast glycerol medium. Their structures were determined by MS and extensive NMR analysis. The absolute configurations of 1-5 were assigned by theoretical calculations of their ECD spectra. Although HSAF and analogues were reported from several microorganisms, their absolute configurations had not been established. The isolation and the absolute configurations of these compounds revealed new insights into the biosynthetic mechanism for formation of the polycycles. Compounds 1-4 exhibited cytotoxic activity against human carcinoma A549, HepG2, and MCF-7 cells with IC50 values ranging from 0.26 to 10.3 ?M. Compounds 2 and 3 showed antifungal activity against Fusarium verticillioides with IC50 value of 47.9 and 6.90 ?g/mL, respectively. PMID:26200218

  10. 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.

  11. Structural properties and quantum effects in protonated helium clusters. II. Quantum Monte Carlo calculations for the smaller aggregates

    NASA Astrophysics Data System (ADS)

    Balta, B.; Gianturco, F. A.; Paesani, F.

    2000-04-01

    The computed interaction potential energy surface between an He atom and the ionic core unit (HHe 2) +, discussed in the preceding paper, is employed here to analyse the structures of the protonated, small clusters of He, and to evaluate the effects of quantum behaviour on the results reached in previous dynamical calculations carried out using ab initio classical dynamics. The method of the present analysis involves numerical solutions of diffusion Monte Carlo (DMC) equations via random walk techniques and allows us to extract global minimum energy configurations for the quantum ground-states of the smaller clusters. The values of the zero point energy, the effect of competitive growth dynamics between various configurations and the evidence for the presence of clear shell structures in the protonated clusters are among the features from the present DMC calculations, which we discuss in this work.

  12. Infrared and NMR spectra, tautomerism, vibrational assignment, normal coordinate analysis, and quantum mechanical calculations of 4-amino-5-pyrimidinecarbonitrile

    NASA Astrophysics Data System (ADS)

    Afifi, Mahmoud S.; Farag, Rabei S.; Shaaban, Ibrahim A.; Wilson, Lee D.; Zoghaib, Wajdi M.; Mohamed, Tarek A.

    2013-07-01

    The infrared (4000-200 cm-1) spectrum for 4-amino-5-pyrimidinecarbonitrile (APC, C5H4N4) was acquired in the solid phase. In addition, the 1H and 13C NMR spectra of APC were obtained in DMSO-d6 along with its mass spectrum. Initially, six isomers were hypothesized and then investigated by means of DFT/B3LYP and MP2(full) quantum mechanical calculations using a 6-31G(d) basis set. Moreover, the 1H and 13C NMR chemical shifts were predicted using a GIAO approximation at the 6-311+G(d,p) basis set and the B3LYP method with (and without) solvent effects using PCM method. The correlation coefficients showed good agreement between the experimental/theoretical chemical shift values of amino tautomers (1 and 2) rather than the eliminated imino tautomers (3-6), in agreement with the current quantum mechanical calculations. Structures 3-6 are less stable than the amino tautomers (1 and 2) by about 5206-8673 cm-1 (62.3-103.7 kJ/mol). The MP2(full)/6-31G(d) computational results favor the amino structure 1 with a pyramidal NH2 moiety and calculated real vibrational frequencies, however; structure 2 is considered a transition state owing to the calculated imaginary frequency. It is worth mentioning that, the calculated structural parameters suggest a strong conjugation between the amino nitrogen and pyrimidine ring. Aided by frequency calculations, normal coordinate analysis, force constants and potential energy distributions (PEDs), a complete vibrational assignment for the observed bands is proposed herein. Finally, NH2 internal rotation barriers for the stable non-planar isomer (1) were carried out using MP2(full)/6-31G(d) optimized structural parameters. Our results are discussed herein and compared to structural parameters for similar molecules whenever appropriate.

  13. Molecular docking, spectroscopic studies and quantum calculations on nootropic drug.

    PubMed

    Uma Maheswari, J; Muthu, S; Sundius, Tom

    2014-04-01

    A systematic vibrational spectroscopic assignment and analysis of piracetam [(2-oxo-1-pyrrolidineacetamide)] have been carried out using FT-IR and FT-Raman spectral data. The vibrational analysis was aided by an electronic structure calculation based on the hybrid density functional method B3LYP using a 6-311G++(d,p) basis set. Molecular equilibrium geometries, electronic energies, IR and Raman intensities, and harmonic vibrational frequencies have been computed. The assignments are based on the experimental IR and Raman spectra, and a complete assignment of the observed spectra has been proposed. The UV-visible spectrum of the compound was recorded and the electronic properties, such as HOMO and LUMO energies and the maximum absorption wavelengths ?max were determined by the time-dependent DFT (TD-DFT) method. The geometrical parameters, vibrational frequencies and absorption wavelengths were compared with the experimental data. The complete vibrational assignments are performed on the basis of the potential energy distributions (PED) of the vibrational modes in terms of natural internal coordinates. The simulated FT-IR, FT-Raman, and UV spectra of the title compound have been constructed. Molecular docking studies have been carried out in the active site of piracetam by using Argus Lab. In addition, the potential energy surface, HOMO and LUMO energies, first-order hyperpolarizability and the molecular electrostatic potential have been computed. PMID:24487180

  14. 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

  15. 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.

  16. 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.

  17. 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.

  18. 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.

  19. Gas-phase structure of 2,2,2-trichloroethyl chloroformate studied by electron diffraction and quantum-chemical calculations.

    PubMed

    Gil, Diego M; Tuttolomondo, Mara E; Blomeyer, Sebastian; Reuter, Christian G; Mitzel, Norbert W; Altabef, Ada Ben

    2016-01-01

    The molecular structure and conformational properties of 2,2,2-trichloroethyl chloroformate, ClC(O)OCH2CCl3 were determined experimentally using gas-phase electron diffraction (GED) and theoretically based on quantum-chemical calculations at the MP2 and DFT levels of theory. Further experimental measurements such as UV-visible, IR and Raman spectroscopy were complemented with the corresponding theoretical studies. All experimental results and calculations confirm the presence of two conformers namely anti-gauche (C1 symmetry) and anti-anti (Cs symmetry). The conformational preference was rationalised by NBO and AIM analyses. Molecular properties such as ionisation potential, electronegativity, chemical potential, chemical hardness and softness were deduced from HOMO-LUMO analyses. The TD-DFT approach was applied to assign the electronic transitions observed in the UV-visible spectrum. A detailed interpretation of the infrared and Raman spectra of the title compound are reported. Using calculated frequencies as a guide, IR and Raman spectra also provide evidence for the presence of both C1 and Cs conformers. PMID:26617390

  20. 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.

  1. 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...

  2. 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.

  3. 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.

  4. 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

  5. Tight-binding calculation of electronic states in a triangular symmetrical quantum well

    NASA Astrophysics Data System (ADS)

    Vlaev, S.; Velasco, V. R.; Garca-Moliner, F.

    1994-08-01

    We study a ssV-shaped symmetrically graded quantum well, which has been investigated optically. The well width is 125 and the Al concentration x varies linearly from x=0.36 at the barriers to x=0 (pure GaAs) in the middle of the well. In the present paper, numerical calculations of the well electronic states are made within the framework of the surface Green function matching method and the sp3s* empirical tight-binding model within virtual-crystal approximation. An algorithm developed recently by the authors is applied to treat graded composition heterostructures. The e1-hh1, e2-hh2, and e1-lh1 calculated transition energies are in fair agreement with experiment. The dependence of the transition energies on the well width and on the Al concentration is studied. A comparison with the rectangular quantum well is made. The transition energies decrease when the well width increases and are always higher than the same energies of the rectangular quantum well. All the transitions are better resolved energetically for the triangular quantum well. The energies of the transitions under study increase when the Al concentration x increases, but this dependence is much stronger for the triangular quantum well. Spatial distributions of spectral strengths of the well states are also obtained.

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. 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.

  11. Comparison of Hugoniots calculated for aluminum in the framework of three quantum-statistical models

    NASA Astrophysics Data System (ADS)

    Kadatskiy, M. A.; Khishchenko, K. V.

    2015-11-01

    The results of calculations of thermodynamic properties of aluminum under shock compression in the framework of the Thomas-Fermi model, the Thomas-Fermi model with quantum and exchange corrections and the Hartree-Fock-Slater model are presented. The influences of the thermal motion and the interaction of ions are taken into account in the framework of three models: the ideal gas, the one-component plasma and the charged hard spheres. Calculations are performed in the pressure range from 1 to 107 GPa. Calculated Hugoniots are compared with available experimental data.

  12. Ab initio quantum chemical calculation as a tool of evaluating diamagnetic susceptibility of magnetically levitating substances

    NASA Astrophysics Data System (ADS)

    Fujiwara, Y.; Tanimoto, Y.

    2009-03-01

    On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 0.005) x (calculated) - (1.22 0.60) x 10-6 in a unit of cm3 mol-1 and good cost performance.

  13. 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.

  14. 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.

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

    NASA Astrophysics Data System (ADS)

    Reeves, Kyle G.; Kanai, Yosuke

    2014-07-01

    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.

  16. 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.

  17. 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.

  18. 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

  19. Shock Hugoniot calculations of polymers using quantum mechanics and molecular dynamics.

    PubMed

    Chantawansri, Tanya L; Sirk, Timothy W; Byrd, Edward F C; Andzelm, Jan W; Rice, Betsy M

    2012-11-28

    Using quantum mechanics (QM) and classical force-field based molecular dynamics (FF), we have calculated the principle shock Hugoniot curves for numerous amorphous polymers including poly[methyl methacrylate] (PMMA), poly[styrene], polycarbonate, as well as both the amorphous and crystalline forms of poly[ethylene]. In the FF calculations, we considered a non-reactive force field (i.e., polymer consistent FF). The QM calculations were performed with density functional theory (DFT) using dispersion corrected atom centered pseudopotentials. Overall, results obtained by DFT show much better agreement with available experimental data than classical force fields. In particular, DFT calculated Hugoniot curves for PMMA up to 74 GPa are in very good agreement with experimental data, where a preliminary study of chain fracture and association was also performed. Structure analysis calculations of the radius of gyration and carbon-carbon radial distribution function were also carried out to elucidate contraction of the polymer chains with increasing pressure. PMID:23206025

  20. Surface Plasmons in Quantum-Sized Noble-Metal Clusters: Quantum Calculations and the Classical Picture of Charge Oscillations

    NASA Astrophysics Data System (ADS)

    Weissker, Hans-Christian; Lpez-Lozano, Xchitl

    2015-03-01

    The localized surface-plasmon resonance (LSPR) in metal clusters corresponds to a collective charge oscillation of quasi-free electrons of the metal. We use the real-time formulation of time-dependent density-functional theory (TDDFT) with pseudopotentials to study the correspondence and differences of the quantum calculations with the classical picture. By means of animations, we discuss the real-time evolution of the electronic density for different geometries. While there is a clear correspondence between the overall picture of a charge oscillation and the actual dynamics in quantum-sized clusters, the situation is much more intricate owing to quantum effects and the atomistic inhomogeneity of the cluster. A fine pattern is present over the volume of the cluster even at moments of zero overall polarization. The difference between Ag and Au is clearly visible. Finally, we discuss the question of collective vs. molecular-like transitions; even for single transitions, the dynamics of the total density can be similar to the picture of a charge oscillation.

  1. 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.

  2. 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.

  3. 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.

  4. Tight-binding calculation of electronic states in an inverse parabolic quantum well

    NASA Astrophysics Data System (ADS)

    Vlaev, S.; Velasco, V. R.; Garca-Moliner, F.

    1995-03-01

    We study an inverse parabolic compositionally graded quantum well. The Al concentration x varies parabolically from xmax=0.12 at the center to xmin=0.02 at the edges across the 130 quantum well. The constant Al concentration at the barriers is xb=0.36. Numerical calculations of the well electronic states are made on the basis of an algorithm developed recently by the authors. The sp3s* spin dependent empirical tight-binding model is used within the virtual crystal approximation. The c1-hh1, c2-hh2, and c2-lh2 calculated transition energies are in good agreement with experiment. The dependence of the transition energies on the Al concentration xmax at the well center and on the well width Nw is studied. Spatial distributions of spectral strengths and their orbital components are also obtained. The ground electron and hole state curves exhibit ``global'' or ``localized'' features depending on the value of xmax.

  5. 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

  6. 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.

  7. Quantum Monte Carlo calculation of the binding energy of the beryllium dimer

    NASA Astrophysics Data System (ADS)

    Deible, Michael J.; Kessler, Melody; Gasperich, Kevin E.; Jordan, Kenneth D.

    2015-08-01

    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.

  8. 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.

  9. 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.

  10. 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.

  11. 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

  12. 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

  13. 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.

  14. 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.

  15. Quantum Monte Carlo Calculation of the Binding Energy of Bilayer Graphene

    NASA Astrophysics Data System (ADS)

    Mostaani, E.; Drummond, N. D.; Fal'ko, V. I.

    2015-09-01

    We report diffusion quantum Monte Carlo calculations of the interlayer binding energy of bilayer graphene. We find the binding energies of the A A -and A B -stacked structures at the equilibrium separation to be 11.5(9) and 17.7 (9 ) meV /atom , respectively. The out-of-plane zone-center optical phonon frequency predicted by our binding-energy curve is consistent with available experimental results. As well as assisting the modeling of interactions between graphene layers, our results will facilitate the development of van der Waals exchange-correlation functionals for density functional theory calculations.

