Sample records for critical quantum chemical

  1. Quantum criticality. (United States)

    Coleman, Piers; Schofield, Andrew J


    As we mark the centenary of Albert Einstein's seminal contribution to both quantum mechanics and special relativity, we approach another anniversary--that of Einstein's foundation of the quantum theory of solids. But 100 years on, the same experimental measurement that puzzled Einstein and his contemporaries is forcing us to question our understanding of how quantum matter transforms at ultra-low temperatures.

  2. CRITIC2: A program for real-space analysis of quantum chemical interactions in solids (United States)

    Otero-de-la-Roza, A.; Johnson, Erin R.; Luaña, Víctor


    We present CRITIC2, a program for the analysis of quantum-mechanical atomic and molecular interactions in periodic solids. This code, a greatly improved version of the previous CRITIC program (Otero-de-la Roza et al., 2009), can: (i) find critical points of the electron density and related scalar fields such as the electron localization function (ELF), Laplacian, … (ii) integrate atomic properties in the framework of Bader’s Atoms-in-Molecules theory (QTAIM), (iii) visualize non-covalent interactions in crystals using the non-covalent interactions (NCI) index, (iv) generate relevant graphical representations including lines, planes, gradient paths, contour plots, atomic basins, … and (v) perform transformations between file formats describing scalar fields and crystal structures. CRITIC2 can interface with the output produced by a variety of electronic structure programs including WIEN2k, elk, PI, abinit, Quantum ESPRESSO, VASP, Gaussian, and, in general, any other code capable of writing the scalar field under study to a three-dimensional grid. CRITIC2 is parallelized, completely documented (including illustrative test cases) and publicly available under the GNU General Public License. Catalogue identifier: AECB_v2_0 Program summary URL: Program obtainable from: CPC Program Library, Queen’s University, Belfast, N. Ireland Licensing provisions: yes No. of lines in distributed program, including test data, etc.: 11686949 No. of bytes in distributed program, including test data, etc.: 337020731 Distribution format: tar.gz Programming language: Fortran 77 and 90. Computer: Workstations. Operating system: Unix, GNU/Linux. Has the code been vectorized or parallelized?: Shared-memory parallelization can be used for most tasks. Classification: 7.3. Catalogue identifier of previous version: AECB_v1_0 Journal reference of previous version: Comput. Phys. Comm. 180 (2009) 157 Nature of problem: Analysis of quantum-chemical

  3. Unconventional Quantum Critical Points


    Xu, Cenke


    In this paper we review the theory of unconventional quantum critical points that are beyond the Landau's paradigm. Three types of unconventional quantum critical points will be discussed: (1). The transition between topological order and semiclassical spin ordered phase; (2). The transition between topological order and valence bond solid phase; (3). The direct second order transition between different competing orders. We focus on the field theory and universality class of these unconventio...

  4. Frustration and quantum criticality. (United States)

    Vojta, Matthias


    This review article is devoted to the interplay between frustrated magnetism and quantum critical phenomena, covering both theoretical concepts and ideas as well as recent experimental developments in correlated-electron materials. The first part deals with local-moment magnetism in Mott insulators and the second part with frustration in metallic systems. In both cases, frustration can either induce exotic phases accompanied by exotic quantum critical points or lead to conventional ordering with unconventional crossover phenomena. In addition, the competition of multiple phases inherent to frustrated systems can lead to multi-criticality. © 2018 IOP Publishing Ltd.

  5. Quantum indistinguishability in chemical reactions. (United States)

    Fisher, Matthew P A; Radzihovsky, Leo


    Quantum indistinguishability plays a crucial role in many low-energy physical phenomena, from quantum fluids to molecular spectroscopy. It is, however, typically ignored in most high-temperature processes, particularly for ionic coordinates, implicitly assumed to be distinguishable, incoherent, and thus well approximated classically. We explore enzymatic chemical reactions involving small symmetric molecules and argue that in many situations a full quantum treatment of collective nuclear degrees of freedom is essential. Supported by several physical arguments, we conjecture a "quantum dynamical selection" (QDS) rule for small symmetric molecules that precludes chemical processes that involve direct transitions from orbitally nonsymmetric molecular states. As we propose and discuss, the implications of the QDS rule include ( i ) a differential chemical reactivity of para- and orthohydrogen, ( ii ) a mechanism for inducing intermolecular quantum entanglement of nuclear spins, ( iii ) a mass-independent isotope fractionation mechanism, ( iv ) an explanation of the enhanced chemical activity of "reactive oxygen species", ( v ) illuminating the importance of ortho-water molecules in modulating the quantum dynamics of liquid water, and ( vi ) providing the critical quantum-to-biochemical linkage in the nuclear spin model of the (putative) quantum brain, among others.

  6. Quantum Critical Higgs

    Directory of Open Access Journals (Sweden)

    Brando Bellazzini


    Full Text Available The appearance of the light Higgs boson at the LHC is difficult to explain, particularly in light of naturalness arguments in quantum field theory. However, light scalars can appear in condensed matter systems when parameters (like the amount of doping are tuned to a critical point. At zero temperature these quantum critical points are directly analogous to the finely tuned standard model. In this paper, we explore a class of models with a Higgs near a quantum critical point that exhibits non-mean-field behavior. We discuss the parametrization of the effects of a Higgs emerging from such a critical point in terms of form factors, and present two simple realistic scenarios based on either generalized free fields or a 5D dual in anti–de Sitter space. For both of these models, we consider the processes gg→ZZ and gg→hh, which can be used to gain information about the Higgs scaling dimension and IR transition scale from the experimental data.

  7. APS Quantum Critical Higgs

    CERN Document Server

    Bellazzini, Brando; Hubisz, Jay; Lee, Seung J.; Serra, Javi; Terning, John


    The appearance of the light Higgs boson at the LHC is difficult to explain, particularly in light of naturalness arguments in quantum field theory. However light scalars can appear in condensed matter systems when parameters (like the amount of doping) are tuned to a critical point. At zero temperature these quantum critical points are directly analogous to the finely tuned standard model. In this paper we explore a class of models with a Higgs near a quantum critical point that exhibits non-mean-field behavior. We discuss the parametrization of the effects of a Higgs emerging from such a critical point in terms of form factors, and present two simple realistic scenarios based on either generalized free fields or a 5D dual in AdS space. For both of these models we consider the processes $gg\\to ZZ$ and $gg\\to hh$, which can be used to gain information about the Higgs scaling dimension and IR transition scale from the experimental data.

  8. Ferroelectric quantum criticality

    International Nuclear Information System (INIS)

    Rowley, S.; Spalek, L.; Scott, J.F.; Lonzarich, G.G.; Saxena, S.S.


    Full text: Materials tuned to the neighbourhood of a zero temperature phase transition often show the emergence of novel quantum phenomena. Much of the effort to study these new emergent effects, like the break down of the conventional Fermi-liquid theory of metals, has been focused in narrow band electronic systems. Ferroelectric crystals provide another class of materials in which to study quantum criticality and its resulting effects. In many cases the ferroelectric phase can be tuned to absolute zero using hydrostatic pressure. Close to such a zero temperature phase transition, the dielectric constant and other quantities change into radically unconventional forms due to the fluctuations experienced in this region. Measurements in pure single crystals of SrTi1 6 O 3 and SrTi1 8 O 3 will be shown and a simple model for describing the Ferroelectric quantum critical point will be outlined. The expected 1/T 2 dependence of the dielectric constant in SrTi1 6 O 3 over a wide temperature range at low temperatures will be highlighted as well as some further novel features. Looking to the future, one might imagine that quantum paraelectric fluctuations could lead to new low temperature states and mediate novel interactions in ferroelectric crystals supporting itinerant electrons.(authors)

  9. Quantum critical Hall exponents

    CERN Document Server

    Lütken, C A


    We investigate a finite size "double scaling" hypothesis using data from an experiment on a quantum Hall system with short range disorder [1-3]. For Hall bars of width w at temperature T the scaling form is w(-mu)T(-kappa), where the critical exponent mu approximate to 0.23 we extract from the data is comparable to the multi-fractal exponent alpha(0) - 2 obtained from the Chalker-Coddington (CC) model [4]. We also use the data to find the approximate location (in the resistivity plane) of seven quantum critical points, all of which closely agree with the predictions derived long ago from the modular symmetry of a toroidal sigma-model with m matter fields [5]. The value nu(8) = 2.60513 ... of the localisation exponent obtained from the m = 8 model is in excellent agreement with the best available numerical value nu(num) = 2.607 +/- 0.004 derived from the CC-model [6]. Existing experimental data appear to favour the m = 9 model, suggesting that the quantum Hall system is not in the same universality class as th...

  10. Quantum Chemical Calculations (United States)

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


    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.

  11. Quantum criticality and black holes. (United States)

    Sachdev, Subir; Müller, Markus


    Many condensed matter experiments explore the finite temperature dynamics of systems near quantum critical points. Often, there are no well-defined quasiparticle excitations, and so quantum kinetic equations do not describe the transport properties completely. The theory shows that the transport coefficients are not proportional to a mean free scattering time (as is the case in the Boltzmann theory of quasiparticles), but are completely determined by the absolute temperature and by equilibrium thermodynamic observables. Recently, explicit solutions of this quantum critical dynamics have become possible via the anti-de Sitter/conformal field theory duality discovered in string theory. This shows that the quantum critical theory provides a holographic description of the quantum theory of black holes in a negatively curved anti-de Sitter space, and relates its transport coefficients to properties of the Hawking radiation from the black hole. We review how insights from this connection have led to new results for experimental systems: (i) the vicinity of the superfluid-insulator transition in the presence of an applied magnetic field, and its possible application to measurements of the Nernst effect in the cuprates, (ii) the magnetohydrodynamics of the plasma of Dirac electrons in graphene and the prediction of a hydrodynamic cyclotron resonance.

  12. Quantum Entanglement and Chemical Reactivity. (United States)

    Molina-Espíritu, M; Esquivel, R O; López-Rosa, S; Dehesa, J S


    The water molecule and a hydrogenic abstraction reaction are used to explore in detail some quantum entanglement features of chemical interest. We illustrate that the energetic and quantum-information approaches are necessary for a full understanding of both the geometry of the quantum probability density of molecular systems and the evolution of a chemical reaction. The energy and entanglement hypersurfaces and contour maps of these two models show different phenomena. The energy ones reveal the well-known stable geometry of the models, whereas the entanglement ones grasp the chemical capability to transform from one state system to a new one. In the water molecule the chemical reactivity is witnessed through quantum entanglement as a local minimum indicating the bond cleavage in the dissociation process of the molecule. Finally, quantum entanglement is also useful as a chemical reactivity descriptor by detecting the transition state along the intrinsic reaction path in the hypersurface of the hydrogenic abstraction reaction corresponding to a maximally entangled state.

  13. Fermion-induced quantum critical points. (United States)

    Li, Zi-Xiang; Jiang, Yi-Fan; Jian, Shao-Kai; Yao, Hong


    A unified theory of quantum critical points beyond the conventional Landau-Ginzburg-Wilson paradigm remains unknown. According to Landau cubic criterion, phase transitions should be first-order when cubic terms of order parameters are allowed by symmetry in the Landau-Ginzburg free energy. Here, from renormalization group analysis, we show that second-order quantum phase transitions can occur at such putatively first-order transitions in interacting two-dimensional Dirac semimetals. As such type of Landau-forbidden quantum critical points are induced by gapless fermions, we call them fermion-induced quantum critical points. We further introduce a microscopic model of SU(N) fermions on the honeycomb lattice featuring a transition between Dirac semimetals and Kekule valence bond solids. Remarkably, our large-scale sign-problem-free Majorana quantum Monte Carlo simulations show convincing evidences of a fermion-induced quantum critical points for N = 2, 3, 4, 5 and 6, consistent with the renormalization group analysis. We finally discuss possible experimental realizations of the fermion-induced quantum critical points in graphene and graphene-like materials.Quantum phase transitions are governed by Landau-Ginzburg theory and the exceptions are rare. Here, Li et al. propose a type of Landau-forbidden quantum critical points induced by gapless fermions in two-dimensional Dirac semimetals.

  14. Multidimensional entropy landscape of quantum criticality (United States)

    Grube, K.; Zaum, S.; Stockert, O.; Si, Q.; Löhneysen, H. V.


    The third law of thermodynamics states that the entropy of any system in equilibrium has to vanish at absolute zero temperature. At nonzero temperatures, on the other hand, matter is expected to accumulate entropy near a quantum critical point, where it undergoes a continuous transition from one ground state to another. Here, we determine, based on general thermodynamic principles, the spatial-dimensional profile of the entropy S near a quantum critical point and its steepest descent in the corresponding multidimensional stress space. We demonstrate this approach for the canonical quantum critical compound CeCu 6-xAux near its onset of antiferromagnetic order. We are able to link the directional stress dependence of S to the previously determined geometry of quantum critical fluctuations. Our demonstration of the multidimensional entropy landscape provides the foundation to understand how quantum criticality nucleates novel phases such as high-temperature superconductivity.

  15. Dynamics of quantum discord in a quantum critical environment

    International Nuclear Information System (INIS)

    Xi Zhengjun; Li Yongming; Lu Xiaoming; Sun Zhe


    We study the dynamics of quantum discord (QD) of two qubits independently coupled to an Ising spin chain in a transverse field, which exhibits a quantum phase transition. For this model, we drive the corresponding Kraus operators, obtain the analytic results of QD and compare the dynamics of QD with the dynamics of relative entropy of entanglement nearby the critical point. It is shown that the impact of the quantum criticality environment on QD can be concentrated in a very narrow region nearby the critical point, so it supplies an efficient way to detect the critical points. In the vicinity of the critical point, the evolution of QD is shown to be more complicated than that of entanglement. Furthermore, we find that separable states can also be used to reflect the quantum criticality of the environment.

  16. Controlling superconductivity by tunable quantum critical points. (United States)

    Seo, S; Park, E; Bauer, E D; Ronning, F; Kim, J N; Shim, J-H; Thompson, J D; Park, Tuson


    The heavy fermion compound CeRhIn5 is a rare example where a quantum critical point, hidden by a dome of superconductivity, has been explicitly revealed and found to have a local nature. The lack of additional examples of local types of quantum critical points associated with superconductivity, however, has made it difficult to unravel the role of quantum fluctuations in forming Cooper pairs. Here, we show the precise control of superconductivity by tunable quantum critical points in CeRhIn5. Slight tin-substitution for indium in CeRhIn5 shifts its antiferromagnetic quantum critical point from 2.3 GPa to 1.3 GPa and induces a residual impurity scattering 300 times larger than that of pure CeRhIn5, which should be sufficient to preclude superconductivity. Nevertheless, superconductivity occurs at the quantum critical point of the tin-doped metal. These results underline that fluctuations from the antiferromagnetic quantum criticality promote unconventional superconductivity in CeRhIn5.

  17. Interplay of quantum and classical fluctuations near quantum critical points

    International Nuclear Information System (INIS)

    Continentino, Mucio Amado


    For a system near a quantum critical point (QCP), above its lower critical dimension d L , there is in general a critical line of second-order phase transitions that separates the broken symmetry phase at finite temperatures from the disordered phase. The phase transitions along this line are governed by thermal critical exponents that are different from those associated with the quantum critical point. We point out that, if the effective dimension of the QCP, d eff = d + z (d is the Euclidean dimension of the system and z the dynamic quantum critical exponent) is above its upper critical dimension d c there is an intermingle of classical (thermal) and quantum critical fluctuations near the QCP. This is due to the breakdown of the generalized scaling relation ψ = νz between the shift exponent ψ of the critical line and the crossover exponent νz, for d + z > d c by a dangerous irrelevant interaction. This phenomenon has clear experimental consequences, like the suppression of the amplitude of classical critical fluctuations near the line of finite temperature phase transitions as the critical temperature is reduced approaching the QCP. (author)

  18. Spotlighting quantum critical points via quantum correlations at finite temperatures

    International Nuclear Information System (INIS)

    Werlang, T.; Ribeiro, G. A. P.; Rigolin, Gustavo


    We extend the program initiated by T. Werlang et al. [Phys. Rev. Lett. 105, 095702 (2010)] in several directions. Firstly, we investigate how useful quantum correlations, such as entanglement and quantum discord, are in the detection of critical points of quantum phase transitions when the system is at finite temperatures. For that purpose we study several thermalized spin models in the thermodynamic limit, namely, the XXZ model, the XY model, and the Ising model, all of which with an external magnetic field. We compare the ability of quantum discord, entanglement, and some thermodynamic quantities to spotlight the quantum critical points for several different temperatures. Secondly, for some models we go beyond nearest neighbors and also study the behavior of entanglement and quantum discord for second nearest neighbors around the critical point at finite temperature. Finally, we furnish a more quantitative description of how good all these quantities are in spotlighting critical points of quantum phase transitions at finite T, bridging the gap between experimental data and those theoretical descriptions solely based on the unattainable absolute zero assumption.

  19. Detecting quantum critical points using bipartite fluctuations. (United States)

    Rachel, Stephan; Laflorencie, Nicolas; Song, H Francis; Le Hur, Karyn


    We show that the concept of bipartite fluctuations F provides a very efficient tool to detect quantum phase transitions in strongly correlated systems. Using state-of-the-art numerical techniques complemented with analytical arguments, we investigate paradigmatic examples for both quantum spins and bosons. As compared to the von Neumann entanglement entropy, we observe that F allows us to find quantum critical points with much better accuracy in one dimension. We further demonstrate that F can be successfully applied to the detection of quantum criticality in higher dimensions with no prior knowledge of the universality class of the transition. Promising approaches to experimentally access fluctuations are discussed for quantum antiferromagnets and cold gases.

  20. A magnetically induced quantum critical point in holography

    NARCIS (Netherlands)

    Gursoy, U.; Gnecchi, A.; Toldo, C.; Papadoulaki, O.

    We investigate quantum critical points in a 2+1 dimensional gauge theory at finite chemical potential χ and magnetic field B. The gravity dual is based on 4D NN = 2 Fayet-Iliopoulos gauged supergravity and the solutions we consider — that are constructed analytically — are extremal, dyonic,

  1. Criticality and entanglement in random quantum systems

    International Nuclear Information System (INIS)

    Refael, G; Moore, J E


    We review studies of entanglement entropy in systems with quenched randomness, concentrating on universal behavior at strongly random quantum critical points. The disorder-averaged entanglement entropy provides insight into the quantum criticality of these systems and an understanding of their relationship to non-random ('pure') quantum criticality. The entanglement near many such critical points in one dimension shows a logarithmic divergence in subsystem size, similar to that in the pure case but with a different universal coefficient. Such universal coefficients are examples of universal critical amplitudes in a random system. Possible measurements are reviewed along with the one-particle entanglement scaling at certain Anderson localization transitions. We also comment briefly on higher dimensions and challenges for the future.

  2. Fermion-induced quantum critical points


    Li, Zi-Xiang; Jiang, Yi-Fan; Jian, Shao-Kai; Yao, Hong


    A unified theory of quantum critical points beyond the conventional Landau?Ginzburg?Wilson paradigm remains unknown. According to Landau cubic criterion, phase transitions should be first-order when cubic terms of order parameters are allowed by symmetry in the Landau?Ginzburg free energy. Here, from renormalization group analysis, we show that second-order quantum phase transitions can occur at such putatively first-order transitions in interacting two-dimensional Dirac semimetals. As such t...

  3. Transport in the quantum critical regime (United States)

    Enss, Tilman


    In this talk I will explain the relevance of the quantum critical point for the phase diagram of the unitary Fermi gas, briefly review theoretical approaches, and present results for the shear viscosity and spin diffusion in strongly interacting Fermi gases. The unitary Fermi gas describes strongly interacting fermions ranging from ultracold atoms near a Feshbach resonance to dilute neutron matter, which share a common universal phase diagram. The behavior at finite temperature is governed by a quantum critical point (QCP) at zero temperature and zero density, and observables can be expressed by universal scaling functions of the distance from the critical point. In the quantum critical regime above the QCP, thermal and quantum fluctuations are equally important, and the absence of a small parameter makes the computation of critical properties demanding. I will mention two theoretical approaches to transport properties in this regime: the large-N expansion in the number of fermion flavors allows for a systematic and controlled expansion even at strong coupling and elucidates the importance of medium effects on scattering. Second, the Luttinger-Ward, or self-consistent T-matrix approach goes beyond the quasiparticle picture and also explains universal high-energy tails. I will present results on the shear viscosity, or internal friction, for mass transport and show that the strongly interacting Fermi gas is an almost perfect quantum fluid. On the other hand, if particles of different spin move in opposite directions, the dynamics are governed by spin diffusion. One can distinguish longitudinal diffusion, when atomic clouds of different spin collide, and transverse diffusion, when the magnetization is wound up in a helix in a spin-echo experiment. Medium scattering and spin rotation have a strong effect on spin diffusion, and I will discuss how spin transport becomes very slow at strong coupling in the quantum degenerate regime and reaches a quantum limit of

  4. Critical behaviors of gravity under quantum perturbations

    Directory of Open Access Journals (Sweden)

    ZHANG Hongsheng


    Full Text Available Phase transition and critical phenomenon is a very interesting topic in thermodynamics and statistical mechanics. Gravity is believed to have deep and inherent relation to thermodynamics. Near the critical point,the perturbation becomes significant. Thus for ordinary matter (governed by interactions besides gravity the critical behavior will become very different if we ignore the perturbations around the critical point,such as mean field theory. We find that the critical exponents for RN-AdS spacetime keep the same values even when we consider the full quantum perturbations. This indicates a key difference between gravity and ordinary thermodynamic system.

  5. Dynamical Response near Quantum Critical Points. (United States)

    Lucas, Andrew; Gazit, Snir; Podolsky, Daniel; Witczak-Krempa, William


    We study high-frequency response functions, notably the optical conductivity, in the vicinity of quantum critical points (QCPs) by allowing for both detuning from the critical coupling and finite temperature. We consider general dimensions and dynamical exponents. This leads to a unified understanding of sum rules. In systems with emergent Lorentz invariance, powerful methods from quantum field theory allow us to fix the high-frequency response in terms of universal coefficients. We test our predictions analytically in the large-N O(N) model and using the gauge-gravity duality and numerically via quantum Monte Carlo simulations on a lattice model hosting the interacting superfluid-insulator QCP. In superfluid phases, interacting Goldstone bosons qualitatively change the high-frequency optical conductivity and the corresponding sum rule.

  6. Emergent symmetry and dimensional reduction at a quantum critical point (United States)

    Schmalian, J.; Batista, C. D.


    We show that the spatial dimensionality of the quantum critical point associated with Bose-Einstein condensation at T=0 is reduced when the underlying lattice comprises a set of layers coupled by a frustrating interaction. For this purpose, we use an heuristic mean field approach that is complemented and justified by a more rigorous renormalization group analysis. Due to the presence of an emergent symmetry, i.e., a symmetry of the ground state that is absent in the underlying Hamiltonian, a three-dimensional interacting Bose system undergoes a chemical potential tuned quantum phase transition that is strictly two-dimensional. Our theoretical predictions for the critical temperature as a function of the chemical potential correspond very well with recent measurements in BaCuSi2O6 .

  7. Critical Kondo destruction and the violation of the quantum-to-classical mapping of quantum criticality

    International Nuclear Information System (INIS)

    Kirchner, Stefan; Si Qimiao


    Antiferromagnetic heavy fermion metals close to their quantum critical points display a richness in their physical properties unanticipated by the traditional approach to quantum criticality, which describes the critical properties solely in terms of fluctuations of the order parameter. This has led to the question as to how the Kondo effect gets destroyed as the system undergoes a phase change. In one approach to the problem, Kondo lattice systems are studied through a self-consistent Bose-Fermi Kondo model within the extended dynamical mean field theory. The quantum phase transition of the Kondo lattice is thus mapped onto that of a sub-Ohmic Bose-Fermi Kondo model. In the present article we address some aspects of the failure of the standard order-parameter functional for the Kondo-destroying quantum critical point of the Bose-Fermi Kondo model.

  8. Universal signatures of fractionalized quantum critical points. (United States)

    Isakov, Sergei V; Melko, Roger G; Hastings, Matthew B


    Ground states of certain materials can support exotic excitations with a charge equal to a fraction of the fundamental electron charge. The condensation of these fractionalized particles has been predicted to drive unusual quantum phase transitions. Through numerical and theoretical analysis of a physical model of interacting lattice bosons, we establish the existence of such an exotic critical point, called XY*. We measure a highly nonclassical critical exponent η = 1.493 and construct a universal scaling function of winding number distributions that directly demonstrates the distinct topological sectors of an emergent Z(2) gauge field. The universal quantities used to establish this exotic transition can be used to detect other fractionalized quantum critical points in future model and material systems.

  9. Quantum Chemical Strain Analysis For Mechanochemical Processes. (United States)

    Stauch, Tim; Dreuw, Andreas


    The use of mechanical force to initiate a chemical reaction is an efficient alternative to the conventional sources of activation energy, i.e., heat, light, and electricity. Applications of mechanochemistry in academic and industrial laboratories are diverse, ranging from chemical syntheses in ball mills and ultrasound baths to direct activation of covalent bonds using an atomic force microscope. The vectorial nature of force is advantageous because specific covalent bonds can be preconditioned for rupture by selective stretching. However, the influence of mechanical force on single molecules is still not understood at a fundamental level, which limits the applicability of mechanochemistry. As a result, many chemists still resort to rules of thumb when it comes to conducting mechanochemical syntheses. In this Account, we show that comprehension of mechanochemistry at the molecular level can be tremendously advanced by quantum chemistry, in particular by using quantum chemical force analysis tools. One such tool is the JEDI (Judgement of Energy DIstribution) analysis, which provides a convenient approach to analyze the distribution of strain energy in a mechanically deformed molecule. Based on the harmonic approximation, the strain energy contribution is calculated for each bond length, bond angle and dihedral angle, thus providing a comprehensive picture of how force affects molecules. This Account examines the theoretical foundations of quantum chemical force analysis and provides a critical overview of the performance of the JEDI analysis in various mechanochemical applications. We explain in detail how this analysis tool is to be used to identify the "force-bearing scaffold" of a distorted molecule, which allows both the rationalization and the optimization of diverse mechanochemical processes. More precisely, we show that the inclusion of every bond, bending and torsion of a molecule allows a particularly insightful discussion of the distribution of mechanical

  10. Quantum chemical studies of estrogenic compounds (United States)

    Quantum chemical methods are potent tools to provide information on the chemical structure and electronic properties of organic molecules. Modern computational chemistry methods have provided a great deal of insight into the binding of estrogenic compounds to estrogenic receptors (ER), an important ...

  11. Retrocausality in Quantum Phenomena and Chemical Evolution

    Directory of Open Access Journals (Sweden)

    Koichiro Matsuno


    Full Text Available The interplay between retrocausality and the time-reversal symmetry of the dynamical law of quantum mechanics underscores the significance of the measurement dynamics with the use of indivisible and discrete quantum particles to be mediated. One example of empirical evidence demonstrating the significance of retrocausality going along with time-reversal symmetry is seen in the operation of a reaction cycle to be expected in chemical evolution. A reaction cycle can hold itself when the causative operation of the cycle remains robust, even when facing frequent retrocausal interventions of a quantum-mechanical origin. Quantum mechanics in and of itself has potential in raising a reaction cycle in the prebiotic phase of chemical evolution, even without any help of artefactual scaffoldings of an external origin.

  12. [Quantum mechanics and brain: a critical review]. (United States)

    Pastor-Gómez, J

    Theories about consciousness are in an initial state of development. In the recent past, diverse theories have been proposed to explain the phenomenon of the consciousness using the Quantum Mechanics (QM) as a fundamental tool. Here, we criticize some of these theories in the light of the current knowledge in neuroscience. The QM theories of consciousness by John Eccles, Dana Zohar and Roger Penrose are discussed. For a better understanding of these theories, some physical principles of the quantum formalism are firstly introduced. We then expose these theories in the authors original formalism and discuss them from a neuroscientist point of view. As currently exposed, the three QM theories of consciousness suffer from important neuroscientist concerns. It is not necessary the use QM to explain different aspects of brain function such as consciousness, which would be better understood using tools from the neurosciences

  13. Quantum criticality of one-dimensional multicomponent Fermi gas with strongly attractive interaction

    International Nuclear Information System (INIS)

    He, Peng; Jiang, Yuzhu; Guan, Xiwen; He, Jinyu


    Quantum criticality of strongly attractive Fermi gas with SU(3) symmetry in one dimension is studied via the thermodynamic Bethe ansatz (TBA) equations. The phase transitions driven by the chemical potential μ, effective magnetic field H 1 , H 2 (chemical potential biases) are analyzed at the quantum criticality. The phase diagram and critical fields are analytically determined by the TBA equations in the zero temperature limit. High accurate equations of state, scaling functions are also obtained analytically for the strong interacting gases. The dynamic exponent z=2 and correlation length exponent ν=1/2 read off the universal scaling form. It turns out that the quantum criticality of the three-component gases involves a sudden change of density of states of one cluster state, two or three cluster states. In general, this method can be adapted to deal with the quantum criticality of multicomponent Fermi gases with SU(N) symmetry. (paper)

  14. Strongly correlated superconductivity and quantum criticality (United States)

    Tremblay, A.-M. S.

    Doped Mott insulators and doped charge-transfer insulators describe classes of materials that can exhibit unconventional superconducting ground states. Examples include the cuprates and the layered organic superconductors of the BEDT family. I present results obtained from plaquette cellular dynamical mean-field theory. Continuous-time quantum Monte Carlo evaluation of the hybridization expansion allows one to study the models in the large interaction limit where quasiparticles can disappear. The normal state which is unstable to the superconducting state exhibits a first-order transition between a pseudogap and a correlated metal phase. That transition is the finite-doping extension of the metal-insulator transition obtained at half-filling. This transition serves as an organizing principle for the normal and superconducting states of both cuprates and doped organic superconductors. In the less strongly correlated limit, these methods also describe the more conventional case where the superconducting dome surrounds an antiferromagnetic quantum critical point. Sponsored by NSERC RGPIN-2014-04584, CIFAR, Research Chair in the Theory of Quantum Materials.

  15. Detection of quantum critical points by a probe qubit. (United States)

    Zhang, Jingfu; Peng, Xinhua; Rajendran, Nageswaran; Suter, Dieter


    Quantum phase transitions occur when the ground state of a quantum system undergoes a qualitative change when an external control parameter reaches a critical value. Here, we demonstrate a technique for studying quantum systems undergoing a phase transition by coupling the system to a probe qubit. It uses directly the increased sensibility of the quantum system to perturbations when it is close to a critical point. Using an NMR quantum simulator, we demonstrate this measurement technique for two different types of quantum phase transitions in an Ising spin chain.

  16. Effective and fundamental quantum fields at criticality

    Energy Technology Data Exchange (ETDEWEB)

    Scherer, Michael


    We employ Wetterich's approach to functional renormalization as a suitable method to investigate universal phenomena in non-perturbative quantum field theories both qualitatively and quantitatively. Therefore we derive and investigate flow equations for a class of chiral Yukawa models with and without gauge bosons and reveal fixed-point mechanisms. In four dimensions chiral Yukawa systems serve as toy models for the standard model Higgs sector and show signatures of asymptotically safe fixed points by a balancing of bosonic and fermionic contributions. In the approximations investigated this renders the theory fundamental and solves the triviality problem. Further, we obtain predictions for the Higgs mass and even for the top mass of our toy model. In three dimensions we compute the critical exponents which define new universality classes and provide benchmark values for systems of strongly correlated chiral fermions. In a Yukawa system of non-relativistic two-component fermions a fixed point dominates the renormalization flow giving rise to universality in the BCS-BEC crossover. We push the functional renormalization method to a quantitative level and we compute the critical temperature and the single-particle gap with a considerable precision for the whole crossover. Finally, we provide further evidence for the asymptotic safety scenario in quantum gravity by confirming the existence of an ultraviolet fixed point under inclusion of a curvature-ghost coupling. (orig.)

  17. Quantum mechanical tunneling in chemical physics

    CERN Document Server

    Nakamura, Hiroki


    Quantum mechanical tunneling plays important roles in a wide range of natural sciences, from nuclear and solid-state physics to proton transfer and chemical reactions in chemistry and biology. Responding to the need for further understanding of multidimensional tunneling, the authors have recently developed practical methods that can be applied to multidimensional systems. Quantum Mechanical Tunneling in Chemical Physics presents basic theories, as well as original ones developed by the authors. It also provides methodologies and numerical applications to real molecular systems. The book offers information so readers can understand the basic concepts and dynamics of multidimensional tunneling phenomena and use the described methods for various molecular spectroscopy and chemical dynamics problems. The text focuses on three tunneling phenomena: (1) energy splitting, or tunneling splitting, in symmetric double well potential, (2) decay of metastable state through tunneling, and (3) tunneling effects in chemical...


    African Journals Online (AJOL)

    Preferred Customer

    SOME QUANTUM CHEMICAL STUDY ON THE STRUCTURAL PROPERTIES OF. THREE UNSYMMETRICAL SCHIFF BASE LIGANDS. Iran Sheikhshoaie1*, VahidSaheb1 and Parisa Iranmanesh2. 1Department of Chemistry, Shahid Bahonar University of Kerman, Iran. 2Department of Chemistry, Payame Nour University ...

  19. New quantum criticality revealed under pressure

    International Nuclear Information System (INIS)

    Watanabe, Shinji; Miyake, Kazumasa


    Unconventional quantum critical phenomena observed in Yb-based periodic crystals such as YbRh 2 Si 2 and β-YbAlB 4 have been one of the central issues in strongly correlated electron systems. The common criticality has been discovered in the quasicrystal Yb 15 Au 51 Al 34 , which surprisingly persists under pressure at least up to P = 1.5 GPa. The T/H scaling where the magnetic susceptibility can be expressed as a single scaling function of the ratio of the temperature T to the magnetic field H has been discovered in the quasicrystal, which is essentially the same as that observed in β-YbAlB 4 . Recently, the T/H scaling as well as the common criticality has also been observed even in the approximant crystal Yb 14 Au 51 Al 35 under pressure. The theory of critical Yb-valence fluctuation gives a natural explanation for these striking phenomena in a unified way. (author)

  20. Quantum mechanical facets of chemical bonds

    International Nuclear Information System (INIS)

    Daudel, R.


    To define the concept of bond is both a central problem of quantum chemistry and a difficult one. The concept of bond appeared little by little in the mind of chemists from empirical observations. From the wave-mechanical viewpoint it is not an observable. Therefore there is no precise operator associated with that concept. As a consequence there is not a unique approach to the idea of chemical bond. This is why it is preferred to present various quantum mechanical facets, e.g. the energetic facet, the density facet, the partitioning facet and the functional facet, of that important concept. (Auth.)