  16. 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

  17. 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.

  18. 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.

  19. Theoretical calculations of thermophysical properties of single-wall carbon nanotube bundles

    NASA Astrophysics Data System (ADS)

    Miao, Ting-Ting; Song, Meng-Xuan; Ma, Wei-Gang; Zhang, Xing

    2011-05-01

    Carbon nanotube bundles are promising thermal interfacial materials due to their excellent thermal and mechanical characteristics. In this study, the phonon dispersion relations and density of states of the single-wall carbon nanotube bundles are calculated by using the force constant model. The calculation results show that the inter-tube interaction leads to a significant frequency raise of the low frequency modes. To verify the applied calculation method, the specific heat of a single single-wall carbon nanotube is calculated first based on the obtained phonon dispersion relations and the results coincide well with the experimental data. Moreover, the specific heat of the bundles is calculated and exhibits a slight reduction at low temperatures in comparison with that of the single tube. The thermal conductivity of the bundles at low temperatures is calculated by using the ballistic transport model. The calculation results indicate that the inter-tube interaction, i.e. van der Waals interaction, hinders heat transfer and cannot be neglected at extremely low temperatures. For (5, 5) bundles, the relative difference of the thermal conductivity caused by ignoring inter-tube effect reaches the maximum value of 26% around 17 K, which indicates the significant inter-tube interaction effect on the thermal conductivity at low temperatures.

  20. Theoretical Studies of the Structure and Dynamics of Quantum Liquid Clusters

    NASA Astrophysics Data System (ADS)

    McMahon, Michele Ann

    Quantum clusters of He and Hz are systems displaying both quantum and finite-size properties. Using variational and diffusion Monte Carlo, we investigate the energetics and structures of a variety of pure and doped clusters. First, we present results for the ground states of He _7 and (H_2)_{N } (N = 6, 7, 13 and 33). Both helium and hydrogen clusters are highly non-classical, but, because of the weaker He-He binding, H_{N} is more delocalized than (H_2)_ {N}. The He clusters are generally structureless spheres with highest particle density near the center. Although still spherical, (H_2)_{N} clusters show some internal structure with residual five-fold symmetry. We next study the rotational states of He_7 and (H_2) _7. As the angular momentum increases, these clusters evolve from spherical to toroidal. By L = 2 for He_7 and L = 6 for (H_2) _7, the clusters become metastable with respect to loss of one particle. The addition of a strongly binding dopant molecule, such as SF_6, induces structuring of the He density into solvation shells about the impurity. We demonstrate that SF_6 is located near the cluster center in He_{39,40 }. We study trial function bias and DMC convergence, showing that the amount of Monte Carlo sampling needed to converge the impurity location is much greater than for He. This distinction may explain discrepancies found in the literature. Our study of Cl_2He _{N} (N = 1, 6 and 20), contrasts isotropic and anisotropic treatments as well as the L = 0 and L = 2 rotational states. The inclusion of anisotropy lowers energies because of the gamma = pi/2 minimum in the Cl_2 -He potential. rm Cl_2H_6 has a ring of helium density, about the Cl-Cl bond, that is largely unchanged from the L = 0 to the L = 2 state. For rm Cl_2He_{20}, the helium density surrounds the central Cl_2 molecule, and both the He and Cl_2 densities delocalize under rotation. Investigation of energy transfer from an excited impurity to an embedding cluster sheds light on the quantum cluster environment. We present a new Golden Rule-based method which uses Laplace transform and DMC techniques to calculate linewidths and energy differences for energy transfer processes. Results are shown for a harmonic oscillator and for impurity-to-cluster transfer in rm Cl_2He_6. This method is general and requires no explicit knowledge of final states.

  1. 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.

  2. Theoretical calculations for using positive electrode compression to increase lead-acid battery life

    NASA Astrophysics Data System (ADS)

    Edwards, Dean B.; Schmitz, Claus

    Investigators have confirmed that applying a small amount of mechanical pressure, approximately 1 bar (10 5 Pa), to the face of the positive electrode can dramatically increase the life of deep cycled, lead acid batteries. In this paper, we calculate the pressures required to stabilize the active material in the positive electrode based on the "Agglomerate of Spheres" model. The calculations agree closely with the experimental observations. In addition to these calculations, we also provide another possible interpretation of the "Agglomerate of Spheres" model and give an improved estimate for the surface tension of lead dioxide, an important physical quantity for the model.

  3. Theoretical calculation of medium-energy proton-induced reactions on Al, Zr, and Pb

    SciTech Connect

    Ramavataram, S.; Divadeenam, M.; Ward, T.E.

    1988-01-01

    The intranuclear cascade model of nuclear reactions was used to calculate double differential cross sections for the (p,xn) reaction. The calculations were performed with a generalized version of the code VEGAS, CLUST. Model predictions are compared with recent experimental data. Calculated fast-particle spectral shapes at low angles are reproduced reasonably well for the experimental data. As one possible improvement to the model, the proton reaction cross sections were estimated independently using the prescriptions of Karol, and DeVries and Peng. The systematic trends that emerge from this analysis are discussed. 12 refs., 5 figs.

  4. 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.

  5. 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.

  6. 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.

  7. Field theoretic calculation of the surface tension for a model electrolyte system

    NASA Astrophysics Data System (ADS)

    Dean, D. S.; Horgan, R. R.

    2004-06-01

    We carry out the calculation of the surface tension for a model electrolyte to first order in a cumulant expansion about a free-field theory equivalent to the Debye-Hckel approximation. In contrast with previous calculations, the surface tension is calculated directly without recourse to integrating thermodynamic relations. The system considered is a monovalent electrolyte with a region at the interface, of width h , from which the ionic species are excluded. In the case where the external dielectric constant ?0 is smaller than the electrolyte solutions dielectric constant ? we show that the calculation at this order can be fully regularized. In the case where h is taken to be zero the Onsager-Samaras limiting law for the excess surface tension of dilute electrolyte solutions is recovered, with corrections coming from a nonzero value of ?0 /? .

  8. 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.

  9. Single crystal structure, spectroscopic (FT-IR, FT-Raman, 1H NMR, 13C NMR) studies, physico-chemical properties and theoretical calculations of 1-(4-chlorophenyl)-3-(4-nitrophenyl)triazene

    NASA Astrophysics Data System (ADS)

    Fereyduni, E.; Rofouei, M. K.; Kamaee, M.; Ramalingam, S.; Sharifkhani, S. M.

    2012-05-01

    In this paper, we will report a combined experimental and theoretical investigation of the molecular structure and spectroscopic parameteres (FT-IR, FT-Raman, 1H NMR, 13C NMR) of 1-(4-chlorophenyl)-3-(4-nitrophenyl)triazene, CNT. The optimized geometry, harmonic vibrational frequencies, infrared intensities and Raman scattering activities were obtained at the B3LYP/6-311++G(d,p) level of theory and thermodynamic functions were calculated at the same level. A detailed interpretation of the Infrared, Raman and NMR spectra of the compound was reported as well. Analysis of experimental NMR chemical shifts was supported by quantum chemical calculations and HOSE code fragment based prediction tool (ACD/NMR). The theoretical results showed an excellent agreement with the experimental values. The physico-chemical properties (such as log P, hydrophobicity, ) were also calculated using three commercially available programs.

  10. 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.

  11. 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.

  12. 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.

  13. Theoretical calculation of the p-emitter length for snapback-free reverse-conducting IGBT

    NASA Astrophysics Data System (ADS)

    Liheng, Zhu; Xingbi, Chen

    2014-06-01

    A physically based equation for predicting required p-emitter length of a snapback-free reverse-conducting insulated gate bipolar transistor (RC-IGBT) with field-stop structure is proposed. The n-buffer resistances above the p-emitter region with anode geometries of linear strip, circular and annular type are calculated, and based on this, the minimum p-emitter lengths of those three geometries are given and verified by simulation. It is found that good agreement was achieved between the numerical calculation and simulation results. Moreover, the calculation results show that the annular case needs the shortest p-emitter length for RC-IGBT to be snapback-free.

  14. 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.

  15. 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.

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

    NASA Astrophysics Data System (ADS)

    Cavassilas, Nicolas; Michelini, Fabienne; Bescond, Marc

    2014-08-01

    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.

  17. 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.

  18. Dynamical structure functions from quantum Monte Carlo calculations of a proper integral transform

    NASA Astrophysics Data System (ADS)

    Roggero, Alessandro; Pederiva, Francesco; Orlandini, Giuseppina

    2013-09-01

    An ab initio method for determining the dynamical structure function of an interacting many-body quantum system has been devised by combining a generalized integral transform method with quantum Monte Carlo (QMC) methods. A kernel has been found that (i) lets the transform be calculable with QMC methods and (ii) is a representation of the ? function, allowing an inversion of the transform with a much higher predictive power than the inverse Laplace transform. As a first application, the excitation spectrum of bulk atomic 4He has been computed, both in the low and intermediate momentum ranges. The peculiar form of the kernel allows us to predict, without using any model, both positions and widths of the collective excitations in the maxon-roton region, as well as the existence of the second collective peak. A prediction of the dispersion of the single-particle modes described by the incoherent part is also presented.

  19. 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

  20. 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

  1. 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).

  2. 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

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

    NASA Astrophysics Data System (ADS)

    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), 10.1103/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), 10.1103/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.

  4. 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

  5. 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.

  6. Calculated surface, image and quantum well states in Ag/Cu(111) system

    NASA Astrophysics Data System (ADS)

    Bejan, Doina

    2013-09-01

    The energy spectrum and the probability densities of the surface, the image and the quantum well (QW) states of the Ag/Cu(111) system have been calculated function of the thickness of the silver film. The layer by layer energy spectrum and probability densities of this system are obtained as a solution of the Schrdinger equation using the discrete variable representation (DVR). In this equation we have used an analytical one-dimensional model potential derived from the potential of Chulkov et al. [1]. Our calculated energy spectrum and probability densities of the surface, image and QW states present coverage dependence in agreement with the experiments and other calculations of the surface states.

  7. 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.

  8. 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...

  9. 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.

  10. Theoretical calculations of rotationally inelastic collisions of He with NaK(A 1?+): Transfer of population, orientation, and alignment

    NASA Astrophysics Data System (ADS)

    Malenda, R. F.; Price, T. J.; Stevens, J.; Uppalapati, S. L.; Fragale, A.; Weiser, P. M.; Kuczala, A.; Talbi, D.; Hickman, A. P.

    2015-06-01

    We have performed extensive calculations to investigate thermal energy, rotationally inelastic collisions of NaK (A1?+) with He. We determined a potential energy surface using a multi-reference configuration interaction wave function as implemented by the GAMESS electronic structure code, and we have performed coupled channel scattering calculations using the Arthurs and Dalgarno formalism. We also calculate the Grawert coefficients B?(j, j') for each j ? j' transition. These coefficients are used to determine the probability that orientation and alignment are preserved in collisions taking place in a cell environment. The calculations include all rotational levels with j or j' between 0 and 50, and total (translational and rotational) energies in the range 0.0002-0.0025 a.u. (44-550 cm-1). The calculated cross sections for transitions with even values of ?j tend to be larger than those for transitions with odd ?j, in agreement with the recent experiments of Wolfe et al. (J. Chem. Phys. 134, 174301 (2011)). The calculations of the energy dependence of the cross sections and the calculations of the fraction of orientation and alignment preserved in collisions also exhibit distinctly different behaviors for odd and even values of ?j. The calculations also indicate that the average fraction of orientation or alignment preserved in a transition becomes larger as j increases. We interpret this behavior using the semiclassical model of Derouard, which also leads to a simple way of visualizing the distribution of the angles between the initial and final angular momentum vectors j and j'. Finally, we compare the exact quantum results for j ? j' transitions with results based on the simpler, energy sudden approximation. That approximation is shown to be quite accurate.

  11. Theoretical calculations of rotationally inelastic collisions of He with NaK(A?(1)?(+)): Transfer of population, orientation, and alignment.

    PubMed

    Malenda, R F; Price, T J; Stevens, J; Uppalapati, S L; Fragale, A; Weiser, P M; Kuczala, A; Talbi, D; Hickman, A P

    2015-06-14

    We have performed extensive calculations to investigate thermal energy, rotationally inelastic collisions of NaK (A(1)?(+)) with He. We determined a potential energy surface using a multi-reference configuration interaction wave function as implemented by the GAMESS electronic structure code, and we have performed coupled channel scattering calculations using the Arthurs and Dalgarno formalism. We also calculate the Grawert coefficients B(?)(j, j') for each j ? j' transition. These coefficients are used to determine the probability that orientation and alignment are preserved in collisions taking place in a cell environment. The calculations include all rotational levels with j or j' between 0 and 50, and total (translational and rotational) energies in the range 0.0002-0.0025 a.u. (?44-550?cm(-1)). The calculated cross sections for transitions with even values of ?j tend to be larger than those for transitions with odd ?j, in agreement with the recent experiments of Wolfe et al. (J. Chem. Phys. 134, 174301 (2011)). The calculations of the energy dependence of the cross sections and the calculations of the fraction of orientation and alignment preserved in collisions also exhibit distinctly different behaviors for odd and even values of ?j. The calculations also indicate that the average fraction of orientation or alignment preserved in a transition becomes larger as j increases. We interpret this behavior using the semiclassical model of Derouard, which also leads to a simple way of visualizing the distribution of the angles between the initial and final angular momentum vectors j and j'. Finally, we compare the exact quantum results for j ? j' transitions with results based on the simpler, energy sudden approximation. That approximation is shown to be quite accurate. PMID:26071704

  12. 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.

  13. Different topologies in three manganese-?-azido 1D compounds: magnetic behavior and DFT-quantum Monte Carlo calculations.

    PubMed

    Mautner, Franz A; Berger, Christian; Scherzer, Michael; Fischer, Roland C; Maxwell, Lindley; Ruiz, Eliseo; Vicente, Ramon

    2015-11-14

    The syntheses and structural characterization of three new monodimensional azido-bridged manganese(ii) complexes with empirical formulae [Mn(N3)2(aminopyz)2]n (1), [Mn(N3)2(4-azpy)2]n (2) and [Mn(N3)2(4-Bzpy)2]n (3) (pyz = pyrazine (1,4-diazine)), 4-azpy = 4-azidopyridine and 4-Bzpy = 4-benzoylpyridine) are reported. 1 is a monodimensional compound with double EO azido bridges, 2 is an alternating monodimensional compound with double end-on and double end-to-end azido bridges in the sequence di-EO-di-EE and 3 is a monodimensional compound with double end-on and double end-to-end azido bridges in the sequence di-EO-di-EO-diEO-di-EO-di-EE. The magnetic properties of 1-3 are reported. Periodic DFT calculations were performed to estimate the J values and quantum Monte Carlo simulations were carried out using the calculated J values to check their accuracy in comparison with the experimental magnetic measurements. From this theoretical analysis, two appealing features of the di-EO Mn(ii) compounds can be extracted: first, the exchange coupling becomes more ferromagnetic when the Mn-N-Mn bridging angle becomes larger and the spin density of the bridging nitrogen atoms has an opposite sign to that of the Mn(ii) centers. PMID:26449346

  14. 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 ( 901809013545 ), 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

  15. Intramolecular hydrogen bonding in N-salicylideneaniline: FT-IR spectrum and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Moosavi-Tekyeh, Zainab; Dastani, Najmeh

    2015-12-01

    FT-IR and FT-Raman spectra of N-salicylideneaniline (SAn) and its deuterated analogue (D-SAn) are recorded, and the theoretical calculations are performed on their molecular structures and vibrational frequencies. The same calculations are performed for SAn in different solutions using the polarizable conductor continuum model (CPCM) method. Comparisons between the spectra obtained and the corresponding theoretical calculations are used to assign the vibrational frequencies for these compounds. The spectral behavior of SAn upon deuteration is also used to distinguish the positions of OH vibrational frequencies. The hydrogen bond strength of SAn is investigated by applying the atoms-in-molecules (AIM) theory, natural bond orbital (NBO) analysis, and geometry calculations. The harmonic vibrational frequencies of SAn are calculated at B3LYP and X3LYP levels of theory using 6-31G*, 6-311G**, and 6-311++G** basis sets. The AIM results support a medium hydrogen bonding in SAn. The observed ?OH/?OD and ?OH/?OD for SAn appear at 2940/2122 and 830/589cm-1, respectively.

  16. Theoretical Calculations of Photoabsorption of Several Alicyclic Molecules in the Vacuum Ultraviolet Region

    SciTech Connect

    Matsuzawa, Nobuyuki; Ishitani, Akihiko; Dixon, David A.; Uda, Tsuyoshi

    2001-06-13

    In order to aid in the design of transparent materials for use as photoresists for F2 lithography (157 nm), we have performed time-dependent density functional theory (TD-DFT) calculations of the photoabsorption of molecules in the vacuum ultraviolet region. The application of this TD-DFT method to the prediction of photoabsorption was benchmarked using model molecules such as formaldehyde, and an empirical equation for correcting the calculated transition energy was obtained. The TD-DFT method with the empirical correction equation provides dramatically more accurate results than those obtained with the CIS (single-excitation configuration interaction) method, which we employed in previous studies. We used it to predict the photoabsorption of various molecules such as methanol, t-butylalcohol, acetic acid, methyl acetate, cycloalkane, norbonane, tricyclodecane, tetrahydropyrane, adamantane, maleic anhydride and their fluorinated derivatives.

  17. Method and Basis Set Analysis of Oxorhenium(V) Complexes for Theoretical Calculations

    PubMed Central

    Demoin, Dustin Wayne; Li, Yawen; Jurisson, Silvia S.; Deakyne, Carol A.

    2012-01-01

    A variety of method and basis set combinations has been evaluated for monooxorhenium(V) complexes with N, O, P, S, Cl, and Se donor atoms. The geometries and energies obtained are compared to both high-level computations and literature structures. These calculations show that the PBE0 method outperforms the B3LYP method with respect to both structure and energetics. The combination of 6-31G** basis set on the nonmetal atoms and LANL2TZ effective core potential on the rhenium center gives reliable equilibrium structures with minimal computational resources for both model and literature compounds. Single-point energy calculations at the PBE0/LANL2TZ,6-311+G* level of theory are recommended for energetics. PMID:23087847

  18. 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.

  19. Theoretical Calculation of Prompt Neutron Spectra from Fission of Curium Isotopes

    NASA Astrophysics Data System (ADS)

    Ohsawa, Takaaki; Tani, Kazuhiro; Kishimoto, Yasufumi

    2003-06-01

    Prompt neutron spectra for Cm-isotopes (242Cm, 243Cm, 244Cm, 245Cm, 246Cm, 248Cm) were calculated on the basis of a modified version of the Madland-Nix model combined with a multimodal fission model. The predicted spectra were found to be in fair agreement with recent data. A slight enhancement of the low-energy component of the spectrum was interpreted in terms of neutron emission during fragment acceleration.

  20. 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.

  1. 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

  2. Ultrafast excited state dynamics of the Na3F cluster: quantum wave packet and classical trajectory calculations compared to experimental results.

    PubMed

    Heitz, M-C; Durand, G; Spiegelman, F; Meier, C; Mitri?, R; Bonaci?-Kouteck, V

    2004-11-22

    Short-time, excited-state dynamics of the lowest isomer of the Na(3)F cluster is studied theoretically in order to interpret the features of recent time-resolved pump-probe ionization experiments [J. M. L'Hermite, V. Blanchet, A. Le Padellec, B. Lamory, and P. Labastie, Eur. Phys. J. D 28, 361 (2004)]. In the present paper, we propose an identification of the vibrational motion responsible for the oscillations in the ion signal, on the basis of quantum mechanical wave packet propagations and classical trajectory calculations. The good agreement between experiment and theory allows for a clear interpretation of the detected dynamics. PMID:15549864

  3. Ultrafast excited state dynamics of the Na3F cluster: Quantum wave packet and classical trajectory calculations compared to experimental results

    NASA Astrophysics Data System (ADS)

    Heitz, M.-C.; Durand, G.; Spiegelman, F.; Meier, C.; Mitri?, R.; Bonac?i?-Kouteck, V.

    2004-11-01

    Short-time, excited-state dynamics of the lowest isomer of the Na3F cluster is studied theoretically in order to interpret the features of recent time-resolved pump-probe ionization experiments [J. M. L'Hermite, V. Blanchet, A. Le Padellec, B. Lamory, and P. Labastie, Eur. Phys. J. D 28, 361 (2004)]. In the present paper, we propose an identification of the vibrational motion responsible for the oscillations in the ion signal, on the basis of quantum mechanical wave packet propagations and classical trajectory calculations. The good agreement between experiment and theory allows for a clear interpretation of the detected dynamics.

  4. 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.

  5. Playing the quantum shuffling game with programmable pocket calculators and microcomputers

    NASA Astrophysics Data System (ADS)

    Sauer, G.

    1981-03-01

    The utilisation of programmable calculators or microcomputers in the classroom for the quantum shuffling game may reinforce the study of statistical physics in unit 9 of the Nuffield advanced physics course since the students are themselves able to work out much more sophisticated applications of the game. Because of the higher speed of computation and the possibilities of graphical representation on the computer screen preference is given to the application of microcomputer games. Copies of the programs described may be obtained from Professor P J Black, Chelsea College Centre for Science Education, Bridges Place, London SW6 4HR or directly from the author at Tulpenweg 3, 6301 Linden, W Germany.

  6. Electric-field control of magnetism in graphene quantum dots: Ab initio calculations

    PubMed Central

    Agapito, Luis A.; Kioussis, Nicholas; Kaxiras, Efthimios

    2011-01-01

    Employing ab initio calculations we predict that the magnetic states of hydrogenated diamond-shaped zigzag graphene quantum dots (GQDs), each exhibiting unique electronic structure, can be selectively tuned with gate voltage, through Stark or hybridization electric-field modulation of the spatial distribution and energy of the spin-polarized molecular orbitals, leading to transitions between these states. Electrical read-out of the GQD magnetic state can be accomplished by exploiting the distinctive electrical properties of the various magnetic configurations. PMID:21765631

  7. 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

  8. 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.

  9. Ground state of doped cuprates from first-principles quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Wagner, Lucas K.

    2015-10-01

    The author reports on high-fidelity simulations of charge carriers in the high-Tc cuprate materials using quantum Monte Carlo techniques applied to the first-principles Hamiltonian. With this high accuracy technique, the doped ground state is found to be a spin polaron, in which charge is localized through a strong interaction with the spin. This spin polaron has calculated properties largely similar to the phenomenology of the cuprates, and may be the object which forms the Fermi surface and charge inhomogeneity in these materials. The spin polaron has some unique features that should be visible in x-ray, EELS, and neutron experiments.

  10. 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.

  11. On the choice of trial function in theoretical calculations of the thermal conductivity

    SciTech Connect

    Pettersson, S. . Dept. of Physics and Astronomy)

    1989-10-01

    The dispersion relations for 17 alkali halides are calculated throughout the entire Brillouin zone with a deformation dipole model. The linearized Boltzmann equation, including only three-phonon scattering processes, is solved by a variational method. Several trial functions and linear combinations are tested. Separate trial functions are assumed for the acoustic and optic branches, respectively, which gives an improved estimate of the importance of optic phonons as heat carriers. The amount of heat carried by optic phonons differ greatly among the investigated crystals, from 2% up to 34%. The introduction of linear combination of trial functions increases the thermal conductivity values by 10-300%. 28 refs., 1 fig., 3 tabs.

  12. 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.

  13. 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.

  14. Theoretical investigations of quantum walks by cold atoms in a double optical lattice

    SciTech Connect

    Satapathy, Nandan; Ramachandran, Hema; Hagman, Henning; Zelan, Martin; Kastberg, Anders

    2009-07-15

    We investigate the feasibility of carrying out quantum walks with cold atoms in a double optical lattice. Monte Carlo simulations of time-of-flight (TOF) detection and absorption imaging were carried out, focusing on a specific experimental implementation. These indicate that absorption imaging would be best suited for detection of quantum walks. With typical experimental parameters a few hundred quantum walk steps will be needed for an unambiguous detection of the quantum walk signature. We show that in special cases, few-step quantum walks can also be detected in our system if one measures the relative population of the atoms in their internal states rather than their displacement in space, that is, measurements are made in the space of the coin operator rather than in that of the displacement operator.

  15. 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).

  16. 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

  17. Theoretical study and rate constants calculation for the reactions X + CF3CH2OCF3 (X = F, Cl, Br).

    PubMed

    Zhang, Hui; Liu, Yang; Liu, Jing-Yao; Li, Ze-Sheng

    2012-03-01

    The multiple-channel reactions X + CF3CH2OCF3 (X = F, Cl, Br) are theoretically investigated. The minimum energy paths (MEP) are calculated at the MP2/6-31 + G(d,p) level, and energetic information is further refined by the MC-QCISD (single-point) method. The rate constants for major reaction channels are calculated by canonical variational transition state theory (CVT) with small-curvature tunneling (SCT) correction over the temperature range 2002000 K. The theoretical three-parameter expressions for the three channels k1a(T) = 1.24 x 10(-15T1.24)exp(-304.81/T), k2a(T) = 7.27 x 10(-15T0.37)exp(-630.69/T), and k3a(T) = 2.84 x 10(-19T2.51)exp(-2725.17/T) cm3 molecule(-1) s(-1) are given. Our calculations indicate that hydrogen abstraction channel is only feasible channel due to the smaller barrier height among five channels considered. PMID:22420027

  18. 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.

  19. 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.

  20. 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.

  1. Infrared spectrum, molecular structure and theoretical calculation of 2-pyridone-6-carboxylic acid

    NASA Astrophysics Data System (ADS)

    Arslan, H.; ?engl, A.; Aygn, S.; Karaday?, N.; Bayar?, S. Haman

    2007-08-01

    The X-ray and infrared spectroscopic analysis of 2-pyridone-6-carboxylic acid are reported. The crystals of investigated molecule belong to P2 1/ c of the monoclinic system, a = 11.714 , b = 3.7088, c = 18.223 and ? = 123.71. The molecule is found in the ketonic form. Comprehensive studies of the molecular structures and vibrational frequencies and infrared intensities of the molecule have been performed by using Hartree-Fock, density functional B3LYP and second-order Moller-Plesset MP2 methods with the 6-31G+(d, p) basis set. The calculated geometrical parameters of investigated molecule in gas phase were compared with the experimental X-ray data.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. 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.

  8. 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.

  9. 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.

  10. Monte Carlo calculation of the quantum partition function via path integral formulations

    SciTech Connect

    Kono, H.; Takasaka, A.; Lin, S.H.