  1. Quantum electrodynamical corrections in critical fields

    International Nuclear Information System (INIS)

    Soff, G.


    We investigate field-theoretical corrections, such as vacuum polarization and self energy to study their influence on strongly bound electrons in heavy and superheavy atoms. In critical fields (Z≅170) for spontaneous e + e - pair creation the coupling constant of the external field Zα exceeds 1 thereby preventing the ordinary perturbative approach of quantum electrodynamical correction which employs an expansion in Zα. For heavy and superheavy elements radiative corrections have to be treated to all orders in Zα. The dominant effect is provided by the Uehling contribution being visualized by the first diagram on the right hand side. It is linear in the external field and thus of order α(Zα). (orig./HSI)

  2. Quantum field theory and critical phenomena

    CERN Document Server

    Zinn-Justin, Jean


    Over the last twenty years quantum field theory has become not only the framework for the discussion of all fundamental interactions except gravity, but also for the understanding of second-order phase transitions in statistical mechanics. This advanced text is based on graduate courses and summer schools given by the author over a number of years. It approaches the subject in terms of path and functional intergrals, adopting a Euclidean metric and using the language of partition and correlation functions. Renormalization and the renormalization group are examined, as are critical phenomena and the role of instantons. Changes for this edition 1. Extensive revision to eliminate a few bugs that had survived the second edition and (mainly) to improve the pedagogical presentation, as a result of experience gathered by lecturing. 2. Additional new topics; holomorphic or coherent state path integral; functional integral and representation of the field theory S-matrix in the holomorphic formalis; non-relativistic li...

  3. molecular dynamics simulations and quantum chemical calculations

    African Journals Online (AJOL)

    The quantum chemical calculations also reveal that the amine group in HDM and the hydroxyl group in HDE which is attached to the imidazoline ring do not result in a significant increase in the HOMO nor the LUMO density which can aid adsorption.HDM has a lower energy gap of 4.434 eV and. 3.824 eV, a higher EHOMO ...

  4. Dimensional reduction at a quantum critical point (United States)

    Sebastian, S. E.; Harrison, N.; Batista, C. D.; Balicas, L.; Jaime, M.; Sharma, P. A.; Kawashima, N.; Fisher, I. R.


    Competition between electronic ground states near a quantum critical point (QCP)-the location of a zero-temperature phase transition driven solely by quantum-mechanical fluctuations-is expected to lead to unconventional behaviour in low-dimensional systems. New electronic phases of matter have been predicted to occur in the vicinity of a QCP by two-dimensional theories, and explanations based on these ideas have been proposed for significant unsolved problems in condensed-matter physics, such as non-Fermi-liquid behaviour and high-temperature superconductivity. But the real materials to which these ideas have been applied are usually rendered three-dimensional by a finite electronic coupling between their component layers; a two-dimensional QCP has not been experimentally observed in any bulk three-dimensional system, and mechanisms for dimensional reduction have remained the subject of theoretical conjecture. Here we show evidence that the Bose-Einstein condensate of spin triplets in the three-dimensional Mott insulator BaCuSi2O6 (refs 12-16) provides an experimentally verifiable example of dimensional reduction at a QCP. The interplay of correlations on a geometrically frustrated lattice causes the individual two-dimensional layers of spin-½ Cu2+ pairs (spin dimers) to become decoupled at the QCP, giving rise to a two-dimensional QCP characterized by linear power law scaling distinctly different from that of its three-dimensional counterpart. Thus the very notion of dimensionality can be said to acquire an `emergent' nature: although the individual particles move on a three-dimensional lattice, their collective behaviour occurs in lower-dimensional space.

  5. Quantum mechanical cluster calculations of critical scintillationprocesses

    Energy Technology Data Exchange (ETDEWEB)

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


    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.

  6. High precision measurements of quantum critical properties for 3D quantum antiferromagnets (United States)

    Meng, Zi Yang; Qing, Yan Qi; Normand, Bruce; Sandvik, Anders


    Using large-scale quantum Monte Carlo (QMC) simulations, we study the quantum phase transitions in three-dimensional S=1/2 dimerized Heisenberg antiferromagnets. We obtain high precision results on the quantum critical properties of the transition from antiferromagnetically ordered phase to the magnetically disordered dimerized phase. With careful finite size scaling analysis and improved estimator of physical observables in the QMC simulations, we are able to extract the precise logarithmic corrections to quantum phase transition in our system governed by the 3+1 O(3) universality class. Finite temperature quantum critical properties in excitation spectra are obtained as well.

  7. Characteristic signatures of quantum criticality driven by geometrical frustration. (United States)

    Tokiwa, Yoshifumi; Stingl, Christian; Kim, Moo-Sung; Takabatake, Toshiro; Gegenwart, Philipp


    Geometrical frustration describes situations where interactions are incompatible with the lattice geometry and stabilizes exotic phases such as spin liquids. Whether geometrical frustration of magnetic interactions in metals can induce unconventional quantum critical points is an active area of research. We focus on the hexagonal heavy fermion metal CeRhSn, where the Kondo ions are located on distorted kagome planes stacked along the c axis. Low-temperature specific heat, thermal expansion, and magnetic Grüneisen parameter measurements prove a zero-field quantum critical point. The linear thermal expansion, which measures the initial uniaxial pressure derivative of the entropy, displays a striking anisotropy. Critical and noncritical behaviors along and perpendicular to the kagome planes, respectively, prove that quantum criticality is driven be geometrical frustration. We also discovered a spin flop-type metamagnetic crossover. This excludes an itinerant scenario and suggests that quantum criticality is related to local moments in a spin liquid-like state.

  8. Critical examination of logical formulations in quantum theory. Statistical inference and Hilbertian distance between quantum states

    International Nuclear Information System (INIS)

    Hadjisawas, Nicolas.


    After a critical study of the logical quantum mechanics formulations of Jauch and Piron, classical and quantum versions of statistical inference are studied. In order to do this, the significance of the Jaynes and Kulback principles (maximum likelihood, least squares principles) is revealed from the theorems established. In the quantum mechanics inference problem, a ''distance'' between states is defined. This concept is used to solve the quantum equivalent of the classical problem studied by Kulback. The ''projection postulate'' proposition is subsequently deduced [fr

  9. Universal Postquench Prethermalization at a Quantum Critical Point (United States)

    Gagel, Pia; Orth, Peter P.; Schmalian, Jörg


    We consider an open system near a quantum critical point that is suddenly moved towards the critical point. The bath-dominated diffusive nonequilibrium dynamics after the quench is shown to follow scaling behavior, governed by a critical exponent that emerges in addition to the known equilibrium critical exponents. We determine this exponent and show that it describes universal prethermalized coarsening dynamics of the order parameter in an intermediate time regime. Implications of this quantum critical prethermalization are: (i) a power law rise of order and correlations after an initial collapse of the equilibrium state and (ii) a crossover to thermalization that occurs arbitrarily late for sufficiently shallow quenches.

  10. Quantum uncertainty in critical systems with three spins interaction

    International Nuclear Information System (INIS)

    Carrijo, Thiago M; Avelar, Ardiley T; Céleri, Lucas C


    In this article we consider two spin-1/2 chains described, respectively, by the thermodynamic limit of the XY model with the usual two site interaction, and an extension of this model (without taking the thermodynamics limit), called XYT, were a three site interaction term is presented. To investigate the critical behaviour of such systems we employ tools from quantum information theory. Specifically, we show that the local quantum uncertainty, a quantity introduced in order to quantify the minimum quantum share of the variance of a local measurement, can be used to indicate quantum phase transitions presented by these models at zero temperature. Due to the connection of this quantity with the quantum Fisher information, the results presented here may be relevant for quantum metrology and quantum thermodynamics. (paper)

  11. Charge frustration and quantum criticality for strongly correlated fermions

    NARCIS (Netherlands)

    Huijse, L.; Halverson, J.; Fendley, P.; Schoutens, K.


    We study a model of strongly correlated electrons on the square lattice which exhibits charge frustration and quantum critical behavior. The potential is tuned to make the interactions supersymmetric. We establish a rigorous mathematical result which relates quantum ground states to certain tiling

  12. Vector boson excitations near deconfined quantum critical points. (United States)

    Huh, Yejin; Strack, Philipp; Sachdev, Subir


    We show that the Néel states of two-dimensional antiferromagnets have low energy vector boson excitations in the vicinity of deconfined quantum critical points. We compute the universal damping of these excitations arising from spin-wave emission. Detection of such a vector boson will demonstrate the existence of emergent topological gauge excitations in a quantum spin system.

  13. New Type of Quantum Criticality in the Pyrochlore Iridates

    Directory of Open Access Journals (Sweden)

    Lucile Savary


    Full Text Available Magnetic fluctuations and electrons couple in intriguing ways in the vicinity of zero-temperature phase transitions—quantum critical points—in conducting materials. Quantum criticality is implicated in non-Fermi liquid behavior of diverse materials and in the formation of unconventional superconductors. Here, we uncover an entirely new type of quantum critical point describing the onset of antiferromagnetism in a nodal semimetal engendered by the combination of strong spin-orbit coupling and electron correlations, and which is predicted to occur in the iridium oxide pyrochlores. We formulate and solve a field theory for this quantum critical point by renormalization group techniques and show that electrons and antiferromagnetic fluctuations are strongly coupled and that both these excitations are modified in an essential way. This quantum critical point has many novel features, including strong emergent spatial anisotropy, a vital role for Coulomb interactions, and highly unconventional critical exponents. Our theory motivates and informs experiments on pyrochlore iridates and constitutes a singular realistic example of a nontrivial quantum critical point with gapless fermions in three dimensions.

  14. Quantum dynamics of fast chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Light, J.C. [Univ. of Chicago, IL (United States)


    The aims of this research are to explore, develop, and apply theoretical methods for the evaluation of the dynamics of gas phase collision processes, primarily chemical reactions. The primary theoretical tools developed for this work have been quantum scattering theory, both in time dependent and time independent forms. Over the past several years, the authors have developed and applied methods for the direct quantum evaluation of thermal rate constants, applying these to the evaluation of the hydrogen isotopic exchange reactions, applied wave packet propagation techniques to the dissociation of Rydberg H{sub 3}, incorporated optical potentials into the evaluation of thermal rate constants, evaluated the use of optical potentials for state-to-state reaction probability evaluations, and, most recently, have developed quantum approaches for electronically non-adiabatic reactions which may be applied to simplify calculations of reactive, but electronically adiabatic systems. Evaluation of the thermal rate constants and the dissociation of H{sub 3} were reported last year, and have now been published.

  15. Quantum critical scaling and fluctuations in Kondo lattice materials (United States)

    Yang, Yi-feng; Pines, David; Lonzarich, Gilbert


    We propose a phenomenological framework for three classes of Kondo lattice materials that incorporates the interplay between the fluctuations associated with the antiferromagnetic quantum critical point and those produced by the hybridization quantum critical point that marks the end of local moment behavior. We show that these fluctuations give rise to two distinct regions of quantum critical scaling: Hybridization fluctuations are responsible for the logarithmic scaling in the density of states of the heavy electron Kondo liquid that emerges below the coherence temperature T∗, whereas the unconventional power law scaling in the resistivity that emerges at lower temperatures below TQC may reflect the combined effects of hybridization and antiferromagnetic quantum critical fluctuations. Our framework is supported by experimental measurements on CeCoIn5, CeRhIn5, and other heavy electron materials. PMID:28559308

  16. Quantum-Chemical Insights from Deep Tensor Neural Networks (United States)

    Schütt, Kristof T.; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus-Robert; Tkatchenko, Alexandre

    Discovery of novel materials can be guided by searching databases of known structures and properties. Indeed, electronic structure calculations and machine learning have recently been combined aiming towards the goal of accelerated discovery of chemicals with desired properties. However, the design of an appropriate descriptor is critical to the success of these approaches. Here we address this issue with deep neural tensor networks (DTNN): a deep learning approach that is able to learn efficient representations of molecules and materials. The mathematical construction of the DTNN model provides statistically rigorous partitioning of extensive molecular properties into atomic contributions - a long-standing challenge for quantum-mechanical calculations of molecules. Beyond achieving accurate energy predictions (1 kcal mol-1) throughout compositional and configurational space, DTNN provide spatially and chemically resolved insights into quantum-mechanical properties of molecular systems beyond those trivially contained in the training data. Thus, we propose DTNN as a versatile framework for understanding complex quantum-mechanical systems based on high-throughput electronic structure calculations. This research is supported by the DFG (MU 987/20-1) and BMBF (01IS14013A).

  17. Universal Entanglement Entropy in 2D Conformal Quantum Critical Points

    Energy Technology Data Exchange (ETDEWEB)

    Hsu, Benjamin; Mulligan, Michael; Fradkin, Eduardo; Kim, Eun-Ah


    We study the scaling behavior of the entanglement entropy of two dimensional conformal quantum critical systems, i.e. systems with scale invariant wave functions. They include two-dimensional generalized quantum dimer models on bipartite lattices and quantum loop models, as well as the quantum Lifshitz model and related gauge theories. We show that, under quite general conditions, the entanglement entropy of a large and simply connected sub-system of an infinite system with a smooth boundary has a universal finite contribution, as well as scale-invariant terms for special geometries. The universal finite contribution to the entanglement entropy is computable in terms of the properties of the conformal structure of the wave function of these quantum critical systems. The calculation of the universal term reduces to a problem in boundary conformal field theory.

  18. Itinerant density instability at classical and quantum critical points (United States)

    Feng, Yejun; van Wezel, Jasper; Flicker, Felix; Wang, Jiyang; Silevitch, D. M.; Littlewood, P. B.; Rosenbaum, T. F.


    Itinerant density waves are model systems for studying quantum critical behavior. In both the model spin- and charge-density-wave systems Cr and NbSe2, it is possible to drive a continuous quantum phase transition with critical pressures below 10 GPa. Using x-ray diffraction techniques, we are able to directly track the evolution of the ordering wave vector Q across the pressure-temperature phase diagram. We find a non-monotonic dependence of Q on pressure. Using a Landau-Ginsburg theoretical framework developed by McMillan for CDWs, we evaluate the importance of the physical terms in driving the formation of ordered states at both the thermal and quantum phase transitions. We find that the itinerant instability is the deciding factor for the emergent order, which is further influenced by the critical fluctuations in both the thermal and quantum limits.

  19. Quantum criticality in your car bumper

    CERN Document Server

    Coleman, P


    Over the past few years, condensed-matter physicists have become fascinated by the phenomenon of quantum phase transitions. We know that new forms of order develop within a material by way of phase transitions and that they can drastically change its properties. (U.K.)

  20. Quantum correction to conductivity close to ferromagnetic quantum critical point in two dimensions

    International Nuclear Information System (INIS)

    Paul, I.; Pepin, C.; Narozhny, B.N.; Maslov, D.L.


    We study the temperature dependence of the conductivity due to quantum interference processes for a two-dimensional disordered itinerant electron system close to a ferromagnetic quantum critical point. Near the quantum critical point, the cross-over between diffusive and ballistic regimes of quantum interference effects occurs at a temperature T* 1/τγ(E F τ) 2 where γ is the parameter associated with the Landau damping of the spin fluctuations, τ is the impurity scattering time, and E F is the Fermi energy. For a generic choice of parameters, T* is smaller than the nominal crossover scale 1/τ. In the ballistic quantum critical regime, the conductivity behaves as T 1/3 . (author)

  1. Quantum chemical calculations of using density functional theory ...

    Indian Academy of Sciences (India)



    Feb 15, 2018 ... Quantum chemical calculations of Cr2O3/SnO2 using density functional theory method ... Quantum chemical calculations have been employed to study the molecular effects produced by. Cr2O3/SnO2 optimised structure. .... optical memory for emerging technologies in areas such as telecommunications ...

  2. Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry. (United States)

    Rappoport, Dmitrij; Galvin, Cooper J; Zubarev, Dmitry Yu; Aspuru-Guzik, Alán


    While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles.

  3. Hall effect in quantum critical charge-cluster glass (United States)

    Wu, Jie; Bollinger, Anthony T.; Sun, Yujie


    Upon doping, cuprates undergo a quantum phase transition from an insulator to a d-wave superconductor. The nature of this transition and of the insulating state is vividly debated. Here, we study the Hall effect in La2-xSrxCuO4 (LSCO) samples doped near the quantum critical point at x ˜ 0.06. Dramatic fluctuations in the Hall resistance appear below TCG ˜ 1.5 K and increase as the sample is cooled down further, signaling quantum critical behavior. We explore the doping dependence of this effect in detail, by studying a combinatorial LSCO library in which the Sr content is varied in extremely fine steps, Δx ˜ 0.00008. We observe that quantum charge fluctuations wash out when superconductivity emerges but can be restored when the latter is suppressed by applying a magnetic field, showing that the two instabilities compete for the ground state.