    1988-05-15

    Using Bennett's Monte Carlo (MC) method, we calculate the quantum partition functions of path integral formulations. First, from numerically exact results for a harmonic oscillator and a double-well potential, we discuss how fast each approximate partition function converges to the exact value as the number of integral variables involved in the formulation is increased. It turns out that most effective and most suitable for the MC simulation is Takahashi and Imada's path integral fomulation based on a modified Trotter formula in which the original potential is replaced with an effective one. This formulation is well balanced between the following two factors: the effect of zero potential energy is underestimated, resulting in an improper increase in the partition function; and, on the other hand, effective potential restricts the motion of fictitious particles born in the formulation so that the partition function value tends to be smaller. Fictitious particles can be treated as classical ones. We therefore can apply Bennett's MC method to calculating the ratio of two quantum partition functions (of a system under consideration and a reference system). As the number of fictitious particles N is increased, choice of reference system becomes less and less important and multistage sampling becomes dispensable. This, to some extent, compensates for the expense that N is larger than the real particle number. The tunneling mechanism of fictitious particles in the simulation is discussed.

  11. 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

  12. 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

  13. Theoretical calculation of the gas-sensing properties of Pt-decorated carbon nanotubes.

    PubMed

    Zhang, Xiaoxing; Dai, Ziqiang; Wei, Li; Liang, Naifeng; Wu, Xiaoqing

    2013-01-01

    The gas-sensing properties of Pt-decorated carbon nanotubes (CNTs), which provide a foundation for the fabrication of sensors, have been evaluated. In this study, we calculated the gas adsorption of Pt-decorated (8,0) single-wall CNTs (Pt-SWCNTs) with SO2, H2S, and CO using GGA/PW91 method based on density functional theory. The adsorption energies and the changes in geometric and electronic structures after absorption were comprehensively analyzed to estimate the responses of Pt-SWCNTs. Results indicated that Pt-SWCNTs can respond to the three gases. The electrical characteristics of Pt-SWCNTs show different changes after adsorption. Pt-SWCNTs donate electrons and increase the number of hole carriers after adsorbing SO2, thereby enhancing its conductivity. When H2S is adsorbed on CNTs, electrons are transferred from H2S to Pt-SWCNTs, converting Pt-SWCNTs from p-type to n-type sensors with improved conductivity. However, Pt-SWCNTs obtain electrons and show decreased conductivity when reacted with CO gas. PMID:24201317

  14. Theoretical investigation of lead vapor adsorption on kaolinite surfaces with DFT calculations.

    PubMed

    Wang, Xinye; Huang, Yaji; Pan, Zhigang; Wang, Yongxing; Liu, Changqi

    2015-09-15

    Kaolinite can be used as the in-furnace sorbent/additive to adsorb lead (Pb) vapor at high temperature. In this paper, the adsorptions of Pb atom, PbO molecule and PbCl2 molecule on kaolinie surfaces were investigated by density functional theory (DFT) calculation. Si surface is inert to Pb vapor adsorption while Al surfaces with dehydroxylation are active for the unsaturated Al atoms and the O atoms losing H atoms. The adsorption energy of PbO is much higher than that of Pb atom and PbCl2. Considering the energy barriers, it is easy for PbO and PbCl2 to adsorb on Al surfaces but difficult to escape. The high energy barriers of de-HCl process cause the difficulties of PbCl2 to form PbOAl2O32SiO2 with kaolinite. Considering the inertia of Si atoms and the activity of Al atoms after dehydroxylation, calcination, acid/alkali treatment and some other treatment aiming at amorphous silica producing and Al activity enhancement can be used as the modification measures to improve the performance of kaolinite as the in-furnace metal capture sorbent. PMID:25880048

  15. A Comparison of Three Theoretical Methods of Calculating Span Load Distribution on Swept Wings

    NASA Technical Reports Server (NTRS)

    VanDorn, Nicholas H.; DeYoung, John

    1947-01-01

    Three methods for calculating span load distribution, those developed by V.M Falkner, Wm. Mutterperl, and J. Weissinger, have been applied to five swept wings. The angles of sweep ranged from -45 degrees to +45 degrees. These methods were examined to establish their relative accuracy and case of application. Experimentally determined loadings were used as a basis for judging accuracy. For the convenience of the readers the computing forms and all information requisite to their application are included in appendixes. From the analysis it was found that the Weissinger method would be best suited to an over-all study of the effects of plan form on the span loading and associated characteristics of wings. The method gave good, but not best, accuracy and involved by far the least computing effort. The Falkner method gave the best accuracy but at a considerable expanse in computing effort and hence appeared to be most useful for a detailed study of a specific wing. The Mutterperl method offered no advantages in accuracy of facility over either of the other methods and hence is not recommended for use.

  16. 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 ?fH per carbon = 722n(-0.72) + 5.2 kJ mol(-1) (n = the number of carbon atoms), which enables an estimation of ?fH 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

  17. 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.

  18. 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 ? ?) of vanillin are as follows: < r(C-C) ring>=1.397(4) ; r(C 1-C aldehyde)=1.471(?) ; r(C 3-O Me)=1.374(9) ; r(C 4-O H)=1.361(?) ; r(O-C Me)=1.428(?) ; r(C dbnd6 O)=1.214(8) ; < r(C-H)>=1.110(11) ; r(O-H)=0.991(?) ; ?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) ; r(C 1-C aldehyde)=1.479(?) ; r(C 4-O Me)=1.369(9) ; r(C 3-O H)=1.357(?) ; r(O-C Me)=1.422(?) ; r(C dbnd6 O)=1.221(9) ; < r(C-H)>=1.114(14) ; r(O-H)=0.995(?) ; ?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) ; r(C 1-C aldehyde)=1.471(?) ; r(C 3-O Et)=1.365(13) ; r(C 4-O H)=1.352(?) ; r(O-C Et)=1.427(?) ; r(C-C Et)=1.494(21) ; r(C dbnd6 O)=1.206(9) ; < r(C-H)>=1.109(10) ; r(O-H)=0.990(?) ; ?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 ?) referring to the last significant digit; left arrows in the parentheses mean that these parameters are bound to the preceding one.

  19. 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.

  20. 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

  1. 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).

  2. 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)

  3. 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

  4. Quantum mechanical scattering calculations for collisions of oxygen + hydrogen ion and oxygen ion + hydrogen

    NASA Astrophysics Data System (ADS)

    Spirko, Jeffery A.

    2001-10-01

    Thermal energy collisions of oxygen atoms with protons (O + H +) may lead to fine-structure excitation of the oxygen or to charge exchange (O+ + H). The reverse process, oxygen-ion collisions with hydrogen, is also possible. Detailed quantum mechanical calculations of these processes are presented here. Cross sections and rate constants for a wide range of energies and temperatures are reported. The first stage of the work was the determination of appropriate potential curves and coupling terms for the OH+ molecule. Large scale electronic structure calculations for the lowest 3? - states are performed using the GAMESS computer code. A large CI wave function is calculated based on single and double excitations from a CASSCF reference space. The block diagonalization method is implemented to determine ``diabatic'' potential curves for the 3? - symmetry; these curves contain the important charge exchange coupling terms. The other necessary potentials, the A 3? and 1 5?- curves, were taken from the literature. The second stage was the solution of the quantum mechanical equations of nuclear motion using coupled channel theory. Cross sections for charge exchange and fine structure excitation are reported. For several transitions, mechanisms based on curve crossings are proposed. The analysis indicates that the scattering cross sections are sensitive to the form of the molecular potentials for the internuclear distances of 10-15 a0. The only point of comparison with experiment is for rate constants for charge exchange, averaged over fine structure levels. The present results lie within the large error bars of the limited experimental data.

  5. 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 10004000 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.

  6. 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.

  7. The Quantum Measurement Problem and Physical reality: A Computation Theoretic Perspective

    NASA Astrophysics Data System (ADS)

    Srikanth, R.

    2006-11-01

    Is the universe computable? If yes, is it computationally a polynomial place? In standard quantum mechanics, which permits infinite parallelism and the infinitely precise specification of states, a negative answer to both questions is not ruled out. On the other hand, empirical evidence suggests that NP-complete problems are intractable in the physical world. Likewise, computational problems known to be algorithmically uncomputable do not seem to be computable by any physical means. We suggest that this close correspondence between the efficiency and power of abstract algorithms on the one hand, and physical computers on the other, finds a natural explanation if the universe is assumed to be algorithmic; that is, that physical reality is the product of discrete sub-physical information processing equivalent to the actions of a probabilistic Turing machine. This assumption can be reconciled with the observed exponentiality of quantum systems at microscopic scales, and the consequent possibility of implementing Shor's quantum polynomial time algorithm at that scale, provided the degree of superposition is intrinsically, finitely upper-bounded. If this bound is associated with the quantum-classical divide (the Heisenberg cut), a natural resolution to the quantum measurement problem arises. From this viewpoint, macroscopic classicality is an evidence that the universe is in BPP, and both questions raised above receive affirmative answers. A recently proposed computational model of quantum measurement, which relates the Heisenberg cut to the discreteness of Hilbert space, is briefly discussed. A connection to quantum gravity is noted. Our results are compatible with the philosophy that mathematical truths are independent of the laws of physics.

  8. 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

  9. 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

  10. 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.)

  11. Calculation of output characteristics of semiconductor quantum-well lasers with account for both electrons and holes

    SciTech Connect

    Sokolova, Z N; Tarasov, I S; Asryan, L V

    2014-09-30

    Using an extended theoretical model, which includes the rate equations for both electrons and holes, we have studied the output characteristics of semiconductor quantum-well lasers. We have found non-trivial dependences of electron and hole concentrations in the waveguide region of the laser on the capture velocities of both types of carriers from the waveguide region into the quantum well. We have obtained the dependences of the internal differential quantum efficiency and optical output power of the laser on the capture velocities of electrons and holes. An increase in the capture velocities has been shown to result in suppression of parasitic recombination in the waveguide region and therefore in a substantial increase in the quantum efficiency and output power. (lasers)

  12. The optical properties and quantum chemical calculations of thienyl and furyl derivatives of pyrene.

    PubMed

    Idzik, Krzysztof R; Cywi?ski, 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

  13. Transmission zero in a quantum dot with strong electron-electron interaction: Perturbative conductance calculations

    NASA Astrophysics Data System (ADS)

    Kim, Sejoong; Lee, Hyun-Woo

    2006-05-01

    A pioneering experiment [E. Schuster, E. Buks, M. Heiblum, D. Mahalu, V. Umansky, and Hadas Shtrikman, Nature 385, 417 (1997)] reported the measurement of the transmission phase of an electron traversing a quantum dot and found the intriguing feature of a sudden phase drop in the conductance valleys. Based on the Friedel sum rule for a spinless effective one-dimensional system, it has been previously argued [H.-W. Lee, Phys. Rev. Lett. 82, 2358 (1999)] that the sudden phase drop should be accompanied by the vanishing of the transmission amplitude, or transmission zero. Here we address roles of strong electron-electron interactions on the electron transport through a two-level quantum dot where one level couples with the leads much more strongly than the other level does [P. G. Silvestrov and Y. Imry, Phys. Rev. Lett. 85, 2565 (2000)]. We perform a perturbative conductance calculation with an explicit account of large charging energy and verify that the resulting conductance exhibits transmission zero, in agreement with the analysis based on the Friedel sum rule.

  14. Quantum mechanical calculations related to ionization and charge transfer in DNA

    NASA Astrophysics Data System (ADS)

    Caut, E.; Valiev, M.; Weare, J. H.; Livin, J.

    2012-07-01

    Ionization and charge migration in DNA play crucial roles in mechanisms of DNA damage caused by ionizing radiation, oxidizing agents and photo-irradiation. Therefore, an evaluation of the ionization properties of the DNA bases is central to the full interpretation and understanding of the elementary reactive processes that occur at the molecular level during the initial exposure and afterwards. Ab initio quantum mechanical (QM) methods have been successful in providing highly accurate evaluations of key parameters, such as ionization energies (IE) of DNA bases. Hence, in this study, we performed high-level QM calculations to characterize the molecular energy levels and potential energy surfaces, which shed light on ionization and charge migration between DNA bases. In particular, we examined the IEs of guanine, the most easily oxidized base, isolated and embedded in base clusters, and investigated the mechanism of charge migration over two and three stacked guanines. The IE of guanine in the human telomere sequence has also been evaluated. We report a simple molecular orbital analysis to explain how modifications in the base sequence are expected to change the efficiency of the sequence as a hole trap. Finally, the application of a hybrid approach combining quantum mechanics with molecular mechanics brings an interesting discussion as to how the native aqueous DNA environment affects the IE threshold of nucleobases.

  15. FragIt: a tool to prepare input files for fragment based quantum chemical calculations.

    PubMed

    Steinmann, Casper; Ibsen, Mikael W; Hansen, Anne S; Jensen, Jan H

    2012-01-01

    Near linear scaling fragment based quantum chemical calculations are becoming increasingly popular for treating large systems with high accuracy and is an active field of research. However, it remains difficult to set up these calculations without expert knowledge. To facilitate the use of such methods, software tools need to be available to support these methods and help to set up reasonable input files which will lower the barrier of entry for usage by non-experts. Previous tools relies on specific annotations in structure files for automatic and successful fragmentation such as residues in PDB files. We present a general fragmentation methodology and accompanying tools called FragIt to help setup these calculations. FragIt uses the SMARTS language to locate chemically appropriate fragments in large structures and is applicable to fragmentation of any molecular system given suitable SMARTS patterns. We present SMARTS patterns of fragmentation for proteins, DNA and polysaccharides, specifically for D-galactopyranose for use in cyclodextrins. FragIt is used to prepare input files for the Fragment Molecular Orbital method in the GAMESS program package, but can be extended to other computational methods easily. PMID:23028546

  16. 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.