  4. Chemical Reactivity as Described by Quantum Chemical Methods

    Directory of Open Access Journals (Sweden)

    F. De Proft


    Full Text Available Abstract: Density Functional Theory is situated within the evolution of Quantum Chemistry as a facilitator of computations and a provider of new, chemical insights. The importance of the latter branch of DFT, conceptual DFT is highlighted following Parr's dictum "to calculate a molecule is not to understand it". An overview is given of the most important reactivity descriptors and the principles they are couched in. Examples are given on the evolution of the structure-property-wave function triangle which can be considered as the central paradigm of molecular quantum chemistry to (for many purposes a structure-property-density triangle. Both kinetic as well as thermodynamic aspects can be included when further linking reactivity to the property vertex. In the field of organic chemistry, the ab initio calculation of functional group properties and their use in studies on acidity and basicity is discussed together with the use of DFT descriptors to study the kinetics of SN2 reactions and the regioselectivity in Diels Alder reactions. Similarity in reactivity is illustrated via a study on peptide isosteres. In the field of inorganic chemistry non empirical studies of adsorption of small molecules in zeolite cages are discussed providing Henry constants and separation constants, the latter in remarkable good agreement with experiments. Possible refinements in a conceptual DFT context are presented. Finally an example from biochemistry is discussed : the influence of point mutations on the catalytic activity of subtilisin.

  5. Quantum critical matter. Quantum phase transitions with multiple dynamics and Weyl superconductors

    International Nuclear Information System (INIS)

    Meng, Tobias


    In this PhD thesis, the physics of quantum critical matter and exotic quantum state close to quantum phase transitions is investigated. We will focus on three different examples that highlight some of the interesting phenomena related to quantum phase transitions. Firstly, we discuss the physics of quantum phase transitions in quantum wires as a function of an external gate voltage when new subbands are activated. We find that at these transitions, strong correlations lead to the formation of an impenetrable gas of polarons, and identify criteria for possible instabilities in the spin- and charge sectors of the model. Our analysis is based on the combination of exact resummations, renormalization group techniques and Luttinger liquid approaches. Secondly, we turn to the physics of multiple divergent time scales close to a quantum critical point. Using an appropriately generalized renormalization group approach, we identify that the presence of multiple dynamics at a quantum phase transition can lead to the emergence of new critical scaling exponents and thus to the breakdown of the usual scaling schemes. We calculate the critical behavior of various thermodynamic properties and detail how unusual physics can arise. It is hoped that these results might be helpful for the interpretation of experimental scaling puzzles close to quantum critical points. Thirdly, we turn to the physics of topological transitions, and more precisely the physics of Weyl superconductors. The latter are the superconducting variant of the topologically non-trivial Weyl semimetals, and emerge at the quantum phase transition between a topological superconductor and a normal insulator upon perturbing the transition with a time reversal symmetry breaking perturbation, such as magnetism. We characterize the topological properties of Weyl superconductors and establish a topological phase diagram for a particular realization in heterostructures. We discuss the physics of vortices in Weyl

  6. Random walks, critical phenomena, and triviality in quantum field theory

    International Nuclear Information System (INIS)

    Fernandez, R.; Froehlich, J.; Sokal, A.D.


    The subject of this book is equilibrium statistical mechanics - in particular the theory of critical phenomena - and quantum field theory. A general review of the theory of critical phenomena in spin systems, field theories, and random-walk and random-surface models is presented. Among the more technical topics treated in this book, the central theme is the use of random-walk representations as a tool to derive correlation inequalities. The consequences of these inequalities for critical-exponent theory and the triviality question in quantum field theory are expounded in detail. The book contains some previously unpublished results. It addresses both the researcher and the graduate student in modern statistical mechanics and quantum field theory. (orig.)

  7. Universal post-quench prethermalization at a quantum critical point (United States)

    Orth, Peter P.; Gagel, Pia; Schmalian, Joerg


    We consider an open system near a quantum critical point that is suddenly moved towards the critical point. The bath-dominated diffusive non-equilibrium dynamics after the quench is shown to follow scaling behavior, governed by a critical exponent that emerges in addition to the known equilibrium critical exponents. We determine this exponent and show that it describes universal prethermalized coarsening dynamics of the order parameter in an intermediate time regime. Implications of this quantum critical prethermalization are a powerlaw rise of order and correlations after an initial collapse of the equilibrium state and a crossover to thermalization that occurs arbitrarily late for sufficiently shallow quenches. [1] P. Gagel, P. P. Orth, J. Schmalian, Phys.Rev. Lett. (in press) arXiv:1406.6387

  8. Vison excitations in near-critical quantum dimer models (United States)

    Strübi, G.; Ivanov, D. A.


    We study vison excitations in a quantum dimer model interpolating between the Rokhsar-Kivelson models on the square and triangular lattices. In the square-lattice case, the model is known to be critical and characterized by U(1) topological quantum numbers. Introducing diagonal dimers brings the model to a Z2 resonating-valence-bond phase. We study variationally the emergence of vison excitations at low concentration of diagonal dimers, close to the critical point. We find that, in this regime, vison excitations are large in size and their structure resembles vortices in type-II superconductors.

  9. The use of quantum chemical methods in corrosion inhibitor studies

    International Nuclear Information System (INIS)

    Gece, Goekhan


    Quantum chemical methods are particularly significant in the study of electrochemistry and provide researchers with a relatively quick way of studying the structure and behaviour of corrosion inhibitors. The originality of this review article is based on the fact that it is the first and unique general reference for all those interested in the use of quantum chemical methods in corrosion inhibitor studies. It begins with a concise summary of the most used quantum chemical parameters and methods and then summarizes the results of research articles in corrosion science over the past 20 years

  10. Field-induced magnetic instability and quantum criticality in the antiferromagnet CeCu2Ge2. (United States)

    Liu, Yi; Xie, Donghua; Wang, Xiaoying; Zhu, Kangwei; Yang, Ruilong


    The magnetic quantum criticality in strongly correlated electron systems has been considered to be closely related with the occurrence of unconventional superconductivity. Control parameters such as magnetic field, pressure or chemical doping are frequently used to externally tune the quantum phase transition for a deeper understanding. Here we report the research of a field-induced quantum phase transition using conventional bulk physical property measurements in the archetypal antiferromagnet CeCu2Ge2, which becomes superconductive under a pressure of about 10 GPa with Tc ~ 0.64 K. We offer strong evidence that short-range dynamic correlations start appearing above a magnetic field of about 5 T. Our demonstrations of the magnetic instability and the field-induced quantum phase transition are crucial for the quantum criticality, which may open a new route in experimental investigations of the quantum phase transition in heavy-fermion systems.

  11. Black holes as critical point of quantum phase transition. (United States)

    Dvali, Gia; Gomez, Cesar

    We reformulate the quantum black hole portrait in the language of modern condensed matter physics. We show that black holes can be understood as a graviton Bose-Einstein condensate at the critical point of a quantum phase transition, identical to what has been observed in systems of cold atoms. The Bogoliubov modes that become degenerate and nearly gapless at this point are the holographic quantum degrees of freedom responsible for the black hole entropy and the information storage. They have no (semi)classical counterparts and become inaccessible in this limit. These findings indicate a deep connection between the seemingly remote systems and suggest a new quantum foundation of holography. They also open an intriguing possibility of simulating black hole information processing in table-top labs.

  12. Black Holes as Critical Point of Quantum Phase Transition

    CERN Document Server

    Dvali, Gia


    We reformulate the quantum black hole portrait in the language of modern condensed matter physics. We show that black holes can be understood as a graviton Bose-Einstein condensate at the critical point of a quantum phase transition, identical to what has been observed in systems of cold atoms. The Bogoliubov modes that become degenerate and nearly gapless at this point are the holographic quantum degrees of freedom responsible for the black hole entropy and the information storage. They have no (semi)classical counterparts and become inaccessible in this limit. These findings indicate a deep connection between the seemingly remote systems and suggest a new quantum foundation of holography. They also open an intriguing possibility of simulating black hole information processing in table-top labs.

  13. Sigmatropic proton shifts: a quantum chemical study. (United States)

    Wang, Yi; Yu, Zhi-Xiang


    A quantum chemical study of [1,j] sigmatropic proton shifts in polyenyl anions and related conjugated systems has been performed. We found that the Woodward-Hoffmann rules can be applied to understand the stereochemical outcome of these sigmatropic rearrangements, showing that [1,j] sigmatropic proton shift occurs antarafacially when j = 4n + 2, while suprafacial proton shift is symmetry-allowed when j = 4n. The activation barriers for [1,j] proton shifts in polyenyl anions C j H j+3 - are 48.2 (j = 2), 32.8 (j = 4), 21.0 (j = 6), 40.5 (j = 8), and 49.1 (j = 10) kcal mol -1 , respectively. This trend can be explained by the trade-off between stereoelectronic requirement and ring strain in the proton shift transition structure. Among these reactions, only the [1,6] proton shift with the lowest activation barrier can occur intramolecularly under mild reaction conditions. The others are unlikely to take place in a direct manner. Consequently, proton shuttles are generally required to facilitate these sigmatropic proton shifts through a protonation/deprotonation mechanism.

  14. Chemical sensors based on quantum cascade lasers (United States)

    Tittel, Frank K.; Kosterev, Anatoliy A.; Rochat, Michel; Beck, Mattias; Faist, Jerome


    There is an increasing need in many chemical sensing applications ranging from industrial process control to environmental science and medical diagnostics for fast, sensitive, and selective gas detection based on laser spectroscopy. The recent availability of novel pulsed and cw quantum cascade distributed feedback (QC-DFB) lasers as mid-infrared spectroscopic sources address this need. A number of spectroscopic techniques have been demonstrated. For example, the authors have employed QC-DFB lasers for the monitoring and quantification of several trace gases and isotopic species in ambient air at ppmv and ppbv levels by means of direct absorption, wavelength modulation, cavity enhanced and cavity ringdown spectroscopy. In this work, pulsed thermoelectrically cooled QC-DFB lasers operating at ~15.6 μm were characterized for spectroscopic gas sensing applications. A new method for wavelength scanning based on the repetition rate modulation was developed. A non-wavelength-selective pyroelectric detector was incorporated in the gas sensor giving an advantage of room-temperature operation and low cost. Absorption lines of CO2 and H2O were observed in ambient air providing information about the concentration of these species.

  15. Geometric Frustration and Dimensional Reduction at a Quantum Critical Point (United States)

    Batista, C. D.; Schmalian, J.; Kawashima, N.; Sengupta, P.; Sebastian, S. E.; Harrison, N.; Jaime, M.; Fisher, I. R.


    We show that the spatial dimensionality of the quantum critical point associated with Bose-Einstein condensation at T=0 is reduced when the underlying lattice comprises layers coupled by a frustrating interaction. Our theoretical predictions for the critical behavior correspond very well with recent measurements in BaCuSi2O6 [ S. E. Sebastian et al., Nature (London)NATUAS0028-0836 441, 617 (2006)].

  16. Partial dynamical symmetry at critical points of quantum phase transitions. (United States)

    Leviatan, A


    We show that partial dynamical symmetries can occur at critical points of quantum phase transitions, in which case underlying competing symmetries are conserved exactly by a subset of states, and mix strongly in other states. Several types of partial dynamical symmetries are demonstrated with the example of critical-point Hamiltonians for first- and second-order transitions in the framework of the interacting boson model, whose dynamical symmetries correspond to different shape phases in nuclei.

  17. Partial Dynamical Symmetry at Critical Points of Quantum Phase Transitions

    International Nuclear Information System (INIS)

    Leviatan, A.


    We show that partial dynamical symmetries can occur at critical points of quantum phase transitions, in which case underlying competing symmetries are conserved exactly by a subset of states, and mix strongly in other states. Several types of partial dynamical symmetries are demonstrated with the example of critical-point Hamiltonians for first- and second-order transitions in the framework of the interacting boson model, whose dynamical symmetries correspond to different shape phases in nuclei

  18. Quantum criticality of quasi one-dimensional topological Anderson insulators

    NARCIS (Netherlands)

    Altland, A.; Bagrets, D.; Fritz, L.; Kamenev, A.; Schmiedt, H.


    We present an analytic theory of quantum criticality in the quasi one-dimensional topological Anderson insulators of class AIII and BDI. We describe the systems in terms of two parameters (g,χ) representing localization and topological properties, respectively. Surfaces of half-integer valued χ

  19. Electron self-trapping at quantum and classical critical points

    NARCIS (Netherlands)

    Auslender, M.I.; Katsnelson, M.I.


    Using Feynman path integral technique estimations of the ground state energy have been found for a conduction electron interacting with order parameter fluctuations near quantum critical points. In some cases only singular perturbation theory in the coupling constant emerges for the electron ground

  20. Universal postquench coarsening and aging at a quantum critical point (United States)

    Gagel, Pia; Orth, Peter P.; Schmalian, Jörg


    The nonequilibrium dynamics of a system that is located in the vicinity of a quantum critical point is affected by the critical slowing down of order-parameter correlations with the potential for novel out-of-equilibrium universality. After a quantum quench, i.e., a sudden change of a parameter in the Hamiltonian, such a system is expected to almost instantly fall out of equilibrium and undergo aging dynamics, i.e., dynamics that depends on the time passed since the quench. Investigating the quantum dynamics of an N -component φ4 model coupled to an external bath, we determine this universal aging and demonstrate that the system undergoes a coarsening, governed by a critical exponent that is unrelated to the equilibrium exponents of the system. We analyze this behavior in the large-N limit, which is complementary to our earlier renormalization-group analysis, allowing in particular the direct investigation of the order-parameter dynamics in the symmetry-broken phase and at the upper critical dimension. By connecting the long-time limit of fluctuations and response, we introduce a distribution function that shows that the system remains nonthermal and exhibits quantum coherence even on long time scales.

  1. Entanglement dynamics in critical random quantum Ising chain with perturbations (United States)

    Huang, Yichen


    We simulate the entanglement dynamics in a critical random quantum Ising chain with generic perturbations using the time-evolving block decimation algorithm. Starting from a product state, we observe super-logarithmic growth of entanglement entropy with time. The numerical result is consistent with the analytical prediction of Vosk and Altman using a real-space renormalization group technique.

  2. Critical current in the Integral Quantum Hall Effect

    International Nuclear Information System (INIS)

    Kostadinov, I.Z.


    A multiparticle theory of the Integral Quantum Hall Effect (IQHE) was constructed operating with pairs wave function as an order parameter. The IQHE is described with bosonic macroscopic states while the fractional QHE with fermionic ones. The calculation of the critical current and Hall conductivity temperature dependence is presented. (author)

  3. Critical Quantum Fluctuations and Localization of the Small Polaron

    NARCIS (Netherlands)

    Raedt, Hans De; Lagendijk, Ad


    The first quantitative evidence of critical quantum fluctuations and superlocalization of the small polaron model in one, two, and three dimensions is presented. Starting from a discrete version of the Feynman path-integral representation of the partition function, the boson field is eliminated

  4. Quantum critical phenomena and conformal invariance

    International Nuclear Information System (INIS)

    Zhe Chang.


    We show that the Abelian bosonization of continuum limit of the 1D Hubbard model corresponds to the 2D explicitly conformal invariant Gaussian model at weak coupling limit. A universality argument is used to extend the equivalence to an entire segment of the critical line of the strongly correlated electron system. An integral equation satisfied by the mapping function between critical lines of the 1D Hubbard model and 2D Gaussian model is obtained and then solved in some limiting cases. By making use of the fact that the free Hubbard system reduces to four fermions and each of them is related to a c = 1/2 conformal field theory, we present exactly the partition function of the Hubbard model on a finite 1D lattice. (author). 16 refs

  5. Quantum Triple Point and Quantum Critical End Points in Metallic Magnets. (United States)

    Belitz, D; Kirkpatrick, T R


    In low-temperature metallic magnets, ferromagnetic (FM) and antiferromagnetic (AFM) orders can exist, adjacent to one another or concurrently, in the phase diagram of a single system. We show that universal quantum effects qualitatively alter the known phase diagrams for classical magnets. They shrink the region of concurrent FM and AFM order, change various transitions from second to first order, and, in the presence of a magnetic field, lead to either a quantum triple point where the FM, AFM, and paramagnetic phases all coexist or a quantum critical end point.

  6. Characterization of the critical submanifolds in quantum ensemble control landscapes

    International Nuclear Information System (INIS)

    Wu Rebing; Rabitz, Herschel; Hsieh, Michael


    The quantum control landscape is defined as the functional that maps the control variables to the expectation values of an observable over the ensemble of quantum systems. Analyzing the topology of such landscapes is important for understanding the origins of the increasing number of laboratory successes in the optimal control of quantum processes. This paper proposes a simple scheme to compute the characteristics of the critical topology of the quantum ensemble control landscapes showing that the set of disjoint critical submanifolds one-to-one corresponds to a finite number of contingency tables that solely depend on the degeneracy structure of the eigenvalues of the initial system density matrix and the observable whose expectation value is to be maximized. The landscape characteristics can be calculated as functions of the table entries, including the dimensions and the numbers of positive and negative eigenvalues of the Hessian quadratic form of each of the connected components of the critical submanifolds. Typical examples are given to illustrate the effectiveness of this method

  7. Quantum critical spin-2 chain with emergent SU(3) symmetry. (United States)

    Chen, Pochung; Xue, Zhi-Long; McCulloch, I P; Chung, Ming-Chiang; Huang, Chao-Chun; Yip, S-K


    We study the quantum critical phase of an SU(2) symmetric spin-2 chain obtained from spin-2 bosons in a one-dimensional lattice. We obtain the scaling of the finite-size energies and entanglement entropy by exact diagonalization and density-matrix renormalization group methods. From the numerical results of the energy spectra, central charge, and scaling dimension we identify the conformal field theory describing the whole critical phase to be the SU(3)_{1} Wess-Zumino-Witten model. We find that, while the Hamiltonian is only SU(2) invariant, in this critical phase there is an emergent SU(3) symmetry in the thermodynamic limit.

  8. Chemical applications of molecular quantum theory

    Energy Technology Data Exchange (ETDEWEB)

    Ungemach, S.R.