  17. 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.

  18. Theoretical calculations for structural, elastic, and thermodynamic properties of RuN{sub 2} under high pressure

    SciTech Connect

    Dong, Bing; Zhou, Xiao-Lin E-mail: lkworld@126.com; Chang, Jing; Liu, Ke E-mail: lkworld@126.com

    2014-08-07

    The structural and elastic properties of RuN{sub 2} were investigated through the first-principles calculation using generalized gradient approximation (GGA) and local density approximation (LDA) within the plane-wave pseudopotential density functional theory. The obtained equilibrium structure and mechanical properties are in excellent agreement with other theoretical results. Then we compared the elastic modulus of RuN{sub 2} with several other isomorphic noble metal nitrides. Results show that RuN{sub 2} can nearly rival with OsN{sub 2} and IrN{sub 2}, which indicate RuN{sub 2} is a potentially ultra-incompressible and hard material. By the elastic stability criteria, it is predicted that RuN{sub 2} is stable in our calculations (0100?GPa). The calculated B/G ratios indicate that RuN{sub 2} possesses brittle nature at 0?GPa and when the pressure increases to 13.4?GPa (for LDA) or 20.8?GPa (for GGA), it begins to prone to ductility. Through the quasi-harmonic Debye model, we also investigated the thermodynamic properties of RuN{sub 2}.

  19. 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.

  20. 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.

  1. Quantum three-body calculation of nonresonant triple-? reaction rate at low temperatures

    NASA Astrophysics Data System (ADS)

    Ogata, Kazuyuki; Kan, Masataka; Kamimura, Masayasu

    2010-06-01

    Triple-? reaction rate is re-evaluated by directly solving the three-body Schrdinger 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 ?-? nonresonant states significantly quenches the Coulomb barrier between the first two ?-particles and the third ?-particle. Consequently, the ?-? 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-? reaction rate by 26 orders of magnitude around 107 K compared with the rate of NACRE.

  2. 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 Schrdinger 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.

  3. Free-Radical-Induced DNA Damage as Approached by Quantum-Mechanical and Monte Carlo Calculations

    NASA Astrophysics Data System (ADS)

    von Sonntag, Clemens

    The free-radical chemistry of DNA and its model systems has been widely studied by experimentalists as well as theoreticians. In the present paper, the important contributions of theory to a better understanding of this complex matter has been reviewed by an experimentalist with an emphasis on the following topics: modeling of DNA damage induced by ionizing radiation, pattern of -OH attack on DNA, ionization potentials and electron affinities of the nucleobases (reduction potentials), hole and electron transfer through DNA, tautomerization and isomerization reactions of DNA radicals, regioselectivity of -OH attack on the nucleobases, selectivity of free-radical attack at the sugar moiety, reactions of alkyl radicals, assignment of transients by quantum-chemical calculations of their electronic transitions, reduction potentials of DNA radicals, and DNA stability and repair. Some pending questions that may be tackled by theoreticians are addressed.

  4. Electronic structure calculations of PbS quantum rods and tubes

    NASA Astrophysics Data System (ADS)

    Pimachev, Artem; Dahnovsky, Yuri

    2014-01-01

    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 Se-Sh 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.

  5. 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

  6. Constraining the Skyrme energy density functional with quantum Monte Carlo calculations

    NASA Astrophysics Data System (ADS)

    Roggero, Alessandro; Mukherjee, Abhishek; Pederiva, Francesco

    2015-11-01

    We study the problem of an impurity in fully polarized (spin-up) low-density neutron matter with the help of an accurate quantum Monte Carlo method in conjunction with a realistic nucleon-nucleon interaction derived from chiral effective field theory at next-to-next-to leading order. Our calculations show that the behavior of the proton spin-down impurity is very similar to that of a polaron in a fully polarized unitary Fermi gas. We show that our results can be used to put tight constraints on the time-odd parts of the Skyrme energy density functional, independent of the time-even parts, in the density regime relevant to neutron-rich nuclei and compact astrophysical objects such as neutron stars and supernovae.

  7. 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.

  8. Quantum-Chemical Calculations of Carbon-Isotope Fractionation in CO2(g), Aqueous Carbonate Species, and Carbonate Minerals

    SciTech Connect

    Rustad, James R.; Nelmes, Sierra L.; Jackson, Virgil E.; Dixon, David A.

    2008-01-24

    Quantum chemical calculations on large supermolecular carbonate-water and carbonate mineral clusters are used to predict equilibrium constants for 13,12C-isotope-exchange reactions between CO2(g), aqueous carbonate species, and the common carbonate minerals. For the aqueous species, we evaluate the influence of the size and conformational variability of the solvation shell, the exchange-correlation functional, and the basis set. The choice of exchange-correlation functional (PBE vs B3LYP), the basis set (6-31G* vs aug-cc-pVDZ), and solvation shell size (first shell only vs first shell and a partial second shell) each produce changes of ~5-10 per mil in the reduced partition function ratio. Conformational variability gives rise to a standard error of ~0.5 per mil using ~10 solute-solvent conformations. The best results are obtained with the B3LYP/ aug-cc-pVDZ combination, but because the improvements in the basis set and exchange correlation functional drive the reduced partition function ratios in opposite directions, reasonably good results are also obtained with the PBE/6-31G* combination. To construct molecular clusters representative of mineral environments, a new method is introduced on the basis of conservation of Pauling bond strength. Using these clusters as models for minerals, calculations of mineral-gas and mineral-aqueous carbon-isotope fractionation factors, are in good agreement with experimental measurements. Carbon-isotope fractionation factors for gas, aqueous, and mineral phases are thus integrated into a single theoretical/computational framework.

  9. Spectroscopic analysis of 3-Bromodiphenylamine with experimental techniques and quantum chemical calculations.

    PubMed

    Sudharsan, A; Seshadri, S; Gnanasambandan, T; Saravanan, R R

    2014-10-15

    In this work, the vibrational spectral analysis was carried out by using FT-Raman and FT-IR spectroscopy in the range 3500-100cm(-1) and 4000-400cm(-1), respectively, for 3-Bromodiphenylamine (3BDPA). Theoretical calculations were performed by using Density Functional Theory (DFT) method with 6-31G(d,p) and 6-311++G(d,p) basis sets. The complete vibrational assignments of wavenumbers were made on the basis of potential energy distribution (PED). The calculated wavenumbers were applied to simulate spectra of the title compound, which show excellent agreement with observed spectra. The frontier orbital energy gap and dipole moment illustrates the high reactivity of the title molecule. The first order hyperpolarizability (?0) and related properties (?, ? and ??) of the molecule were also calculated. Stability of the molecule arising from hyperconjugative interactions and charge delocalization were analyzed using natural bond orbital (NBO) analysis. The results show that electron density (ED) in the ?(*) and ?(*) anti-bonding orbitals and second order delocalization energies (E2) confirm the occurrence of intramolecular charge transfer (ICT) within the molecule. Molecular electrostatic potential (MEP) and HOMO-LUMO energy levels are also constructed. The thermodynamic properties of the title compound were calculated at different temperatures and the results reveals the heat capacity (C), and entropy (S) increases with rise in temperature. PMID:24835947

  10. Density functional theory calculations of the electric-field-induced Dirac cones and quantum valley Hall state in ABA-stacked trilayer graphene

    NASA Astrophysics Data System (ADS)

    Lee, Kyu Won; Lee, Cheol Eui

    2015-12-01

    We have investigated ABA-stacked trilayer graphene under a perpendicular electric field by using the density functional theory (DFT) calculations, which may contribute to the resolution of the discrepancies between experimental and theoretical results on the electric-field-induced band gap and topological phase transition. We found that the electric field opens a band gap at a low field and closes the gap at a high field, supporting one of the experimental results. While the seven electric-field-induced Dirac cones with mass gaps predicted in recent tight-binding (TB) models are confirmed, our DFT calculations demonstrate a phase transition from a quantum valley Hall insulator to a semimetal, contrasting to the TB model prediction of a topological phase transition between topologically nontrivial insulators at a high electric field.

  11. Electronic structure calculation of single and coupled self-assembled quantum dots

    NASA Astrophysics Data System (ADS)

    Mlinar, Vladan

    There are two main contributions of this thesis. First, from the theoretical point of view, we find that different treatments of the nanostructure-barrier interface in the framework of multiband effective-mass theory, result in the existence of non-physical solutions for the hole energy levels of a nanostructure. Our proposed improvement is an approach based on the envelope-function theory for nanostructures developed by Burt and Foreman. In structures with a large difference of the structural parameters between the constituent materials, such as InAs/GaAs quantum nanostructures, the conventional multiband models lead to non-physical solutions. Second, we investigate underlying physics of the theoretically less investigated QD systems. Variation of electronic and optical properties of InAs/GaAs QDs and QDM grown on [11k] substrates, where k=1,2,3 were analyzed and we found that: (i) The QD size in the growth direction determines the degree of influence of the substrate orientation: the flatter the dots, the larger the difference from the reference [001] case. (ii) The small variation of inter-dot distance in eight QD molecule qualitatively changes the transition energy dependence on the substrate orientation. (iii) Size of the QD in the growth direction determines the influence of the (In,Ga)As capping layer on the optical properties of [11k] grown InAs QDs, where k=1,2,3. Next, two cases of type II QDs where hole is localized outside the dot, were discussed: InP/InGaP QDs and QDMs in an external magnetic field, and InAs QDs capped with Ga(As,Sb). Competition between confinement, quantum mechanical coupling, and strain influence the exciton diamagnetic shift in single QD and double and triple QDM is investigated in details. Available experimental data were successfully described by one of the optically active exciton states of the lowest lying exciton quartet. Finally, the electronic and optical properties of unstrained GaAs self-assembled QDs with precisely known sizes and shape, placed in an external magnetic field are investigated. For magnetic fields applied both, in growth direction and perpendicular to it (B?50T), we found good agreement between our predicted exciton diamagnetic shift and recent experimental magneto-photoluminescence data.

  12. 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.

  13. Theoretical study of quantum capacitance and associated delay in armchair-edge graphene nanoribbons

    NASA Astrophysics Data System (ADS)

    Hassan, Asif; Hossain, Md. Faruque; Rana, Md. Sohel; Kouzani, Abbas Z.

    2015-09-01

    This work presents a comprehensive investigation of the quantum capacitance and the associated effects on the carrier transit delay in armchair-edge graphene nanoribbons (A-GNRs) based on semi-analytical method. We emphasize on the realistic analysis of bandgap with taking edge effects into account by means of modified tight binding (TB) model. The results show that the edge effects have significant influence in defining the bandgap which is a necessary input in the accurate analyses of capacitance. The quantum capacitance is discussed in both nondegenerate (low gate voltage) and degenerate (high gate voltage) regimes. We observe that the classical capacitance limits the total gate (external) capacitance in the degenerate regime, whereas, quantum capacitance limits the external gate capacitance in the nondegenerate regime. The influence of gate capacitances on the gate delay is studied extensively to demonstrate the optimization of switching time. Moreover, the high-field behavior of a GNR is studied in the degenerate and nondegenerate regimes. We find that a smaller intrinsic capacitance appears in the channel due to high velocity carrier, which limits the quantum capacitance and thus limit the gate delay. Such detail analysis of GNRs considering a realistic model would be useful for the optimized design of GNR-based nanoelectronic devices.

  14. 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.

  15. 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…

  16. 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.

  17. Experimental and theoretical study of optical properties and quantum size phenomena in the BiVO4/TiO2 nanostructures

    NASA Astrophysics Data System (ADS)

    Zalfani, M.; Mahdouani, M.; Bourguiga, R.; Su, B. L.

    2015-07-01

    Novel BiVO4/3DOM TiO2 nanostructure has been synthesized by hydrothermal method. BiVO4 nanoparticles and TiO2 inverse opal structure have also been prepared as reference. The prepared samples were characterized by Diffuse reflectance UV-Visible and photoluminescence (PL) spectroscopy. The absorption spectra of BiVO4/TiO2 nanocomposite samples show an absorption edge in the visible region, suggesting the potential application of this composite as an active visible-light driven photocatalysts. Theoretically quantum confinement phenomena and size dependent optical properties of BiVO4 quantum dots have been also studied. Using the effective mass approximation model, we computed the optical properties for spherical BiVO4 nanoparticles incorporated in TiO2 matrix. The size dependent of charge carrier's energies were calculated. The result shows that the confinement energy decreases with increase the size of BiVO4 nanoparticles. Dielectric properties of the BiVO4 nanoparticles were investigated and it was found that the dielectric constant decreases significantly as the size is reduced as a result the exciton energy decreases. It has been also found that the radiative recombination lifetime is concurrently enhanced with decreasing BiVO4 QDs size.

  18. 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.

  19. 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.

  20. Half-Lives for Proton Emission, Alpha Decay, Cluster Radioactivity, and Cold Fission Processes Calculated in a Unified Theoretical Framework

    NASA Astrophysics Data System (ADS)

    Duarte, S. B.; Tavares, O. A. P.; Guzmn, F.; Dimarco, A.; Garca, F.; Rodrguez, O.; Gonalves, M.