    Molecular systems of chemical interest are investigated with the aid of molecular quantum theory. The self-consistent field (SCF) method is used to predict the molecular structures of ClF/sub 2/, ClF/sub 4/ and Cl/sub 3/ radicals, and the ions ClF/sub 2//sup +/, ClF/sub 2//sup -/, ClF/sub 4//sup +/ and ClF/sub 4//sup -/. The ClF/sub 2/ and Cl/sub 3/ radicals are predicted to be bent with bond angles of 145.2/sup 0/ and 158.6/sup 0/, respectively, while the ions ClF/sub 2//sup +/ and ClF/sub 2//sup -/ are predicted to be bent with a bond angle of 97.4/sup 0/ and linear, respectively. The geometry predictions for the ClF/sub 4/ radical and the ClF/sub 4//sup +/ ion are found to be notably basis set dependent. The ClF/sub 4//sup -/ ion is predicted to be square-planar. Multi-configuration self-consistent field (MCSCF) calculations have yielded the dipole moment function for the /sup 1/sigma/sup +/ state of HI, which qualitatively confirms the experimental finding that the dipole derivative at R/sub e/ is negative. The /sup 2/sigma/sup +/ F + H/sub 2/ potential energy surface is studied extensively with the configuration interaction (CI) method. The most complete calculations yield an activation energy of 2.74 kcal/mole and an exothermicity of 30.0 kcal/mole. The production of a potential energy surface of ''chemical accuracy'' for this system is found to be more difficult than previously believed. The simplest hydrophobic model, the water-methane system, is studied with the SCF method in order to determine the nature and magnitude of the interaction. The most favorable geometric arrangement corresponds to an attraction of 0.5 kcal/mole.

  9. Entanglement dynamics in critical random quantum Ising chain with perturbations

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Yichen, E-mail:


    We simulate the entanglement dynamics in a critical random quantum Ising chain with generic perturbations using the time-evolving block decimation algorithm. Starting from a product state, we observe super-logarithmic growth of entanglement entropy with time. The numerical result is consistent with the analytical prediction of Vosk and Altman using a real-space renormalization group technique. - Highlights: • We study the dynamical quantum phase transition between many-body localized phases. • We simulate the dynamics of a very long random spin chain with matrix product states. • We observe numerically super-logarithmic growth of entanglement entropy with time.

  10. Quantum-chemical insights from deep tensor neural networks (United States)

    Schütt, Kristof T.; Arbabzadah, Farhad; Chmiela, Stefan; Müller, Klaus R.; Tkatchenko, Alexandre


    Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol-1) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems.

  11. Superconductivity versus quantum criticality: Effects of thermal fluctuations (United States)

    Wang, Huajia; Wang, Yuxuan; Torroba, Gonzalo


    We study the interplay between superconductivity and non-Fermi liquid behavior of a Fermi surface coupled to a massless SU(N ) matrix boson near the quantum critical point. The presence of thermal infrared singularities in both the fermionic self-energy and the gap equation invalidates the Eliashberg approximation, and makes the quantum-critical pairing problem qualitatively different from that at zero temperature. Taking the large N limit, we solve the gap equation beyond the Eliashberg approximation, and obtain the superconducting temperature Tc as a function of N . Our results show an anomalous scaling between the zero-temperature gap and Tc. For N greater than a critical value, we find that Tc vanishes with a Berezinskii-Kosterlitz-Thouless scaling behavior, and the system retains non-Fermi liquid behavior down to zero temperature. This confirms and extends previous renormalization-group analyses done at T =0 , and provides a controlled example of a naked quantum critical point. We discuss the crucial role of thermal fluctuations in relating our results with earlier work where superconductivity always develops due to the special role of the first Matsubara frequency.

  12. Subvacuum effects in quantum critical theories from a holographic approach (United States)

    Yeh, Chen-Pin; Lee, Da-Shin


    The subvacuum phenomena, induced by the squeezed vacuum of the strongly coupled quantum critical fields with a dynamical scaling z , are explored by a probe particle. The holographic description corresponds to a string moving in (4 +1 )-dimensional Lifshitz geometry with gravitational wave perturbations. The dynamics of the particle can be realized from the motion of the endpoint of the string at the boundary. We then examine the particle's velocity dispersion, influenced by the squeezed vacuum states of strongly coupled quantum critical fields. With appropriate choices of squeezing parameters, the velocity dispersion is found to be smaller than the value caused by the normal vacuum fluctuations of the fields. This leads to the subvacuum effect. We find that the large coupling constant of the quantum fields tends to counteract the effect in the reduction of velocity dispersion, though this phenomenon is in principle observable. The effect of the squeezed vacuum on the decoherence dynamics of a quantum particle is also investigated. Coherence loss can be shown to be less severe in certain squeezed vacuums than in normal vacuum. This recovery of coherence is understood as recoherence, another manifestation of the subvacuum phenomena. We make some estimates of the degree of recoherence and find that, contrary to the velocity dispersion case, the recoherence effect is enhanced by the large coupling constant. Finally we compare the findings in our earlier works when the particle is influenced by a weakly coupled relativistic field with the dynamical scaling z =1 .

  13. Kinetic measurements and quantum chemical calculations on low ...

    Indian Academy of Sciences (India)

    Home; Journals; Journal of Chemical Sciences; Volume 127; Issue 7. Kinetic measurements and quantum chemical calculations on low spin Ni(II)/(III) macrocyclic complexes in aqueous and sulphato medium. Anuradha Sankaran E J Padma Malar Venkatapuram Ramanujam Vijayaraghavan. Regular Articles Volume 127 ...

  14. Entanglement entropy of 2D conformal quantum critical points: hearing the shape of a quantum drum. (United States)

    Fradkin, Eduardo; Moore, Joel E


    The entanglement entropy of a pure quantum state of a bipartite system A union or logical sumB is defined as the von Neumann entropy of the reduced density matrix obtained by tracing over one of the two parts. In one dimension, the entanglement of critical ground states diverges logarithmically in the subsystem size, with a universal coefficient that for conformally invariant critical points is related to the central charge of the conformal field theory. We find that the entanglement entropy of a standard class of z=2 conformal quantum critical points in two spatial dimensions, in addition to a nonuniversal "area law" contribution linear in the size of the AB boundary, generically has a universal logarithmically divergent correction, which is completely determined by the geometry of the partition and by the central charge of the field theory that describes the critical wave function.

  15. Thermal conductivity at a disordered quantum critical point

    International Nuclear Information System (INIS)

    Hartnoll, Sean A.; Ramirez, David M.; Santos, Jorge E.


    Strongly disordered and strongly interacting quantum critical points are difficult to access with conventional field theoretic methods. They are, however, both experimentally important and theoretically interesting. In particular, they are expected to realize universal incoherent transport. Such disordered quantum critical theories have recently been constructed holographically by deforming a CFT by marginally relevant disorder. In this paper we find additional disordered fixed points via relevant disordered deformations of a holographic CFT. Using recently developed methods in holographic transport, we characterize the thermal conductivity in both sets of theories in 1+1 dimensions. The thermal conductivity is found to tend to a constant at low temperatures in one class of fixed points, and to scale as T 0.3 in the other. Furthermore, in all cases the thermal conductivity exhibits discrete scale invariance, with logarithmic in temperature oscillations superimposed on the low temperature scaling behavior. At no point do we use the replica trick.

  16. Entropy Flow Through Near-Critical Quantum Junctions (United States)

    Friedan, Daniel


    This is the continuation of Friedan (J Stat Phys, 2017. doi: 10.1007/s10955-017-1752-8). Elementary formulas are derived for the flow of entropy through a circuit junction in a near-critical quantum circuit close to equilibrium, based on the structure of the energy-momentum tensor at the junction. The entropic admittance of a near-critical junction in a bulk-critical circuit is expressed in terms of commutators of the chiral entropy currents. The entropic admittance at low frequency, divided by the frequency, gives the change of the junction entropy with temperature—the entropic "capacitance". As an example, and as a check on the formalism, the entropic admittance is calculated explicitly for junctions in bulk-critical quantum Ising circuits (free fermions, massless in the bulk), in terms of the reflection matrix of the junction. The half-bit of information capacity per end of critical Ising wire is re-derived by integrating the entropic "capacitance" with respect to temperature, from T=0 to T=∞.

  17. Isomorphism of critical and off-critical operator spaces in two-dimensional quantum field theory

    Energy Technology Data Exchange (ETDEWEB)

    Delfino, G. [International School of Advanced Studies (SISSA), Trieste (Italy)]|[INFN sezione di Trieste (Italy); Niccoli, G. [Univ. de Cergy-Pontoise (France). LPTM


    For the simplest quantum field theory originating from a non-trivial fixed point of the renormalization group, the Lee-Yang model, we show that the operator space determined by the particle dynamics in the massive phase and that prescribed by conformal symmetry at criticality coincide. (orig.)

  18. Superuniversal transport near a (2 +1 ) -dimensional quantum critical point (United States)

    Rose, F.; Dupuis, N.


    We compute the zero-temperature conductivity in the two-dimensional quantum O (N ) model using a nonperturbative functional renormalization-group approach. At the quantum critical point we find a universal conductivity σ*/σQ (with σQ=q2/h the quantum of conductance and q the charge) in reasonable quantitative agreement with quantum Monte Carlo simulations and conformal bootstrap results. In the ordered phase the conductivity tensor is defined, when N ≥3 , by two independent elements, σA(ω ) and σB(ω ) , respectively associated with SO (N ) rotations which do and do not change the direction of the order parameter. Whereas σA(ω →0 ) corresponds to the response of a superfluid (or perfect inductance), the numerical solution of the flow equations shows that limω→0σB(ω ) /σQ=σB*/σQ is a superuniversal (i.e., N -independent) constant. These numerical results, as well as the known exact value σB*/σQ=π /8 in the large-N limit, allow us to conjecture that σB*/σQ=π /8 holds for all values of N , a result that can be understood as a consequence of gauge invariance and asymptotic freedom of the Goldstone bosons in the low-energy limit.

  19. Impurities near an antiferromagnetic-singlet quantum critical point

    International Nuclear Information System (INIS)

    Mendes-Santos, T.; Costa, N. C.; Batrouni, G.


    Heavy-fermion systems and other strongly correlated electron materials often exhibit a competition between antiferromagnetic (AF) and singlet ground states. We examine the effect of impurities in the vicinity of such an AF-singlet quantum critical point (QCP), through an appropriately defined “impurity susceptibility” χimp, using exact quantum Monte Carlo simulations. Our key finding is a connection within a single calculational framework between AF domains induced on the singlet side of the transition and the behavior of the nuclear magnetic resonance (NMR) relaxation rate 1/T1. Furthermore, we show that local NMR measurements provide a diagnostic for the location of the QCP, which agrees remarkably well with the vanishing of the AF order parameter and large values of χimp.

  20. Single-copy entanglement in critical quantum spin chains

    International Nuclear Information System (INIS)

    Eisert, J.; Cramer, M.


    We consider the single-copy entanglement as a quantity to assess quantum correlations in the ground state in quantum many-body systems. We show for a large class of models that already on the level of single specimens of spin chains, criticality is accompanied with the possibility of distilling a maximally entangled state of arbitrary dimension from a sufficiently large block deterministically, with local operations and classical communication. These analytical results--which refine previous results on the divergence of block entropy as the rate at which maximally entangled pairs can be distilled from many identically prepared chains--are made quantitative for general isotropic translationally invariant spin chains that can be mapped onto a quasifree fermionic system, and for the anisotropic XY model. For the XX model, we provide the asymptotic scaling of ∼(1/6)log 2 (L), and contrast it with the block entropy

  1. Critical reflections on the Chemical Leasing concept

    NARCIS (Netherlands)

    Lozano, Rodrigo; Carpenter, Angela; Lozano, Francisco J.

    Chemical Leasing has been developed as a collaborative business model to complement the two main approaches (policy initiatives and scientific/ technological) used to foster green chemistry and sustainable chemistry. Chemical Leasing is based on using chemicals more efficiently, reducing waste, and

  2. Quantum chemical approach to estimating the thermodynamics of metabolic reactions. (United States)

    Jinich, Adrian; Rappoport, Dmitrij; Dunn, Ian; Sanchez-Lengeling, Benjamin; Olivares-Amaya, Roberto; Noor, Elad; Even, Arren Bar; Aspuru-Guzik, Alán


    Thermodynamics plays an increasingly important role in modeling and engineering metabolism. We present the first nonempirical computational method for estimating standard Gibbs reaction energies of metabolic reactions based on quantum chemistry, which can help fill in the gaps in the existing thermodynamic data. When applied to a test set of reactions from core metabolism, the quantum chemical approach is comparable in accuracy to group contribution methods for isomerization and group transfer reactions and for reactions not including multiply charged anions. The errors in standard Gibbs reaction energy estimates are correlated with the charges of the participating molecules. The quantum chemical approach is amenable to systematic improvements and holds potential for providing thermodynamic data for all of metabolism.

  3. Experimental and quantum chemical studies on corrosion inhibition ...

    Indian Academy of Sciences (India)

    The corrosion inhibition effect of fluconazole (FLU) was investigated on steel in 1 M hydrochloric acid solution. Weight loss measurements and atomic force microscope analysis were utilized to investigate the corrosion inhibition properties and film formation behaviour of FLU. Quantum chemical approach was also used to ...

  4. Experimental and quantum chemical studies on corrosion inhibition ...

    Indian Academy of Sciences (India)

    The results showed that FLU can act as a good cor- rosion inhibitor for steel in hydrochloric acid solution at different temperatures and it can inhibit steel corrosion up to 95%. The adsorption followed the Langmuir isotherm and the thermodynamic parameters were also determined and discussed. Quantum chemical studies ...

  5. Estimates of Quantum Chemical Molecular Characteristics for Complete Basis Sets

    Czech Academy of Sciences Publication Activity Database

    Zahradník, Rudolf; Šroubková, Libuše


    Roč. 43, 3/4 (2003), s. 243-265 ISSN 0021-2148 Institutional research plan: CEZ:AV0Z4040901 Keywords : ab initio calculations * basis set extrapolations * quantum chemical Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.722, year: 2003

  6. Structural, vibrational, NMR, quantum chemical, DNA binding and ...

    Indian Academy of Sciences (India)

    Structural, vibrational, NMR, quantum chemical, DNA binding and protein docking studies of two flexible imine oximes. YUNUS KAYAa,b. aDepartment of Chemistry, Faculty of Arts and Sciences, Uludag University, 16059 Bursa, Turkey. bDepartment of Chemistry, Faculty of Natural Sciences, Architecture, and Engineering, ...

  7. Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution

    DEFF Research Database (Denmark)

    Carbonell-Sanroma, Eduard; Brandimarte, Pedro; Balog, Richard


    Bottom-up chemical reactions of selected molecular precursors on a gold surface can produce high quality graphene nanoribbons (GNRs). Here, we report on the formation of quantum dots embedded in an armchair GNR by substitutional inclusion of pairs of boron atoms into the GNR backbone. The boron...

  8. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola


    Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo...

  9. Experimental and quantum chemical studies on corrosion inhibition ...

    Indian Academy of Sciences (India)

    transfer resistance and double-layer capacitance that confirmed strong adsorption of inhibitors on the MS surface. The inhibition action of these compounds was assumed to occur via adsorption on the steel surface through the active centres contained in the molecules. Furthermore, quantum chemical calculations have ...

  10. Experimental and quantum chemical studies on corrosion inhibition ...

    Indian Academy of Sciences (India)

    Abstract. The corrosion inhibition effect of fluconazole (FLU) was investigated on steel in 1 M hydrochloric acid solution. Weight loss measurements and atomic force microscope analysis were utilized to investigate the corrosion inhibition properties and film formation behaviour of FLU. Quantum chemical approach was also ...

  11. Experimental and quantum chemical studies on corrosion inhibition

    Indian Academy of Sciences (India)

    The corrosion inhibition effect of fluconazole (FLU) was investigated on steel in 1 M hydrochloric acid solution. Weight loss measurements and atomic force microscope analysis were utilized to investigate the corrosion inhibition properties and film formation behaviour of FLU. Quantum chemical approach was also used to ...

  12. Synthesis, quantum chemical computations and x-ray ...

    African Journals Online (AJOL)

    Benyza N


    May 1, 2017 ... Journal of Fundamental and Applied Sciences is licensed under a Creative Commons Attribution-NonCommercial 4.0. International License. Libraries Resource Directory. We are listed under Research Associations category. SYNTHESIS, QUANTUM CHEMICAL COMPUTATIONS AND X-RAY.

  13. Quantum chemical calculations of using density functional theory ...

    Indian Academy of Sciences (India)



    Feb 15, 2018 ... Abstract. Quantum chemical calculations have been employed to study the molecular effects produced by. Cr2O3/SnO2 optimised structure. The theoretical parameters of the transparent conducting metal oxides were calculated using DFT/B3LYP/LANL2DZ method. The optimised bond parameters such as ...

  14. Quantum chemical study of mechanisms of dissociation and ...

    Indian Academy of Sciences (India)

    Quantum chemical study of mechanisms of dissociation and isomerization reactions in some molecules and radicals of astrophysical significance: Cyanides and related molecules. V P GUPTA∗ and ARCHNA SHARMA. Department of Physics, University of Jammu, Jammu-Tawi 180 006, India. ∗Corresponding author: ...

  15. The critical point of quantum chromodynamics through lattice and ...

    Indian Academy of Sciences (India)

    Abstract. This talk discusses methods of extending lattice computations at finite temperature into regions of finite chemical potential, and the conditions under which such results from the lattice may be compared to experiments. Such comparisons away from a critical point are absolutely essential for quantitative use of lattice ...

  16. Remote Chemical Sensing Using Quantum Cascade Lasers

    Energy Technology Data Exchange (ETDEWEB)

    Harper, Warren W.; Schultz, John F.


    Spectroscopic chemical sensing research at Pacific Northwest National Laboratory (PNNL) is focused on developing advanced sensors for detecting the production of nuclear, chemical, or biological weapons; use of chemical weapons; or the presence of explosives, firearms, narcotics, or other contraband of significance to homeland security in airports, cargo terminals, public buildings, or other sensitive locations. For most of these missions, the signature chemicals are expected to occur in very low concentrations, and in mixture with ambient air or airborne waste streams that contain large numbers of other species that may interfere with spectroscopic detection, or be mistaken for signatures of illicit activity. PNNL’s emphasis is therefore on developing remote and sampling sensors with extreme sensitivity, and resistance to interferents, or selectivity. PNNL’s research activities include: 1. Identification of signature chemicals and quantification of their spectral characteristics, 2. Identification and development of laser and other technologies that enable breakthroughs in sensitivity and selectivity, 3. Development of promising sensing techniques through experimentation and modeling the physical phenomenology and practical engineering limitations affecting their performance, and 4. Development and testing of data collection methods and analysis algorithms. Close coordination of all aspects of the research is important to ensure that all parts are focused on productive avenues of investigation. Close coordination of experimental development and numerical modeling is particularly important because the theoretical component provides understanding and predictive capability, while the experiments validate calculations and ensure that all phenomena and engineering limitations are considered.

  17. Critical exponents for the Reggeon quantum spin model

    International Nuclear Information System (INIS)

    Brower, R.C.; Furman, M.A.


    The Reggeon quantum spin (RQS) model on the transverse lattice in D dimensional impact parameter space has been conjectured to have the same critical behaviour as the Reggeon field theory (RFT). Thus from a high 'temperature' series of ten (D=2) and twenty (D=1) terms for the RQS model the authors extrapolate to the critical temperature T=Tsub(c) by Pade approximants to obtain the exponents eta=0.238 +- 0.008, z=1.16 +- 0.01, γ=1.271 +- 0.007 for D=2 and eta=0.317 +- 0.002, z=1.272 +- 0.007, γ=1.736 +- 0.001, lambda=0.57 +- 0.03 for D=1. These exponents naturally interpolate between the D=0 and D=4-epsilon results for RFT as expected on the basis of the universality conjecture. (Auth.)

  18. Quantum critical scaling for field-induced quantum phase transition in a periodic Anderson-like model polymer chain

    Energy Technology Data Exchange (ETDEWEB)

    Ding, L.J., E-mail:; Zhong, Y.


    Highlights: • The quantum critical scaling is investigated by Green’s function theory. • The obtained power-law critical exponents (β, δ and α) obey the critical scaling relation α + β(1 + δ) = 2. • The scaling hypothesis equations are proposed to verify the scaling analysis. - Abstract: The quantum phase transition and thermodynamics of a periodic Anderson-like polymer chain in a magnetic field are investigated by Green’s function theory. The T-h phase diagram is explored, wherein a crossover temperature T{sup ∗} denoting the gapless phase crossover into quantum critical regimes, smoothly connects near the critical fields to the universal linear line T{sup ∗} ∼ (h − h{sub c,s}), and ends at h{sub c,s}, providing a new route to capture quantum critical point (QCP). The quantum critical scaling around QCPs is demonstrated by analyzing magnetization, specific heat and Grüneisen parameter Γ{sub h}, which provide direct access to distill the power-law critical exponents (β, δ and α) obeying the critical scaling relation α + β(1 + δ) = 2, analogous to the quantum spin system. Furthermore, scaling hypothesis equations are proposed to check the scaling analysis, for which all the data collapse onto a single curve or two independent branches for the plot against an appropriate scaling variable, indicating the self-consistency and reliability of the obtained critical exponents.

  19. Fermi-surface collapse and dynamical scaling near a quantum-critical point (United States)

    Friedemann, Sven; Oeschler, Niels; Wirth, Steffen; Krellner, Cornelius; Geibel, Christoph; Steglich, Frank; Paschen, Silke; Kirchner, Stefan; Si, Qimiao


    Quantum criticality arises when a macroscopic phase of matter undergoes a continuous transformation at zero temperature. While the collective fluctuations at quantum-critical points are being increasingly recognized as playing an important role in a wide range of quantum materials, the nature of the underlying quantum-critical excitations remains poorly understood. Here we report in-depth measurements of the Hall effect in the heavy-fermion metal YbRh2Si2, a prototypical system for quantum criticality. We isolate a rapid crossover of the isothermal Hall coefficient clearly connected to the quantum-critical point from a smooth background contribution; the latter exists away from the quantum-critical point and is detectable through our studies only over a wide range of magnetic field. Importantly, the width of the critical crossover is proportional to temperature, which violates the predictions of conventional theory and is instead consistent with an energy over temperature, E/T, scaling of the quantum-critical single-electron fluctuation spectrum. Our results provide evidence that the quantum-dynamical scaling and a critical Kondo breakdown simultaneously operate in the same material. Correspondingly, we infer that macroscopic scale-invariant fluctuations emerge from the microscopic many-body excitations associated with a collapsing Fermi-surface. This insight is expected to be relevant to the unconventional finite-temperature behavior in a broad range of strongly correlated quantum systems. PMID:20668246

  20. Thermodynamic quantum critical behavior of the anisotropic Kondo necklace model

    Energy Technology Data Exchange (ETDEWEB)

    Reyes, D. [Centro Brasileiro de Pesquisas Fisicas, Rua Dr. Xavier Sigaud, 150-Urca, 22290-180 RJ (Brazil)], E-mail:; Continentino, M.A. [Instituto de Fisica, Universidade Federal Fluminense, Campus da Praia Vermelha, Niteroi, RJ 24.210-340 (Brazil); Wang Hanting [Beijing National Laboratory of Condensed Matter Physics and Institute of Physics, Chinese Academy of Sciences, Beijing 100080 (China)


    The Ising-like anisotropy parameter {delta} in the Kondo necklace model is analyzed using the bond-operator method at zero and finite temperatures for arbitrary d dimensions. A decoupling scheme on the double time Green's functions is used to find the dispersion relation for the excitations of the system. At zero temperature and in the paramagnetic side of the phase diagram, we determine the spin gap exponent {nu}z{approx}0.5 in three dimensions and anisotropy between 0{<=}{delta}{<=}1, a result consistent with the dynamic exponent z=1 for the Gaussian character of the bond-operator treatment. On the other hand, in the antiferromagnetic phase at low but finite temperatures, the line of Neel transitions is calculated for {delta}<<1. For d>2 it is only re-normalized by the anisotropy parameter and varies with the distance to the quantum critical point (QCP) |g| as, T{sub N}{proportional_to}|g|{sup {psi}} where the shift exponent {psi}=1/(d-1). Nevertheless, in two dimensions, a long-range magnetic order occurs only at T=0 for any {delta}<<1. In the paramagnetic phase, we also find a power law temperature dependence on the specific heat at the quantum critical trajectoryJ/t=(J/t){sub c}, T{yields}0. It behaves as C{sub V}{proportional_to}T{sup d} for {delta}{<=}1 and {approx}1, in concordance with the scaling theory for z=1.

  1. Electrochemical, surface analytical and quantum chemical studies ...

    Indian Academy of Sciences (India)

    The corrosion inhibition efficiencies of these molecules and the global chemical reactivity relate to some parameters, such as EHOMO, ELUMO, gap energy ( E), electronegativity (χ), global hardness (η) and the fraction of electrons transferred from the inhibitor molecule to the metallic atom ( N). In addition, the local reactivity ...

  2. Chemical Fingerprinting Program for RSRM Critical Materials (United States)

    McClennen, William H.; Fife, Dennis J.; Killpack, Michael O.; Golde, Rick P.; Cash, Steve (Technical Monitor)


    This viewgraph presentation provides information on the chemical fingerprinting of RSRM (Reusable Sold Rocket Motor) components. A chemical fingerprint can be used to identify a material, to differentiate it from similar looking materials, or lead to its source. It can also identify unexpected changes to a vendor or supplier's material, and monitor aging.

  3. Use of ab initio quantum chemical methods in battery technology

    Energy Technology Data Exchange (ETDEWEB)

    Deiss, E. [Paul Scherrer Inst. (PSI), Villigen (Switzerland)


    Ab initio quantum chemistry can nowadays predict physical and chemical properties of molecules and solids. An attempt should be made to use this tool more widely for predicting technologically favourable materials. To demonstrate the use of ab initio quantum chemistry in battery technology, the theoretical energy density (energy per volume of active electrode material) and specific energy (energy per mass of active electrode material) of a rechargeable lithium-ion battery consisting of a graphite electrode and a nickel oxide electrode has been calculated with this method. (author) 1 fig., 1 tab., 7 refs.

  4. Two-loop disorder effects on the nematic quantum criticality in d-wave superconductors

    International Nuclear Information System (INIS)

    Wang, Jing


    The gapless nodal fermions exhibit non-Fermi liquid behaviors at the nematic quantum critical point that is supposed to exist in some d-wave cuprate superconductors. This non-Fermi liquid state may be turned into a disorder-dominated diffusive metal if the fermions also couple to a disordered potential that generates a relevant perturbation in the sense of renormalization group theory. It is therefore necessary to examine whether a specific disorder is relevant or not. We study the interplay between critical nematic fluctuation and random chemical potential by performing renormalization group analysis. The parameter that characterizes the strength of random chemical potential is marginal at the one-loop level, but becomes marginally relevant after including the two-loop corrections. Thus even weak random chemical potential leads to diffusive motion of nodal fermions and the significantly critical behaviors of physical implications, since the strength flows eventually to large values at low energies. - Highlights: • The gapless nodal fermions exhibit non-Fermi liquid behaviors at the nematic QCP. • The strength of random chemical potential is marginal at the one-loop level. • The strength becomes marginally relevant after including the two-loop corrections. • The diffusive metallic state is induced by the marginally relevant disorder. • The behaviors of some physical observables are presented at the nematic QCP

  5. Chemical accuracy from quantum Monte Carlo for the benzene dimer

    Energy Technology Data Exchange (ETDEWEB)

    Azadi, Sam, E-mail: [Department of Earth Science and Thomas Young Centre, University College London, London WC1E 6BT (United Kingdom); Cohen, R. E. [London Centre for Nanotechnology, University College London, London WC1E 6BT, United Kingdom and Extreme Materials Initiative, Geophysical Laboratory, Carnegie Institution of Washington, Washington, D.C. 20015 (United States)


    We report an accurate study of interactions between benzene molecules using variational quantum Monte Carlo (VMC) and diffusion quantum Monte Carlo (DMC) methods. We compare these results with density functional theory using different van der Waals functionals. In our quantum Monte Carlo (QMC) calculations, we use accurate correlated trial wave functions including three-body Jastrow factors and backflow transformations. We consider two benzene molecules in the parallel displaced geometry, and find that by highly optimizing the wave function and introducing more dynamical correlation into the wave function, we compute the weak chemical binding energy between aromatic rings accurately. We find optimal VMC and DMC binding energies of −2.3(4) and −2.7(3) kcal/mol, respectively. The best estimate of the coupled-cluster theory through perturbative triplets/complete basis set limit is −2.65(2) kcal/mol [Miliordos et al., J. Phys. Chem. A 118, 7568 (2014)]. Our results indicate that QMC methods give chemical accuracy for weakly bound van der Waals molecular interactions, comparable to results from the best quantum chemistry methods.

  6. Chemical dynamics in the gas phase: Time-dependent quantum mechanics of chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

    Gray, S.K. [Argonne National Laboratory, IL (United States)


    A major goal of this research is to obtain an understanding of the molecular reaction dynamics of three and four atom chemical reactions using numerically accurate quantum dynamics. This work involves: (i) the development and/or improvement of accurate quantum mechanical methods for the calculation and analysis of the properties of chemical reactions (e.g., rate constants and product distributions), and (ii) the determination of accurate dynamical results for selected chemical systems, which allow one to compare directly with experiment, determine the reliability of the underlying potential energy surfaces, and test the validity of approximate theories. This research emphasizes the use of recently developed time-dependent quantum mechanical methods, i.e. wave packet methods.

  7. Critical properties of effective gauge theories for novel quantum fluids

    Energy Technology Data Exchange (ETDEWEB)

    Smoergrav, Eivind


    Critical properties of U(1) symmetric gauge theories are studied in 2+1 dimensions, analytically through duality transformations and numerically through Monte Carlo simulations. Physical applications range from quantum phase transitions in two dimensional insulating materials to superfluid and superconducting properties of light atoms such as hydrogen under extreme pressure. A novel finite size scaling method, utilizing the third moment M{sub 3} of the action, is developed. Finite size scaling analysis of M{sub 3} yields the ratio (1 + alpha)/ny and 1/ny separately, so that critical exponents alpha and ny can be obtained independently without invoking hyperscaling. This thesis contains eight research papers and an introductory part covering some basic concepts and techniques. Paper 1: The novel M{sub 3} method is introduced and employed together with Monte Carlo simulations to study the compact Abelian Higgs model in the adjoint representation with q = 2. Paper 2: We study phase transitions in the compact Abelian Higgs model for fundamental charge q = 2; 3; 4; 5. Various other models are studied to benchmark the M{sub 3} method. Paper 3: This is a proceeding paper based on a talk given by F. S. Nogueira at the Aachen EPS HEP 2003 conference. A review of the results from Paper 1 and Paper 2 on the compact Abelian Higgs model together with some results on q = 1 obtained by F. S. Nogueira, H. Kleinert, and A. Sudboe is given. Paper 4: The effect of a Chern-Simons (CS) term in the phase structure of two Abelian gauge theories is studied. Paper 5: We study the critical properties of the N-component Ginzburg-Landau theory. Paper 6: We consider the vortices in the 2-component Ginzburg-Landau model in a finite but low magnetic field. The ground state is a lattice of co centered vortices in both order parameters. We find two novel phase transitions. i) A 'vortex sub-lattice melting' transition where vortices in the field with lowest phase stiffness (&apos

  8. Quantum Chemical Modeling of Homogeneous Water Oxidation Catalysis. (United States)

    Liao, Rong-Zhen; Siegbahn, Per E M


    The design of efficient and robust water oxidation catalysts has proven challenging in the development of artificial photosynthetic systems for solar energy harnessing and storage. Tremendous progress has been made in the development of homogeneous transition-metal complexes capable of mediating water oxidation. To improve the efficiency of the catalyst and to design new catalysts, a detailed mechanistic understanding is necessary. Quantum chemical modeling calculations have been successfully used to complement the experimental techniques to suggest a catalytic mechanism and identify all stationary points, including transition states for both O-O bond formation and O 2 release. In this review, recent progress in the applications of quantum chemical methods for the modeling of homogeneous water oxidation catalysis, covering various transition metals, including manganese, iron, cobalt, nickel, copper, ruthenium, and iridium, is discussed. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  9. Quantum critical phase with infinite projected entangled paired states (United States)

    Poilblanc, Didier; Mambrini, Matthieu


    A classification of SU(2)-invariant projected entangled paired states (PEPS) on the square lattice, based on a unique site tensor, has been recently introduced by Mambrini et al. [M. Mambrini, R. Orús, and D. Poilblanc, Phys. Rev. B 94, 205124 (2016), 10.1103/PhysRevB.94.205124]. It is not clear whether such SU(2)-invariant PEPS can either (i) exhibit long-range magnetic order (such as in the Néel phase) or (ii) describe a genuine quantum critical point (QCP) or quantum critical phase (QCPh) separating two ordered phases. Here, we identify a specific family of SU(2)-invariant PEPS of the classification which provides excellent variational energies for the J1-J2 frustrated Heisenberg model, especially at J2=0.5 , corresponding to the approximate location of the QCP or QCPh separating the Néel phase from a dimerized phase. The PEPS are built from virtual states belonging to the 1/2⊗N⊕0 SU(2) representation, i.e., with N "colors" of virtual spin-1/2 . Using a full-update infinite-PEPS approach directly in the thermodynamic limit, based on the corner transfer matrix renormalization algorithm supplemented by a conjugate gradient optimization scheme, we provide evidence of (i) the absence of magnetic order and of (ii) diverging correlation lengths (i.e., showing no sign of saturation with increasing environment dimension) in both the singlet and triplet channels, when the number of colors N ≥3 . We argue that such a PEPS gives a qualitative description of the QCP or QCPh of the J1-J2 model.