    2002-03-01

    Half-life values of spontaneous nuclear decay processes are presented in the framework of the effective liquid drop model (ELDM) using the combination of varying mass asymmetry shape description for the mass transfer (VMAS) and Werner-Wheeler's inertia coefficient (WW). The calculated half lives of ground-state to ground-state transitions for proton emission, alpha decay, cluster radioactivity, and cold fission processes are compared with experimental data. These comparisons show that the ELDM is a very efficient model to describe these different decay processes in a same, unified, theoretical framework. A table listing the predicted half-life values, ?c, is presented for all possible cases of spontaneous nuclear breakup such that -7.30?log10?c [s]?27.50 and log10(?/?c)>-17.0, where ? is the total half life of the parent nucleus.

  1. Electron-ion recombination of Fe{sup 12+} forming Fe{sup 11+}: Laboratory measurements and theoretical calculations

    SciTech Connect

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

    2014-06-10

    We have measured dielectronic recombination (DR) for Fe{sup 12+} forming Fe{sup 11+} 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.

  2. 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.

  3. 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 ? ?) of the most abundant conformer of carvone are as follows: < r(C-C)>=1.520(3) ; < r(C?C)>=1.360(5) ; r(C?O)=1.225(5) ; < r(C-H)>=1.104(4); =121.1(5); =110.4(5); ?C-CO-C=117.1(14); =111.1(13). Angle brackets denote average values and parenthesized values are the estimated limits of error (3 ?) referring to the last significant digit.

  4. 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.

  5. 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.

  6. 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.

  7. Raman spectroscopic features of the neutral vacancy in diamond from ab initio quantum-mechanical calculations.

    PubMed

    Baima, Jacopo; Zelferino, Alessandro; Olivero, Paolo; Erba, Alessandro; Dovesi, Roberto

    2016-01-21

    Quantum-mechanical ab initio calculations are performed to elucidate the vibrational spectroscopic features of a common irradiation-induced defect in diamond, i.e. the neutral vacancy. Raman spectra are computed analytically through a Coupled-Perturbed-Hartree-Fock/Kohn-Sham approach as a function of both different defect spin states and defect concentration. The experimental Raman features of defective diamond located in the 400-1300 cm(-1) spectral range, i.e. below the first-order line of pristine diamond at 1332 cm(-1), are well reproduced, thus corroborating the picture according to which, at low damage densities, this spectral region is mostly affected by non-graphitic sp(3) defects. No peaks above 1332 cm(-1) are found, thus ruling out previous tentative assignments of different spectral features (at 1450 and 1490 cm(-1)) to the neutral vacancy. The perturbation introduced by the vacancy to the thermal nuclear motion of carbon atoms in the defective lattice is discussed in terms of atomic anisotropic displacement parameters (ADPs), computed from converged lattice dynamics calculations. PMID:26686374

  8. 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.

  9. 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.

  10. 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.

  11. Quantum Monte Carlo calculations of nuclei with A{le}7

    SciTech Connect

    Pudliner, B.S.; Pandharipande, V.R.; Carlson, J.; Pieper, S.C.; Wiringa, R.B.

    1997-10-01

    We report quantum Monte Carlo calculations of ground and low-lying excited states for nuclei with A{le}7 using a realistic Hamiltonian containing the Argonne v{sub 18} two-nucleon and Urbana IX three-nucleon potentials. A detailed description of the Green{close_quote}s-function Monte Carlo algorithm for systems with state-dependent potentials is given and a number of tests of its convergence and accuracy are performed. We find that the Hamiltonian being used results in ground states of both {sup 6}Li and {sup 7}Li that are stable against breakup into subclusters, but somewhat underbound compared to experiment. We also have results for {sup 6}He, {sup 7}He, and their isobaric analogs. The known excitation spectra of all these nuclei are reproduced reasonably well and we predict a number of excited states in {sup 6}He and {sup 7}He. We also present spin-polarized one-body and several different two-body density distributions. These are the first microscopic calculations that directly produce nuclear shell structure from realistic interactions that fit NN scattering data. {copyright} {ital 1997} {ital The American Physical Society}

  12. 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).

  13. 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).

  14. 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.

  15. 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

  16. Accurate quantum dynamics calculations of vibrational spectrum of dideuteromethane CH2D2.

    PubMed

    Yu, Hua-Gen

    2015-05-21

    We report a rigorous variational study of the infrared (IR) vibrational spectra of both CH2D2 and (13)CH2D2 isotopomers using an exact molecular Hamiltonian. Calculations are carried out using a recently developed multi-layer Lanczos algorithm based on the accurate refined Wang and Carrington potential energy surface of methane and the low-order truncated ab initio dipole moment surface of Yurchenko et al. [J. Mol. Spectrosc. 291, 69 (2013)]. All well converged 357 vibrational energy levels up to 6100 cm(-1) of CH2D2 are obtained, together with a comparison to previous calculations and 91 experimental bands available. The calculated frequencies are in excellent agreement with the experimental results and give a root-mean-square error of 0.67?cm(-1). In particular, we also compute the transition intensities from the vibrational ground state for both isotopomers. Based on the theoretical results, 20 experimental bands are suggested to be re-assigned. Surprisingly, an anomalous C isotopic effect is discovered in the n?5 modes of CH2D2. The predicted IR spectra provide useful information for understanding those unknown bands. PMID:26001461

  17. 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.

  18. Decades of Theoretical Work on Protonated Hydrates

    NASA Astrophysics Data System (ADS)

    Kochanski, E.; Kelterbaum, R.; Klein, S.; Rohmer, M. M.; Rahmouni, A.

    Theoretical studies on protonated hydrates (PH) are illustrative of the progress realized in theoretical chemistry over several decades. The evolution of such studies is presented. The main methods used (quantum chemistry, Monte Carlo or Molecular Dynamics calculations...) and the problems encountered are briefly recalled. Some of the results obtained are commented.

  19. 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

  20. 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.

  1. 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

  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, ?. 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. 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.

  4. Theoretical study on electromagnetically induced transparency in molecular aggregate models using quantum Liouville equation method

    SciTech Connect

    Minami, Takuya; Nakano, Masayoshi

    2015-01-22

    Electromagnetically induced transparency (EIT), which is known as an efficient control method of optical absorption property, is investigated using the polarizability spectra and population dynamics obtained by solving the quantum Liouville equation. In order to clarify the intermolecular interaction effect on EIT, we examine several molecular aggregate models composed of three-state monomers with the dipole-dipole coupling. On the basis of the present results, we discuss the applicability of EIT in molecular aggregate systems to a new type of optical switch.

  5. 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.

  6. Simple theoretical analysis of the photoemission from quantum confined effective mass superlattices of optoelectronic materials.

    PubMed

    De, Debashis; Bhattacharya, Sitangshu; Adhikari, S M; Kumar, A; Bose, P K; Ghatak, K P

    2011-01-01

    The photoemission from quantum wires and dots of effective mass superlattices of optoelectronic materials was investigated on the basis of newly formulated electron energy spectra, in the presence of external light waves, which controls the transport properties of ultra-small electronic devices under intense radiation. The effect of magnetic quantization on the photoemission from the aforementioned superlattices, together with quantum well superlattices under magnetic quantization, has also been investigated in this regard. It appears, taking HgTe/Hg(1-) (x)Cd(x)Te and In(x)Ga(1-) (x)As/InP effective mass superlattices, that the photoemission from these quantized structures is enhanced with increasing photon energy in quantized steps and shows oscillatory dependences with the increasing carrier concentration. In addition, the photoemission decreases with increasing light intensity and wavelength as well as with increasing thickness exhibiting oscillatory spikes. The strong dependence of the photoemission on the light intensity reflects the direct signature of light waves on the carrier energy spectra. The content of this paper finds six different applications in the fields of low dimensional systems in general. PMID:22003442

  7. Electronic structure of silicon nitride according to ab initio quantum-chemical calculations and experimental data

    SciTech Connect

    Nekrashevich, S. S. Gritsenko, V. A.; Klauser, R.; Gwo, S.

    2010-10-15

    Charge transfer {Delta}Q = 0.35e at the Si-N bond in silicon nitride is determined experimentally using photoelectron spectroscopy, and the ionic formula of silicon nitride Si{sub 3}{sup +1.4}N{sub 4}{sup -1.05} is derived. The electronic structure of {alpha}-Si{sub 3}N{sub 4} is studied ab initio using the density functional method. The results of calculations (partial density of states) are compared with experimental data on X-ray emission spectroscopy of amorphous Si{sub 3}N{sub 4}. The electronic structure of the valence band of amorphous Si{sub 3}N{sub 4} is studied using synchrotron radiation at different excitation energies. The electron and hole effective masses m{sub e}{sup *} {approx} m{sub h}{sup *} {approx} 0.5m{sub e} are estimated theoretically. The calculated values correspond to experimental results on injection of electrons and holes into silicon nitride.

  8. Molecular structure, spectroscopic assignments and other quantum chemical calculations of anticancer drugs - A review.

    PubMed

    Ghasemi, A S; Deilam, M; Sharifi-Rad, J; Ashrafi, F; Hoseini-Alfatemi, S M

    2015-01-01

    In many texts, both theoretical and experimental studies on molecular structure and spectroscopic assignments of anticancer medicines have been reported. Molecular geometry parameters have been experimentally obtained by x-ray structure determination method and optimized using computational chemistry method like density functional theory. In this review, we consider calculations based on density function theory at B3LYP/6-31G (d,p) and B3LYP/6-311++G (d,p) levels of theory. Based on optimized geometric parameters of the molecules, molecular structures (length of bonds, bond angles and torsion angles) and vibrational assignments have been obtained. Molecular stability and bond strength have been investigated by applying natural bond orbital (NBO) analysis. Other molecular properties such as mulliken population analysis, thermodynamic properties and polarizabitities of these drugs have been reported. Calculated energies of HOMO and LUMO show that charge transfer occurs in the molecular. Information about the size, shape, charge density distribution and site of molecular chemical reactivity has been obtained by mapping electron density isosurface of electrostatic and compared with experiment data. PMID:26638891

  9. Relevance of silicate surface morphology in interstellar H2 formation. Insights from quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Navarro-Ruiz, Javier; Martnez-Gonzlez, Jos ngel; 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.

  10. Thermal Decomposition of NCN: Shock-Tube Study, Quantum Chemical Calculations, and Master-Equation Modeling.

    PubMed

    Busch, Anna; Gonzlez-Garca, Nria; Lendvay, Gyrgy; 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

  11. 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.

  12. 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).

  13. 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.

  14. Elucidating triplet-sensitized photolysis mechanisms of sulfadiazine and metal ions effects by quantum chemical calculations.

    PubMed

    Wang, Se; Song, Xuedan; Hao, Ce; Gao, Zhanxian; Chen, Jingwen; Qiu, Jieshan

    2015-03-01

    Sulfadiazine (SDZ) mainly proceeds triplet-sensitized photolysis with dissolved organic matter (DOM) in the aquatic environment. However, the mechanisms underlying the triplet-sensitized photolysis of SDZ with DOM have not been fully worked out. In this study, we investigated the mechanisms of triplet-sensitized photolysis of SDZ(0) (neutral form) and SDZ(-) (anionic form) with four DOM analogues, i.e., fluorenone (FL), thioxanthone (TX), 2-acetonaphthone (2-AN), and 4-benzoylbenzoic acid (CBBP), and three metal ions (i.e., Mg(2+), Ca(2+), and Zn(2+)) effects using quantum chemical calculations. Results indicated that the triplet-sensitized photolysis mechanism of SDZ(0) with FL, TX, and 2-AN was hydrogen transfer, and with CBBP was electron transfer along with proton transfer (for complex SDZ(0)-CBBP2) and hydrogen transfer (for complex SDZ(0)-CBBP1). The triplet-sensitized photolysis mechanisms of SDZ(-) with FL, TX, and CBBP was electron transfer along with proton transfer, and with 2-AN was hydrogen transfer. The triplet-sensitized photolysis product of both SDZ(0) and SDZ(-) was a sulfur dioxide extrusion product (4-(2-iminopyrimidine-1(2H)-yl)aniline), but the formation routs of the products for SDZ(0) and SDZ(-) were different. In addition, effects of the metal ions on the triplet-sensitized photolysis of SDZ(0) and SDZ(-) were different. The metal ions promoted the triplet-sensitized photolysis of SDZ(0), but inhibited the triplet-sensitized photolysis of SDZ(-). PMID:25496743

  15. 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. © 2015 Wiley Periodicals, Inc. PMID:26561362

  16. 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

  17. 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.

  18. A general rigorous quantum dynamics algorithm to calculate vibrational energy levels of pentaatomic molecules

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen

    2009-08-01

    An exact variational algorithm is presented for calculating vibrational energy levels of pentaatomic molecules without any dynamical approximation. The quantum mechanical Hamiltonian of the system is expressed in a set of orthogonal coordinates defined by four scattering vectors in the body-fixed frame. The eigenvalue problem is solved using a two-layer Lanczos iterative diagonalization method in a mixed grid/basis set. A direct product potential-optimized discrete variable representation (PO-DVR) basis is used for the radial coordinates while a non-direct product finite basis representation (FBR) is employed for the angular variables. The two-layer Lanczos method requires only the actions of the Hamiltonian operator on the Lanczos vectors, where the potential-vector products are accomplished via a pseudo-spectral transform technique. By using Jacobi, Radau and orthogonal satellite vectors, we have proposed 21 types of orthogonal coordinate systems so that the algorithm is capable of describing most five-atom systems with small and/or large amplitude vibrational motions. Finally, an universal program ( PetroVib) has been developed. Its applications to the molecules CH and HO2-, and the van der Waals cluster HeCl are also discussed.