  10. Quantum-critical scaling of fidelity in 2D pairing models

    International Nuclear Information System (INIS)

    Adamski, Mariusz; Jȩdrzejewski, Janusz; Krokhmalskii, Taras


    The laws of quantum-critical scaling theory of quantum fidelity, dependent on the underlying system dimensionality D, have so far been verified in exactly solvable 1D models, belonging to or equivalent to interacting, quadratic (quasifree), spinless or spinfull, lattice-fermion models. The obtained results are so appealing that in quest for correlation lengths and associated universal critical indices ν, which characterize the divergence of correlation lengths on approaching critical points, one might be inclined to substitute the hard task of determining an asymptotic behavior at large distances of a two-point correlation function by an easier one, of determining the quantum-critical scaling of the quantum fidelity. However, the role of system's dimensionality has been left as an open problem. Our aim in this paper is to fill up this gap, at least partially, by verifying the laws of quantum-critical scaling theory of quantum fidelity in a 2D case. To this end, we study correlation functions and quantum fidelity of 2D exactly solvable models, which are interacting, quasifree, spinfull, lattice-fermion models. The considered 2D models exhibit new, as compared with 1D ones, features: at a given quantum-critical point there exists a multitude of correlation lengths and multiple universal critical indices ν, since these quantities depend on spatial directions, moreover, the indices ν may assume larger values. These facts follow from the obtained by us analytical asymptotic formulae for two-point correlation functions. In such new circumstances we discuss the behavior of quantum fidelity from the perspective of quantum-critical scaling theory. In particular, we are interested in finding out to what extent the quantum fidelity approach may be an alternative to the correlation-function approach in studies of quantum-critical points beyond 1D.

  11. Universal conductance and conductivity at critical points in integer quantum Hall systems. (United States)

    Schweitzer, L; Markos, P


    The sample averaged longitudinal two-terminal conductance and the respective Kubo conductivity are calculated at quantum critical points in the integer quantum Hall regime. In the limit of large system size, both transport quantities are found to be the same within numerical uncertainty in the lowest Landau band, and , respectively. In the second-lowest Landau band, a critical conductance is obtained which indeed supports the notion of universality. However, these numbers are significantly at variance with the hitherto commonly believed value . We argue that this difference is due to the multifractal structure of critical wave functions, a property that should generically show up in the conductance at quantum critical points.

  12. Theory of finite-entanglement scaling at one-dimensional quantum critical points. (United States)

    Pollmann, Frank; Mukerjee, Subroto; Turner, Ari M; Moore, Joel E


    Studies of entanglement in many-particle systems suggest that most quantum critical ground states have infinitely more entanglement than noncritical states. Standard algorithms for one-dimensional systems construct model states with limited entanglement, which are a worse approximation to quantum critical states than to others. We give a quantitative theory of previously observed scaling behavior resulting from finite entanglement at quantum criticality. Finite-entanglement scaling in one-dimensional systems is governed not by the scaling dimension of an operator but by the "central charge" of the critical point. An important ingredient is the universal distribution of density-matrix eigenvalues at a critical point [P. Calabrese and A. Lefevre, Phys. Rev. A 78, 032329 (2008)10.1103/PhysRevA.78.032329]. The parameter-free theory is checked against numerical scaling at several quantum critical points.

  13. Fermionic quantum critical point of spinless fermions on a honeycomb lattice

    International Nuclear Information System (INIS)

    Wang, Lei; Corboz, Philippe; Troyer, Matthias


    Spinless fermions on a honeycomb lattice provide a minimal realization of lattice Dirac fermions. Repulsive interactions between nearest neighbors drive a quantum phase transition from a Dirac semimetal to a charge-density-wave state through a fermionic quantum critical point, where the coupling of the Ising order parameter to the Dirac fermions at low energy drastically affects the quantum critical behavior. Encouraged by a recent discovery (Huffman and Chandrasekharan 2014 Phys. Rev. B 89 111101) of the absence of the fermion sign problem in this model, we study the fermionic quantum critical point using the continuous-time quantum Monte Carlo method with a worm-sampling technique. We estimate the transition point V/t=1.356(1) with the critical exponents ν=0.80(3) and η=0.302(7). Compatible results for the transition point are also obtained with infinite projected entangled-pair states. (paper)

  14. Energy scales and magnetoresistance at a quantum critical point

    Energy Technology Data Exchange (ETDEWEB)

    Shaginyan, V.R. [Petersburg Nuclear Physics Institute, RAS, Gatchina, 188300 (Russian Federation); Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel); CTSPS, Clark Atlanta University, Atlanta, GA 30314 (United States)], E-mail:; Amusia, M.Ya. [Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel); Msezane, A.Z. [CTSPS, Clark Atlanta University, Atlanta, GA 30314 (United States); Popov, K.G. [Komi Science Center, Ural Division, RAS, 3a Chernova street, Syktyvkar, 167982 (Russian Federation); Stephanovich, V.A. [Opole University, Institute of Mathematics and Informatics, Opole, 45-052 (Poland)


    The magnetoresistance (MR) of CeCoIn{sub 5} is notably different from that in many conventional metals. We show that a pronounced crossover from negative to positive MR at elevated temperatures and fixed magnetic fields is determined by the scaling behavior of quasiparticle effective mass. At a quantum critical point (QCP) this dependence generates kinks (crossover points from fast to slow growth) in thermodynamic characteristics (like specific heat, magnetization, etc.) at some temperatures when a strongly correlated electron system transits from the magnetic field induced Landau-Fermi liquid (LFL) regime to the non-Fermi liquid (NFL) one taking place at rising temperatures. We show that the above kink-like peculiarity separates two distinct energy scales in QCP vicinity - low temperature LFL scale and high temperature one related to NFL regime. Our comprehensive theoretical analysis of experimental data permits to reveal for the first time new MR and kinks scaling behavior as well as to identify the physical reasons for above energy scales.

  15. Surface emitting ring quantum cascade lasers for chemical sensing (United States)

    Szedlak, Rolf; Hayden, Jakob; Martín-Mateos, Pedro; Holzbauer, Martin; Harrer, Andreas; Schwarz, Benedikt; Hinkov, Borislav; MacFarland, Donald; Zederbauer, Tobias; Detz, Hermann; Andrews, Aaron Maxwell; Schrenk, Werner; Acedo, Pablo; Lendl, Bernhard; Strasser, Gottfried


    We review recent advances in chemical sensing applications based on surface emitting ring quantum cascade lasers (QCLs). Such lasers can be implemented in monolithically integrated on-chip laser/detector devices forming compact gas sensors, which are based on direct absorption spectroscopy according to the Beer-Lambert law. Furthermore, we present experimental results on radio frequency modulation up to 150 MHz of surface emitting ring QCLs. This technique provides detailed insight into the modulation characteristics of such lasers. The gained knowledge facilitates the utilization of ring QCLs in combination with spectroscopic techniques, such as heterodyne phase-sensitive dispersion spectroscopy for gas detection and analysis.

  16. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola


    Several mechanisms for the peroxide oxidation of organosilanes to alcohols are compared by quantum chemical calculations, including solvation with the PCM method. Without doubt, the reaction proceeds via anionic, pentacoordinate silicate species, but a profound difference is found between in vacuo...... and solvated reaction profiles, as expected. In the solvents investigated (CH2Cl2 and MeOH), the most favorable mechanism is addition of peroxide anion to a fluorosilane (starting material or formed in situ), followed by a concerted migration and dissociation of hydroxide anion. In the gas phase, and possibly...

  17. Ab initio Quantum Chemical and Experimental Reaction Kinetics Studies in the Combustion of Bipropellants (United States)


    NUMBER (Include area code) 24 March 2017 Briefing Charts 01 March 2017 - 31 March 2017 Ab initio Quantum Chemical and Experimental Reaction Kinetics...Laboratory AFRL/RQRS 1 Ara Road Edwards AFB, CA 93524 *Email: Ab initio Quantum Chemical and Experimental Reaction ...Clearance 17161 Zador et al., Prog. Energ. Combust. Sci., 37 371 (2011) Why Quantum Chemical Reaction Kinetics Studies? DISTRIBUTION A: Approved for

  18. Zero-field quantum critical point in CeCoIn5. (United States)

    Tokiwa, Y; Bauer, E D; Gegenwart, P


    Quantum criticality in the normal and superconducting states of the heavy-fermion metal CeCoIn5 is studied by measurements of the magnetic Grüneisen ratio ΓH and specific heat in different field orientations and temperatures down to 50 mK. A universal temperature over magnetic field scaling of ΓH in the normal state indicates a hidden quantum critical point at zero field. Within the superconducting state, the quasiparticle entropy at constant temperature increases upon reducing the field towards zero, providing additional evidence for zero-field quantum criticality.

  19. Quantum wavepacket ab initio molecular dynamics: an approach for computing dynamically averaged vibrational spectra including critical nuclear quantum effects. (United States)

    Sumner, Isaiah; Iyengar, Srinivasan S


    We have introduced a computational methodology to study vibrational spectroscopy in clusters inclusive of critical nuclear quantum effects. This approach is based on the recently developed quantum wavepacket ab initio molecular dynamics method that combines quantum wavepacket dynamics with ab initio molecular dynamics. The computational efficiency of the dynamical procedure is drastically improved (by several orders of magnitude) through the utilization of wavelet-based techniques combined with the previously introduced time-dependent deterministic sampling procedure measure to achieve stable, picosecond length, quantum-classical dynamics of electrons and nuclei in clusters. The dynamical information is employed to construct a novel cumulative flux/velocity correlation function, where the wavepacket flux from the quantized particle is combined with classical nuclear velocities to obtain the vibrational density of states. The approach is demonstrated by computing the vibrational density of states of [Cl-H-Cl]-, inclusive of critical quantum nuclear effects, and our results are in good agreement with experiment. A general hierarchical procedure is also provided, based on electronic structure harmonic frequencies, classical ab initio molecular dynamics, computation of nuclear quantum-mechanical eigenstates, and employing quantum wavepacket ab initio dynamics to understand vibrational spectroscopy in hydrogen-bonded clusters that display large degrees of anharmonicities.

  20. Holographic aspects of black holes, matrix models and quantum criticality

    NARCIS (Netherlands)

    Papadoulaki, O.


    In one word the core subject of this thesis is holography. What we mean by holography broadly is the mapping of a gravitational theory in D dimensions to a quantum mechanics system or quantum field theory in one less dimension In chapter 1, we give a basic and self-contained introduction of the

  1. A critical analysis of the quantum theory of measurement

    International Nuclear Information System (INIS)

    Fer, F.


    Keeping strictly in the positivist and probabilistic, hence hilbertian frame of Quantum Mechanics, the author tries to ascertain whether or not Quantum Mechanics, starting from its axioms, reaches the aim of any physical theory, that is, comparison with experiment. The answer is: no, as long as it keeps close to the existing axiomatics, and also to accurate mathematics. (Auth.)

  2. A non-critical string approach to black holes, time and quantum dynamics

    CERN Document Server

    Ellis, John R.; Nanopoulos, Dimitri V.


    We review our approach to time and quantum dynamics based on non-critical string theory, developing its relationship to previous work on non-equilibrium quantum statistical mechanics and the microscopic arrow of time. We exhibit specific non-factorizing contributions to the {\

  3. Quantum criticality in electron-doped BaFe2-xNixAs2. (United States)

    Zhou, R; Li, Z; Yang, J; Sun, D L; Lin, C T; Zheng, Guo-qing


    A quantum critical point is a point in a system's phase diagram at which an order is completely suppressed at absolute zero temperature (T). The presence of a quantum critical point manifests itself in the finite-T physical properties, and often gives rise to new states of matter. Superconductivity in the cuprates and in heavy fermion materials is believed by many to be mediated by fluctuations associated with a quantum critical point. In the recently discovered iron-pnictide superconductors, we report transport and NMR measurements on BaFe(2-x)Ni(x)As₂ (0≤x≤0.17). We find two critical points at x(c1)=0.10 and x(c2)=0.14. The electrical resistivity follows ρ=ρ₀+AT(n), with n=1 around x(c1) and another minimal n=1.1 at x(c2). By NMR measurements, we identity x(c1) to be a magnetic quantum critical point and suggest that x(c2) is a new type of quantum critical point associated with a nematic structural phase transition. Our results suggest that the superconductivity in carrier-doped pnictides is closely linked to the quantum criticality.

  4. Critical components for diamond-based quantum coherent devices

    International Nuclear Information System (INIS)

    Greentree, Andrew D; Olivero, Paolo; Draganski, Martin; Trajkov, Elizabeth; Rabeau, James R; Reichart, Patrick; Gibson, Brant C; Rubanov, Sergey; Huntington, Shane T; Jamieson, David N; Prawer, Steven


    The necessary elements for practical devices exploiting quantum coherence in diamond materials are summarized, and progress towards their realization documented. A brief review of future prospects for diamond-based devices is also provided

  5. Quantum critical scaling at the edge of Fermi liquid stability in a cuprate superconductor. (United States)

    Butch, Nicholas P; Jin, Kui; Kirshenbaum, Kevin; Greene, Richard L; Paglione, Johnpierre


    In the high-temperature cuprate superconductors, the pervasiveness of anomalous electronic transport properties suggests that violation of conventional Fermi liquid behavior is closely tied to superconductivity. In other classes of unconventional superconductors, atypical transport is well correlated with proximity to a quantum critical point, but the relative importance of quantum criticality in the cuprates remains uncertain. Here, we identify quantum critical scaling in the electron-doped cuprate material La(2-x)Ce(x)CuO(4) with a line of quantum critical points that surrounds the superconducting phase as a function of magnetic field and charge doping. This zero-temperature phase boundary, which delineates a metallic Fermi liquid regime from an extended non-Fermi liquid ground state, closely follows the upper critical field of the overdoped superconducting phase and gives rise to an expanse of distinct non-Fermi liquid behavior at finite temperatures. Together with signatures of two distinct flavors of quantum fluctuations, these facts suggest that quantum criticality plays a significant role in shaping the anomalous properties of the cuprate phase diagram.

  6. Quantum chemical calculations on structures of actinide complexes

    International Nuclear Information System (INIS)

    Satoru, Tsushima; Tobias, Reich


    The results of our recent theoretical calculations on the structures and the hydration numbers of actinide complexes are discussed together with EXAFS data. The hydration number determined from the calculated Gibbs free energy (inclusive of the solvation energy) was found to be different from the hydration number determined from the electronic energy at 0 K, 0 atm. The roles of entropy and solvation energy were found to be important with regard to the stability of the actinide complexes. The structures of the aqueous uranyl complexes obtained by EXAFS measurements were compared with the structures obtained by 'gas phase' quantum chemical calculations. The importance of including the secondary co-ordination shell and counter-ions is discussed in this paper. (authors)

  7. Criticality of the anisotropic quantum Heisenberg model on a simple cubic lattice

    International Nuclear Information System (INIS)

    Mariz, A.M.; Tsallis, C.; Santos, R.M.Z. dos; Santos, Raimundo R. dos.


    Within a Real Space Renormalization Group Framework, the criticality (phase diagram, and critical thermal and crossover exponents) of the spin 1/2 - anisotropic quantum Heisenberg ferromagnet on a simple cubic lattice is studied. The results obtained are in antisfactory agreement with known results whenever available. (Author) [pt

  8. Non-linear quantum critical dynamics and fluctuation-dissipation ratios far from equilibrium

    Energy Technology Data Exchange (ETDEWEB)

    Zamani, Farzaneh [Max Planck Institute for the Physics of Complex Systems, Nöthnitzer Str. 38, 01187 Dresden (Germany); Max Planck Institute for Chemical Physics of Solids, Nöthnitzer Str. 40, 01187 Dresden (Germany); Ribeiro, Pedro [CeFEMA, Instituto Superior Tcnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa (Portugal); Russian Quantum Center, Novaya Street 100 A, Skolkovo, Moscow Area, 143025 (Russian Federation); Kirchner, Stefan, E-mail: [Center for Correlated Matter, Zhejiang University, Hangzhou, Zhejiang 310058 (China)


    Non-thermal correlations of strongly correlated electron systems and the far-from-equilibrium properties of phases of condensed matter have become a topical research area. Here, an overview of the non-linear dynamics found near continuous zero-temperature phase transitions within the context of effective temperatures is presented. In particular, we focus on models of critical Kondo destruction. Such a quantum critical state, where Kondo screening is destroyed in a critical fashion, is realized in a number of rare earth intermetallics. This raises the possibility of experimentally testing for the existence of fluctuation-dissipation relations far from equilibrium in terms of effective temperatures. Finally, we present an analysis of a non-interacting, critical reference system, the pseudogap resonant level model, in terms of effective temperatures and contrast these results with those obtained near interacting quantum critical points. - Highlights: • Critical Kondo destruction explains the unusual properties of quantum critical heavy fermion compounds. • We review the concept of effective temperatures in models of critical Kondo destruction. • We compare effective temperatures found near non-interacting and fully interacting fixed points. • A comparison with non-interacting quantum impurity models is presented.

  9. Cation solvation with quantum chemical effects modeled by a size-consistent multi-partitioning quantum mechanics/molecular mechanics method. (United States)

    Watanabe, Hiroshi C; Kubillus, Maximilian; Kubař, Tomáš; Stach, Robert; Mizaikoff, Boris; Ishikita, Hiroshi


    In the condensed phase, quantum chemical properties such as many-body effects and intermolecular charge fluctuations are critical determinants of the solvation structure and dynamics. Thus, a quantum mechanical (QM) molecular description is required for both solute and solvent to incorporate these properties. However, it is challenging to conduct molecular dynamics (MD) simulations for condensed systems of sufficient scale when adapting QM potentials. To overcome this problem, we recently developed the size-consistent multi-partitioning (SCMP) quantum mechanics/molecular mechanics (QM/MM) method and realized stable and accurate MD simulations, using the QM potential to a benchmark system. In the present study, as the first application of the SCMP method, we have investigated the structures and dynamics of Na + , K + , and Ca 2+ solutions based on nanosecond-scale sampling, a sampling 100-times longer than that of conventional QM-based samplings. Furthermore, we have evaluated two dynamic properties, the diffusion coefficient and difference spectra, with high statistical certainty. Furthermore the calculation of these properties has not previously been possible within the conventional QM/MM framework. Based on our analysis, we have quantitatively evaluated the quantum chemical solvation effects, which show distinct differences between the cations.