  19. 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

  20. The molecular structure of gaseous 1,4-dioxane: An electron-diffraction reinvestigation aided by theoretical calculations

    NASA Astrophysics Data System (ADS)

    Fargher, Mitchell; Hedberg, Lise; Hedberg, Kenneth

    2014-08-01

    The structure of the molecule 1,4-dioxane (DIOX) has some features in common with other ring systems previously studied in this laboratory. In contrast to 1,4-cyclohexanedione, however, which consists both of a twisted boat form of D2 symmetry and a chair form of C2h symmetry, DIOX was reported, in two much earlier studies, to exist only as the chair form. The results of our work are in agreement with the earlier conclusions that gaseous DIOX exists either entirely, or essentially entirely (less than a few percent) in the chair form. Our work is much more extensive than the previous studies, and, aided by high-level theoretical molecular orbital- and normal-coordinate calculations, yielded the following bond distances (rg/) and bond angles (??/deg). = 1.104 (4), C-O = 1.420 (2), C-C = 1.514 (4), = 105.4 (55), H-C-H = 108.0 (26), C-C-O = 111.1 (3), C-O-C = 110.9 (10). The flap angle - the angle by which the COC plane is tilted up from the plane of the four carbon atoms - is equal to 50.6 (7). The structure is discussed and compared with the previous work and with predictions from theory.

  1. 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.

  2. 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

  3. Effect of terrestrial radiation on brightness temperature at lunar nearside: Based on theoretical calculation and data analysis

    NASA Astrophysics Data System (ADS)

    Wei, Guangfei; Li, Xiongyao; Wang, Shijie

    2015-02-01

    Terrestrial radiation is another possible source of heat in lunar thermal environment at its nearside besides the solar illumination. On the basis of Clouds and the Earth's Radiant Energy System (CERES) data products, the effect of terrestrial radiation on the brightness temperature (TBe) of the lunar nearside has been theoretically calculated. It shows that the mafic lunar mare with high TBe is more sensitive to terrestrial radiation than the feldspathic highland with low TBe value. According to the synchronous rotation of the Moon, we extract TBe on lunar nearside using the microwave radiometer data from the first Chinese lunar probe Chang'E-1 (CE-1). Consistently, the average TBe at Mare Serenitatis is about 1.2 K while the highland around the Geber crater (19.4S, 13.9E) is relatively small at ?0.4 K. Our results indicate that there is no significant effect of terrestrial radiation on TBe at the lunar nearside. However, to extract TBe accurately, effects of heat flow, rock abundance and subsurface rock fragments which are more significant should be considered in the future work.

  4. Theoretical study of electronic absorptions in aminopyridines - TCNE CT complexes by quantum chemical methods, including solvent.

    PubMed

    Mach, Pavel; Juhsz, Gyrgy; Kyse?, Ondrej

    2013-11-01

    The geometric and electronic structure of donor-acceptor complexes of TCNE with aniline, o-, m- and p- aminopyridines and pyridine has been studied in gas phase and in solution using CC2, TDDFT and CIS methods. Concerning interaction energy between particular donor and TCNE acceptor it is fairly described by both CC2 (MP2) and DFT-D approaches. Transition energies in gas phase calculated by CC2 approach are in good agreement with available experimental data for aniline. TDDFT calculations with LC-BLYP functional (with standard value of range separation factor ??=?0.47) gives transition energies too high although not as high as CIS. The red solvent shifts, calculated by PCM model with CIS method are qualitative correct, but error in the range of 0.1-0.2 eV should be expected. PMID:22566155

  5. 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.

  6. 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.

  7. THE IONIC PATHWAYS OF LITHIUM CHEMISTRY IN THE EARLY UNIVERSE: QUANTUM CALCULATIONS FOR LiH{sup +} REACTING WITH H

    SciTech Connect

    Bovino, S.; Gianturco, F. A.; Stoecklin, T.

    2010-01-10

    To better understand the overall role of lithium chemistry in the early universe, reactive quantum calculations involving LiH{sup +} have been carried out and rate coefficients have been obtained. The reactive quantum calculations have been performed using a negative imaginary potential method. Infinite-order sudden approximation and the coupled state approximation have been used to simplify the angular coupling dynamics. Rate coefficients are obtained from the reactive cross sections by further integration over Boltzmann distribution of velocities. The results from the present calculations suggest that, at low redshifts (z), LiH{sup +} should be amenable to observation as imprinted on the cosmic background radiation, in contrast with its neutral counterpart. At higher z, the ionic species may disappear through both depletion reaction and three-body break-up processes.

  8. 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.

  9. Quantum-classical calculation of the absorption and emission spectral shapes of oligothiophenes at low and room temperature by first-principle calculations.

    PubMed

    Improta, Roberto; Ferrer, Francisco J Avila; Stendardo, Emiliano; Santoro, Fabrizio

    2014-10-20

    We report a thorough computational characterization of the low- and room-temperature absorption and emission spectra of a series of oligothiophenes that contain between three and seven thiophene units. Our computational approach is based on time-dependent (TD) density functional calculations with the CAM-B3LYP functional. The effect of vibrations is included without resorting to any empirical parameters either at a fully quantum level or with a hybrid quantum-classical protocol. This latter approach is introduced to describe the relevant broadening effects in absorption at room temperature and is based on the partition of the vibrational modes into two sets: the inter-ring torsions treated at the anharmonic level in a classical way and the remaining modes described at the quantum level. The contribution of the quantum modes to the spectrum is computed by using a harmonic approximation, which accounts for Duschinsky mixing and changes in the vibrational frequencies associated with the electronic transition; a path-integral TD approach is adopted to account for the effect of temperature. The spectra simulated at low temperatures are in very good agreement with their experimental counterparts, which indicates that our calculations can quantitatively reproduce the effect of chain lengthening on the position and the shape of the spectra. Good agreement is also obtained at room temperature, for which we show that the classical description of the broadening, owing to the inter-ring torsions, reproduces the loss of the vibronic structure observed in the experiment and introduces only a slight overestimation of the spectral width. PMID:25110885

  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. 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.

  14. 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.

  15. 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.

  16. Multi-Jastrow trial wavefunctions for electronic structure calculations with quantum Monte Carlo.

    PubMed

    Bouaba, Thomas; Brada, Benot; Caffarel, Michel

    2010-07-28

    A new type of electronic trial wavefunction suitable for quantum Monte Carlo calculations of molecular systems is presented. In contrast with the standard Jastrow-Slater form built with a unique global Jastrow term, it is proposed to introduce individual Jastrow factors attached to molecular orbitals. Such a form is expected to be more physical since it allows to describe differently the local electronic correlations associated with various molecular environments (1s-core orbitals, 3d-magnetic orbitals, localized two-center sigma-orbitals, delocalized pi-orbitals, atomic lone pairs, etc.). In contrast with the standard form, introducing different Jastrow terms allows us to change the nodal structure of the wavefunction, a point which is important in the context of building better nodes for more accurate fixed-node diffusion Monte Carlo (FN-DMC) calculations. Another important aspect resulting from the use of local Jastrow terms is the possibility of defining and preoptimizing local and transferable correlated units for building complex trial wavefunctions from simple parts. The practical aspects associated with the computation of the intricate derivatives of the multi-Jastrow trial function are presented in detail. Some first illustrative applications for atoms of increasing size (O, S, and Cu) and for the potential energy curve and spectroscopic constants of the FH molecule are presented. In the case of the copper atom, the use of the multi-Jastrow form at the variational Monte Carlo level has allowed us to improve significantly the value of the total ground-state energy (about 75% of the correlation energy with only one determinant and three atomic orbital Jastrow factors). In the case of the FH molecule (fluorine hydride), it has been found that the multi-Jastrow nodes lead to an almost exact FN-DMC value of the dissociation energy [D(0)=-140.7(4) kcal/mol instead of the estimated nonrelativistic Born-Oppenheimer exact value of -141.1], which is not the case with standard nodes, D(0)=-138.3(4) kcal/mol. PMID:20687637

  17. Multi-Jastrow trial wavefunctions for electronic structure calculations with quantum Monte Carlo

    NASA Astrophysics Data System (ADS)

    Bouaba, Thomas; Brada, Benot; Caffarel, Michel

    2010-07-01

    A new type of electronic trial wavefunction suitable for quantum Monte Carlo calculations of molecular systems is presented. In contrast with the standard Jastrow-Slater form built with a unique global Jastrow term, it is proposed to introduce individual Jastrow factors attached to molecular orbitals. Such a form is expected to be more physical since it allows to describe differently the local electronic correlations associated with various molecular environments (1s-core orbitals, 3d-magnetic orbitals, localized two-center ?-orbitals, delocalized ?-orbitals, atomic lone pairs, etc.). In contrast with the standard form, introducing different Jastrow terms allows us to change the nodal structure of the wavefunction, a point which is important in the context of building better nodes for more accurate fixed-node diffusion Monte Carlo (FN-DMC) calculations. Another important aspect resulting from the use of local Jastrow terms is the possibility of defining and preoptimizing local and transferable correlated units for building complex trial wavefunctions from simple parts. The practical aspects associated with the computation of the intricate derivatives of the multi-Jastrow trial function are presented in detail. Some first illustrative applications for atoms of increasing size (O, S, and Cu) and for the potential energy curve and spectroscopic constants of the FH molecule are presented. In the case of the copper atom, the use of the multi-Jastrow form at the variational Monte Carlo level has allowed us to improve significantly the value of the total ground-state energy (about 75% of the correlation energy with only one determinant and three atomic orbital Jastrow factors). In the case of the FH molecule (fluorine hydride), it has been found that the multi-Jastrow nodes lead to an almost exact FN-DMC value of the dissociation energy [D0=-140.7(4) kcal/mol instead of the estimated nonrelativistic Born-Oppenheimer exact value of -141.1], which is not the case with standard nodes, D0=-138.3(4) kcal/mol.

  18. 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

  19. Quantum confined Stark effect in Gaussian quantum wells: A tight-binding study

    SciTech Connect

    Ramrez-Morales, A.; Martnez-Orozco, J. C.; Rodrguez-Vargas, I.

    2014-05-15

    The main characteristics of the quantum confined Stark effect (QCSE) are studied theoretically in quantum wells of Gaussian profile. The semi-empirical tight-binding model and the Green function formalism are applied in the numerical calculations. A comparison of the QCSE in quantum wells with different kinds of confining potential is presented.

  20. 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.

  1. 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

  2. Theoretical comparison of efficiencies of photoluminescence up-conversion mechanisms in semiconductor quantum well structures: Auger recombination versus a two-step two-photon absorption

    NASA Astrophysics Data System (ADS)

    Arya, K.; Yu, Peter Y.

    1998-03-01

    In recent experiments, photoluminescence at frequencies far above the excitation laser frequency is observed in semiconductor hetero-structure materials. For example, in GaAs/GaInP_2, photoluminescence at 1.93 eV was observed while the excitation photon energy is 1.54 eV(F.A.J.M. Driessen et al, Appl. Phys. Lett. 67, 2813 (1995); Z.P. Su et al, Solid State Comm. 99, 933 (1996).). There is a controversy about the different mechanisms, Auger recombination versus a two-step two-photon absorption, responsible for the up-conversion. We report here the theoretical results for the up-conversion efficiency calculated for a single quantum well based on both mechanisms. We find that both processes contribute to the up-conversion^1. However, the two-step two-photon absorption mechanism dominates over the Auger process for the parameters common in most experiments, namely, photo-excited carrier densities < 10^17 cm-3 and well width ~ 100P>

  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. 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...

  5. 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.

  6. 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.

  7. Accelerating quantum chemistry calculations with graphical processing units - toward in high-density (HD) silico drug discovery.

    PubMed

    Hagiwara, Yohsuke; Ohno, Kazuki; Orita, Masaya; Koga, Ryota; Endo, Toshio; Akiyama, Yutaka; Sekijima, Masakazu

    2013-09-01

    The growing power of central processing units (CPU) has made it possible to use quantum mechanical (QM) calculations for in silico drug discovery. However, limited CPU power makes large-scale in silico screening such as virtual screening with QM calculations a challenge. Recently, general-purpose computing on graphics processing units (GPGPU) has offered an alternative, because of its significantly accelerated computational time over CPU. Here, we review a GPGPU-based supercomputer, TSUBAME2.0, and its promise for next generation in silico drug discovery, in high-density (HD) silico drug discovery. PMID:24010935

  8. Ab Initio Quantum Calculations of Reactions in Astrophysical Ices: Acetaldehyde and Acetone with Ammonia

    NASA Astrophysics Data System (ADS)

    Chen, L.; Woon, D. E.

    2009-06-01

    Complex organic molecules, including amino acid precursors, have been observed in young stellar objects. Both laboratory and theoretical studies have shown that ice chemistry can play an important role in low-temperature synthetic pathways, with water serving as a catalyst that can significantly enhance reaction rates by lowering barriers or eliminating them altogether. Reactions between carbonyl species and ammonia are particularly promising, as shown in previous studies of the formaldehyde-ammonia reaction. In this study, we explore the reactions of ammonia with two larger carbonyl species, acetaldehyde and acetone, embedded in a water ice cluster. To examine the explicit impact of the water, we gradually increase the size of the cluster from 4H_2O to 12H_2O. Cluster calculations were performed at the MP2/{6-31}+G^{**} or B3LYP/{6-31}+G^{**} level. In order to account for the electrostatic contribution from bulk ice, the Polarizable Continuum Model (PCM) and Isodensity Surface Polarized Continuum Model (IPCM) were used to model reaction field solvation effects. For both acetaldehyde and acetone, the reactant is a charge transfer complex (a partial charge-transfer complex in small clusters and full proton-transfer complex in larger clusters). Rearrangement to amino-hydroxylated products can occur by surmounting a small reaction barrier. Stereo-selectivity is observed in the case of acetaldehyde. P. Ehrenfreund and S. B. Charnley, Ann. Rev. Astron. Astrophys. 38, 427 (2000). W. A. Schutte, L. J. Allamandola, and S. A. Sandford, Science 259, 1143 (1993) W. A. Schutte, L. J. Allamandola, and S. A. Sandford, Icarus 104, 118 (1993) D. E. Woon, Icarus 142, 550 (1999) S. P. Walch, C. W. Bauschicher, Jr., A. Ricca and E. L. O. Bakes, Chem. Phys. Lett, 333, 6 (2001)

  9. Accurate quantum wave packet calculations for the F + HCl ? Cl + HF reaction on the ground 12A? potential energy surface

    PubMed Central

    Bulut, Niyazi; K?os, Jacek; Alexander, Millard H.

    2012-01-01

    We present converged exact quantum wave packet calculations of reaction probabilities, integral cross sections, and thermal rate coefficients for the title reaction. Calculations have been carried out on the ground 12A? global adiabatic potential energy surface of Deskevich et al. [J. Chem. Phys.136, 224303 (2006)10.1063/1.2192505]. Converged wave packet reaction probabilities at selected values of the total angular momentum up to a partial wave of J = 140 with the HCl reagent initially selected in the v = 0, j = 016 rovibrational states have been obtained for the collision energy range from threshold up to 0.8 eV. The present calculations confirm an important enhancement of reactivity with rotational excitation of the HCl molecule. First, accurate integral cross sections and rate constants have been calculated and compared with the available experimental data. PMID:22423835

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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

  17. 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.

  18. Calculations of time-dependent observables in non-Hermitian quantum mechanics: The problem and a possible solution

    SciTech Connect

    Gilary, Ido; Fleischer, Avner; Moiseyev, Nimrod

    2005-07-15

    The solutions of the time-independent Schroedinger equation for non-Hermitian (NH) Hamiltonians have been extensively studied and calculated in many different fields of physics by using L{sup 2} methods that originally have been developed for the calculations of bound states. The existing non-Hermitian formalism breaks down when dealing with wave packets (WPs). An open question is how time-dependent expectation values can be calculated when the Hamiltonian is NH? Using the F-product formalism that was recently proposed by Moiseyev and Lein [J. Phys. Chem. 107, 7181 (2003)] we calculate the time-dependent expectation values of different observable quantities for a simple well-known study test case model Hamiltonian. We carry out a comparison between these results and those obtained from conventional (i.e., Hermitian) quantum mechanics (QM) calculations. The remarkable agreement between these results emphasizes the fact that in NH QM, unlike standard QM, there is no need to split the entire space into two regions, i.e., the interaction region and its surrounding. Our results open a door for a type of WP propagation calculations within the NH QM formalism that until now were impossible. In particular our work is relevant to the many different fields in physics and chemistry where complex absorbing potentials are introduced in order to reduce the propagation calculations to a restricted region in space where the artificial reflections from the edge of the numerical grid or box are avoided.

  19. Quantum calculations of highly excited vibrational spectrum of sulfur dioxide. III. Emission spectra from the C 1B2 state

    NASA Astrophysics Data System (ADS)

    Xie, Daiqian; Ma, Guobin; Guo, Hua

    1999-11-01

    We report quantum mechanical calculations of the X?C emission spectra of SO2 at the red wing of the C absorption band. The near equilibrium potential energy surface of the C 1B2 state is deduced by fitting experimental vibrational frequencies using an exact quantum mechanical Hamiltonian. Low-lying vibrational eigenenergies on this double minimum potential agree well with experimental frequencies and the corresponding eigenstates show some interesting features. Both spectral positions and intensities of the X?C transitions are obtained up to 16 000 cm-1 using a Chebyshev based spectral method, which does not explicitly construct vibrational eigenfunctions in the X state. The emission spectra are in reasonably good agreement with experimental measurements.

  20. 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 peptides electron spin density and intrinsically expressed by the protonation state of the peptides 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.

  1. 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.

  2. Quantum chemical calculations predict biological function: the case of T cell receptor interaction with a peptide/MHC class I

    PubMed Central

    Antipas, Georgios S. E.; Germenis, Anastasios E.

    2015-01-01

    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. PMID:25713797

  3. 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.

  4. A theoretical vibrational spectroscopic study with density functional theory and force field refinement calculation methods on free 4-aminopyrimidine molecule

    NASA Astrophysics Data System (ADS)

    Balci, K.; Akyuz, S.

    2005-06-01

    A detailed investigation of the geometric structure, force field, electro-optical parameters, relative IR intensities and harmonic vibrational wavenumbers of free 4-aminopyrimidine molecule (4APM) in the electronically ground state has been carried out by using both the DFT-B3LYP (with 6-31++G(d,p) double and 6-311++G(d,p) triple basis sets) and force field refinement calculation methods. The vibrational wavenumbers calculated with DFT method were scaled by using two different methods: (1) scaling with dual scaling factors, (2) deriving the scaling factors from the graph of observed versus calculated wavenumbers. In the case of force field refinement method, the force constants of the pyrimidine were slightly refined so as to fit the calculated wavenumbers to the experimental ones. In order to define the contributions of the internal coordinates of the molecule on its each normal vibrational mode, P.E.D. calculations were performed. In wavenumber and PED calculations, both methods have yield results in agreement with the experimental assignment and also with each other, particularly for ring vibrations. The relative IR intensities calculated by the force field refinement method are considerably in good agreement with experimental ones, however, the results of the IR intensities, obtained from the DFT method are found to be significantly different from the experimental values.

  5. Molecular structure, spectroscopic characterization of (S)-2-Oxopyrrolidin-1-yl Butanamide and ab initio, DFT based quantum chemical calculations.

    PubMed

    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 (1)H NMR and (13)C 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. PMID:25956325

  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. 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.

  8. Matrix-isolation FT-IR spectroscopic study and theoretical DFT(B3LYP)/6-31 ++ G ** calculations of the vibrational and conformational properties of tyrosine

    NASA Astrophysics Data System (ADS)

    Ramaekers, Riet; Pajak, Joanna; Rospenk, Maria; Maes, Guido

    2005-05-01

    The complicated conformational isomerism of tyrosine is studied by experimental matrix-isolation FT-IR spectroscopy combined with theoretical DFT(B3LYP)/6-31 ++ G ** calculations. Not less than 18 possible conformations of tyrosine have been considered theoretically. The results revealed that the most and the less stable forms of neutral tyrosine have the same conformation of the main part of amino acid (conformation II) but they differ in orientation of the phenyl ring. The calculated values of the relative energies suggest that all conformations would be detectable in the experimental spectrum. However, it appeared that it is not possible to distinguish in the experimental spectrum between the bands due to the forms with the same conformation of the main part of amino acid but a different orientation of the phenol ring.

  9. Theoretical calculation on ICI reduction using digital coherent superposition of optical OFDM subcarrier pairs in the presence of laser phase noise.

    PubMed

    Yi, Xingwen; Xu, Bo; Zhang, Jing; Lin, Yun; Qiu, Kun

    2014-12-15

    Digital coherent superposition (DCS) of optical OFDM subcarrier pairs with Hermitian symmetry can reduce the inter-carrier-interference (ICI) noise resulted from phase noise. In this paper, we show two different implementations of DCS-OFDM that have the same performance in the presence of laser phase noise. We complete the theoretical calculation on ICI reduction by using the model of pure Wiener phase noise. By Taylor expansion of the ICI, we show that the ICI power is cancelled to the second order by DCS. The fourth order term is further derived out and only decided by the ratio of laser linewidth to OFDM subcarrier symbol rate, which can greatly simplify the system design. Finally, we verify our theoretical calculations in simulations and use the analytical results to predict the system performance. DCS-OFDM is expected to be beneficial to certain optical fiber transmissions. PMID:25607068

  10. An evolutionary algorithm to calculate the ground state of a quantum system

    NASA Astrophysics Data System (ADS)

    Grigorenko, I.; Garcia, M. E.

    2000-09-01

    We present a new method based on evolutionary algorithms which permits to determine efficiently the ground state of the time-independent Schrdinger equation for arbitrary external potentials. The approach relies on the variational principle. The ground-state wave function of a given Hamiltonian is found by using the procedure of survival of the fittest, starting from a population of wave functions. To perform the search for the fittest wave function we have extended a genetic algorithm to treat quantum mechanical problems. We present results for different one dimensional external potentials and compare them with analytical solutions and with other numerical methods. Our approach yields very good convergence in all cases. Potential applications of the quantum genetic algorithm presented here to more dimensions and many-body problems are discussed.

  11. 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.

  12. 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.

  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 Power Spectra of the Rolling and Yawing Moments on a Wing in Random Turbulence

    NASA Technical Reports Server (NTRS)

    Eggleston, John M; Diederich, Franklin W

    1957-01-01

    The correlation functions and power spectra of the rolling and yawing moments on an airplane wing due to the three components of continuous random turbulence are calculated. The rolling moments to the longitudinal (horizontal) and normal (vertical) components depend on the spanwise distributions of instantaneous gust intensity, which are taken into account by using the inherent properties of symmetry of isotropic turbulence. The results consist of expressions for correlation functions or spectra of the rolling moment in terms of the point correlation functions of the two components of turbulence. Specific numerical calculations are made for a pair of correlation functions given by simple analytic expressions which fit available experimental data quite well. Calculations are made for four lift distributions. Comparison is made with the results of previous analyses which assumed random turbulence along the flight path and linear variations of gust velocity across the span.

  15. 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.

  16. Scanning tunneling microscopy observation and theoretical calculation of the adsorption of adenine on Si(100)2 1 surfaces

    NASA Astrophysics Data System (ADS)

    Kasaya, Megumi; Tabata, Hitoshi; Kawai, Tomoji

    1995-11-01

    Scanning tunneling microscopy (STM) images of adenine molecules on Si(100)2 1 surfaces have shown for the first time that the adenine is adsorbed on a Si dimer row. The double bright molecular images are located on the neighboring two Si dimer rows and have ellipsoidal shapes. An extended Hckel molecular orbital calculation of the adenine adsorbed on the Si cluster gives the form of the hybridized orbital in this system. This calculation explains the adsorption site and the surface local density of states corresponding to the observed STM images.

  17. 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.

  18. Formation and dissociation of protonated cytosinecytosine base pairs in i-motifs by ab initio quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao-Hu; Li, Ming; Wang, Yan-Ting; Ouyang, Zhong-Can

    2014-02-01

    Formation and dissociation mechanisms of CC+ base pairs in acidic and alkaline environments are investigated, employing ab initio quantum chemical calculations. Our calculations suggest that, in an acidic environment, a cytosine monomer is first protonated and then dimerized with an unprotonated cytosine monomer to form a CC+ base pair; in an alkaline environment, a protonated cytosine dimer is first unprotonated and then dissociated into two cytosine monomers. In addition, the force for detaching a CC+ base pair was found to be inversely proportional to the distance between the two cytosine monomers. These results provide a microscopic mechanism to qualitatively explain the experimentally observed reversible formation and dissociation of i-motifs.

  19. 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 nanoparticles 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 molecules individual electrons to the collective dielectric response of the nanoparticle.

  20. Theoretical calculations of rotationally inelastic collisions of He with NaK(A?{sup 1}?{sup +}): Transfer of population, orientation, and alignment

    SciTech Connect

    Malenda, R. F.; Price, T. J.; Stevens, J.; Uppalapati, S. L.; Fragale, A.; Weiser, P. M.; Kuczala, A.; Hickman, A. P.; Talbi, D.

    2015-06-14

    We have performed extensive calculations to investigate thermal energy, rotationally inelastic collisions of NaK (A{sup 1}?{sup +}) with He. We determined a potential energy surface using a multi-reference configuration interaction wave function as implemented by the GAMESS electronic structure code, and we have performed coupled channel scattering calculations using the Arthurs and Dalgarno formalism. We also calculate the Grawert coefficients B{sub ?}(j, j?) for each j ? j? transition. These coefficients are used to determine the probability that orientation and alignment are preserved in collisions taking place in a cell environment. The calculations include all rotational levels with j or j? between 0 and 50, and total (translational and rotational) energies in the range 0.00020.0025 a.u. (?44550?cm{sup ?1}). The calculated cross sections for transitions with even values of ?j tend to be larger than those for transitions with odd ?j, in agreement with the recent experiments of Wolfe et al. (J. Chem. Phys. 134, 174301 (2011)). The calculations of the energy dependence of the cross sections and the calculations of the fraction of orientation and alignment preserved in collisions also exhibit distinctly different behaviors for odd and even values of ?j. The calculations also indicate that the average fraction of orientation or alignment preserved in a transition becomes larger as j increases. We interpret this behavior using the semiclassical model of Derouard, which also leads to a simple way of visualizing the distribution of the angles between the initial and final angular momentum vectors j and j?. Finally, we compare the exact quantum results for j ? j? transitions with results based on the simpler, energy sudden approximation. That approximation is shown to be quite accurate.