  10. Quantum Critical Origin of the Superconducting Dome in SrTiO_{3}. (United States)

    Edge, Jonathan M; Kedem, Yaron; Aschauer, Ulrich; Spaldin, Nicola A; Balatsky, Alexander V


    We expand the well-known notion that quantum criticality can induce superconductivity by proposing a concrete mechanism for superconductivity due to quantum ferroelectric fluctuations. To this end, we investigate the origin of superconductivity in doped SrTiO_{3} using a combination of density functional and strong coupling theories within the framework of quantum criticality. Our density functional calculations of the ferroelectric soft mode frequency as a function of doping reveal a crossover related to quantum paraelectricity at a doping level coincident with the experimentally observed top of the superconducting dome. Thus, we suggest a model in which the soft mode fluctuations provide the pairing interaction for superconductivity carriers. Within our model, the low doping limit of the superconducting dome is explained by the emergence of the Fermi surface, and the high doping limit by departure from the quantum critical regime. We predict that the highest critical temperature will increase and shift to lower carrier doping with increasing ^{18}O isotope substitution, a scenario that is experimentally verifiable. Our model is applicable to other quantum paraelectrics, such as KTaO_{3}.

  11. Quantum Critical Origin of the Superconducting Dome in SrTiO3 (United States)

    Edge, Jonathan M.; Kedem, Yaron; Aschauer, Ulrich; Spaldin, Nicola A.; Balatsky, Alexander V.


    We expand the well-known notion that quantum criticality can induce superconductivity by proposing a concrete mechanism for superconductivity due to quantum ferroelectric fluctuations. To this end, we investigate the origin of superconductivity in doped SrTiO3 using a combination of density functional and strong coupling theories within the framework of quantum criticality. Our density functional calculations of the ferroelectric soft mode frequency as a function of doping reveal a crossover related to quantum paraelectricity at a doping level coincident with the experimentally observed top of the superconducting dome. Thus, we suggest a model in which the soft mode fluctuations provide the pairing interaction for superconductivity carriers. Within our model, the low doping limit of the superconducting dome is explained by the emergence of the Fermi surface, and the high doping limit by departure from the quantum critical regime. We predict that the highest critical temperature will increase and shift to lower carrier doping with increasing 18O isotope substitution, a scenario that is experimentally verifiable. Our model is applicable to other quantum paraelectrics, such as KTaO3 .

  12. The quantum dynamics of electronically nonadiabatic chemical reactions (United States)

    Truhlar, Donald G.


    Considerable progress was achieved on the quantum mechanical treatment of electronically nonadiabatic collisions involving energy transfer and chemical reaction in the collision of an electronically excited atom with a molecule. In the first step, a new diabatic representation for the coupled potential energy surfaces was created. A two-state diabatic representation was developed which was designed to realistically reproduce the two lowest adiabatic states of the valence bond model and also to have the following three desirable features: (1) it is more economical to evaluate; (2) it is more portable; and (3) all spline fits are replaced by analytic functions. The new representation consists of a set of two coupled diabatic potential energy surfaces plus a coupling surface. It is suitable for dynamics calculations on both the electronic quenching and reaction processes in collisions of Na(3p2p) with H2. The new two-state representation was obtained by a three-step process from a modified eight-state diatomics-in-molecules (DIM) representation of Blais. The second step required the development of new dynamical methods. A formalism was developed for treating reactions with very general basis functions including electronically excited states. Our formalism is based on the generalized Newton, scattered wave, and outgoing wave variational principles that were used previously for reactive collisions on a single potential energy surface, and it incorporates three new features: (1) the basis functions include electronic degrees of freedom, as required to treat reactions involving electronic excitation and two or more coupled potential energy surfaces; (2) the primitive electronic basis is assumed to be diabatic, and it is not assumed that it diagonalizes the electronic Hamiltonian even asymptotically; and (3) contracted basis functions for vibrational-rotational-orbital degrees of freedom are included in a very general way, similar to previous prescriptions for locally

  13. Bound on quantum computation time: Quantum error correction in a critical environment

    International Nuclear Information System (INIS)

    Novais, E.; Mucciolo, Eduardo R.; Baranger, Harold U.


    We obtain an upper bound on the time available for quantum computation for a given quantum computer and decohering environment with quantum error correction implemented. First, we derive an explicit quantum evolution operator for the logical qubits and show that it has the same form as that for the physical qubits but with a reduced coupling strength to the environment. Using this evolution operator, we find the trace distance between the real and ideal states of the logical qubits in two cases. For a super-Ohmic bath, the trace distance saturates, while for Ohmic or sub-Ohmic baths, there is a finite time before the trace distance exceeds a value set by the user.

  14. Bifurcation in Ground-state Fidelity and Quantum Criticality in Two-leg Potts Ladder

    Directory of Open Access Journals (Sweden)

    Sheng-Hao LI


    Full Text Available We have investigated an intriguing connection between bifurcations, reduced fidelity per lattice site, local order parameter, universal order parameter, entropy and quantum phase transitions in the ground state for quantum three-state Potts model with two coupled infinite-size ladder system, in the context of the tensor network algorithm. The tensor network algorithm produces degenerate symmetry-breaking ground-state wave functions arising from the Z3 symmetry breaking, each of results from a randomly chosen initial state. We expect that our approach might provide further insights into critical phenomena in quantum many-body infinite lattice systems in condensed matter physics.

  15. Quantum chemical calculations of vibrational spectra of para-ethylbenzenesulfonic acid

    International Nuclear Information System (INIS)

    Zelenkovskij, V.M.; Bez''yazychnaya, T.V.; Soldatov, V.S.


    Quantum chemical calculations of vibrational spectra of para-ethylbenzenesulfonic acid have been conducted by means of a non-empirical SCF MO LCAO method with the use of the 6-31G(d) basis set. Calculated IR and Raman frequencies are assigned to vibrations of specific atomic groups. It is shown that para-ethylbenzenesulfonic acid can serve as a reasonable quantum chemical model in calculations of vibrational spectra for polystyrene sulfonic resins of various degrees of hydration. (authors) Key words IR absorption and Raman scattering spectra - quantum chemical calculations - para-ethylbenzenesulfonic acid

  16. Protein Structure Validation and Refinement Using Chemical Shifts Derived from Quantum Mechanics

    DEFF Research Database (Denmark)

    Bratholm, Lars Andersen

    to within 3 A. Furthermore, a fast quantum mechanics based chemical shift predictor was developed together with methodology for using chemical shifts in structure simulations. The developed predictor was used for renement of several protein structures and for reducing the computational cost of quantum...... mechanics / molecular mechanics (QM/MM) computations of chemical shieldings. Several improvements to the predictor is ongoing, where among other things, kernel based machine learning techniques have successfully been used to improve the quantum mechanical level of theory used in the predictions....

  17. Critical current anomaly at the topological quantum phase transition in a Majorana Josephson junction

    Energy Technology Data Exchange (ETDEWEB)

    Huang, Hong [School of Physics, Sun Yat-sen University, Guangzhou 510275 (China); Liang, Qi-Feng [Department of Physics, Shaoxing University, Shaoxing 312000 (China); Yao, Dao-Xin, E-mail: [School of Physics, Sun Yat-sen University, Guangzhou 510275 (China); Wang, Zhi, E-mail: [School of Physics, Sun Yat-sen University, Guangzhou 510275 (China)


    Majorana bound states in topological Josephson junctions induce a 4π period current-phase relation. Direct detection of the 4π periodicity is complicated by the quasiparticle poisoning. We reveal that Majorana bound states are also signaled by the anomalous enhancement on the critical current of the junction. We show the landscape of the critical current for a nanowire Josephson junction under a varying Zeeman field, and reveal a sharp step feature at the topological quantum phase transition point, which comes from the anomalous enhancement of the critical current at the topological regime. In multi-band wires, the anomalous enhancement disappears for an even number of bands, where the Majorana bound states fuse into Andreev bound states. This anomalous critical current enhancement directly signals the existence of the Majorana bound states, and also provides a valid signature for the topological quantum phase transition. - Highlights: • We introduce the critical current step as a signal for the topological quantum phase transition. • We study the quantum phase transition in the topological nanowire under a rotating Zeeman field. • We show that the critical current anomaly gradually disappears for systems with more sub-bands.

  18. Quantum critical point in high-temperature superconductors

    Energy Technology Data Exchange (ETDEWEB)

    Shaginyan, V.R. [Petersburg Nuclear Physics Institute, RAS, Gatchina 188300 (Russian Federation); Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel)], E-mail:; Amusia, M.Ya. [Racah Institute of Physics, Hebrew University, Jerusalem 91904 (Israel); Popov, K.G. [Komi Science Center, Ural Division, RAS, Syktyvkar 167982 (Russian Federation); Stephanovich, V.A. [Opole University, Institute of Mathematics and Informatics, Opole 45-052 (Poland)], E-mail:


    Recently, in high-T{sub c} superconductors (HTSC), exciting measurements have been performed revealing their physics in superconducting and pseudogap states and in normal one induced by the application of magnetic field, when the transition from non-Fermi liquid to Landau-Fermi liquid behavior occurs. We employ a theory, based on fermion condensation quantum phase transition which is able to explain facts obtained in the measurements. We also show, that in spite of very different microscopic nature of HTSC, heavy-fermion metals and 2D {sup 3}He, the physical properties of these three classes of substances are similar to each other.

  19. Rounding by disorder of first-order quantum phase transitions: emergence of quantum critical points. (United States)

    Goswami, Pallab; Schwab, David; Chakravarty, Sudip


    We give a heuristic argument for disorder rounding of a first-order quantum phase transition into a continuous phase transition. From both weak and strong disorder analysis of the N-color quantum Ashkin-Teller model in one spatial dimension, we find that, for N > or =3, the first-order transition is rounded to a continuous transition and the physical picture is the same as the random transverse field Ising model for a limited parameter regime. The results are strikingly different from the corresponding classical problem in two dimensions where the fate of the renormalization group flows is a fixed point corresponding to N-decoupled pure Ising models.

  20. Origin of chaos near critical points of quantum flow. (United States)

    Efthymiopoulos, C; Kalapotharakos, C; Contopoulos, G


    The general theory of motion in the vicinity of a moving quantum nodal point (vortex) is studied in the framework of the de Broglie-Bohm trajectory method of quantum mechanics. Using an adiabatic approximation, we find that near any nodal point of an arbitrary wave function psi there is an unstable point (called the X point) in a frame of reference moving with the nodal point. The local phase portrait forms always a characteristic pattern called the "nodal-point- X -point complex." We find general formulas for this complex as well as necessary and sufficient conditions of validity of the adiabatic approximation. We demonstrate that chaos emerges from the consecutive scattering events of the orbits with nodal-point- X -point complexes. The scattering events are of two types (called type I and type II). A theoretical model is constructed yielding the local value of the Lyapunov characteristic numbers in scattering events of both types. The local Lyapunov characteristic number scales as an inverse power of the speed of the nodal point in the rest frame, implying that it scales proportionally to the size of the nodal-point- X -point complex. It is also an inverse power of the distance of a trajectory from the X point's stable manifold far from the complex. This distance plays the role of an effective "impact parameter." The results of detailed numerical experiments with different wave functions, possessing one, two, or three moving nodal points, are reported. Examples are given of regular and chaotic trajectories, and the statistics of the Lyapunov characteristic numbers of the orbits are found and compared to the number of encounter events of each orbit with the nodal-point- X -point complexes. The numerical results are in agreement with the theory, and various phenomena appearing at first as counterintuitive find a straightforward explanation.

  1. Fluctuations in a superconducting quantum critical point of multi-band metals

    Energy Technology Data Exchange (ETDEWEB)

    Ramires, A [Instituto de Fisica, Universidade Federal Fluminense, Campus da Praia Vermelha, Niteroi, RJ, 24.210-340 (Brazil); Continentino, M A, E-mail: [Centro Brasileiro de Pesquisas Fisicas, Rua Dr Xavier Sigaud 150, 22290-180, Rio de Janeiro, RJ (Brazil)


    In multi-band metals quasi-particles arising from different atomic orbitals coexist at a common Fermi surface. Superconductivity in these materials may appear due to interactions within a band (intra-band) or among the distinct metallic bands (inter-band). Here we consider the suppression of superconductivity in the intra-band case due to hybridization. The fluctuations at the superconducting quantum critical point (SQCP) are obtained by calculating the response of the system to a fictitious space- and time-dependent field, which couples to the superconducting order parameter. The appearance of superconductivity is related to the divergence of a generalized susceptibility. For a single-band superconductor this coincides with the Thouless criterion. For fixed chemical potential and large hybridization, the superconducting state has many features in common with breached pair superconductivity with unpaired electrons at the Fermi surface. The T = 0 phase transition from the superconductor to the normal state is in the universality class of the density-driven Bose-Einstein condensation. For a fixed number of particles and in the strong coupling limit, the system still has an instability to the normal state with increasing hybridization.

  2. Quantum criticality in CaRuO.sub.3./sub. - influence of Ti substitution

    Czech Academy of Sciences Publication Activity Database

    Baran, A.; Zorkovská, A.; Kajňaková, M.; Šebek, Josef; Šantavá, Eva; Bradaric, I.; Feher, A.


    Roč. 249, č. 8 (2012), 1607-1612 ISSN 0370-1972 Institutional research plan: CEZ:AV0Z10100520 Keywords : magnetism * non-Fermi liquids * phase separation * quantum criticality * ruthenates Subject RIV: BM - Solid Matter Physics ; Magnetism Impact factor: 1.489, year: 2012

  3. Breakup of a Stoner model for the two-dimensional ferromagnetic quantum critical point (United States)

    Dzero, M.; Gor'kov, L. P.


    Generalization of the results by A. V. Chubukov et al. [Phys. Rev. Lett. 90, 077002 (2003)] leads to the conclusion that the ferromagnetic quantum critical point cannot be described by a Stoner model because of a strong interplay between the paramagnetic fluctuations and the Cooper channel, at least in two dimensions.

  4. Trigonometric Cherednik algebra at critical level and quantum many-body problems

    NARCIS (Netherlands)

    Emsiz, E.; Opdam, E.M.; Stokman, J.V.


    For any module over the affine Weyl group we construct a representation of the associated trigonometric Cherednik algebra A(k) at critical level in terms of Dunkl type operators. Under this representation the center of A(k) produces quantum conserved integrals for root system generalizations of

  5. Matter fields near quantum critical point in (2+1)-dimensional U(1) gauge theory

    International Nuclear Information System (INIS)

    Liu Guozhu; Li Wei; Cheng Geng


    We study chiral phase transition and confinement of matter fields in (2+1)-dimensional U(1) gauge theory of massless Dirac fermions and scalar bosons. The vanishing scalar boson mass, r=0, defines a quantum critical point between the Higgs phase and the Coulomb phase. We consider only the critical point r=0 and the Coulomb phase with r>0. The Dirac fermion acquires a dynamical mass when its flavor is less than certain critical value N f c , which depends quantitatively on the flavor N b and the scalar boson mass r. When N f f c , the matter fields carrying internal gauge charge are all confined if r≠0 but are deconfined at the quantum critical point r=0. The system has distinct low-energy elementary excitations at the critical point r=0 and in the Coulomb phase with r≠0. We calculate the specific heat and susceptibility of the system at r=0 and r≠0, which can help to detect the quantum critical point and to judge whether dynamical fermion mass generation takes place.

  6. Topology and Edge Modes in Quantum Critical Chains (United States)

    Verresen, Ruben; Jones, Nick G.; Pollmann, Frank


    We show that topology can protect exponentially localized, zero energy edge modes at critical points between one-dimensional symmetry-protected topological phases. This is possible even without gapped degrees of freedom in the bulk—in contrast to recent work on edge modes in gapless chains. We present an intuitive picture for the existence of these edge modes in the case of noninteracting spinless fermions with time-reversal symmetry (BDI class of the tenfold way). The stability of this phenomenon relies on a topological invariant defined in terms of a complex function, counting its zeros and poles inside the unit circle. This invariant can prevent two models described by the same conformal field theory (CFT) from being smoothly connected. A full classification of critical phases in the noninteracting BDI class is obtained: Each phase is labeled by the central charge of the CFT, c ∈1/2 N , and the topological invariant, ω ∈Z . Moreover, c is determined by the difference in the number of edge modes between the phases neighboring the transition. Numerical simulations show that the topological edge modes of critical chains can be stable in the presence of interactions and disorder.

  7. Quantum chemical studies of trace gas adsorption on ice nanoparticles (United States)

    Schrems, Otto; Ignatov, Stanislav K.; Gadzhiev, Oleg B.; Masunov, Artem E.


    We have investigated the interaction of atmospheric trace gases with crystalline water ice particles of nanoscale size by modern quantum chemical methods. Small ice particles which can be formed in different altitudes play an important role in chemistry and physics of the Earth atmosphere. Knowledge about the uptake and incorporation of atmospheric trace gases in ice particles as well as their interactions with water molecules is very important for the understanding of processes at the air/ice interface. The interaction of the atmospheric trace gases with atmospheric ice nanoparticles is also an important issue for the development of modern physicochemical models. Usually, the interactions between trace gases and small particles considered theoretically apply small-size model complexes or the surface models representing only fragments of the ideal surface. Ice particles consisting of 48, 72, 216 and 270 water molecules with a distorted structure of hexagonal water ice Ih were studied using the new SCC-DFTBA method combining well the advantages of the DFT theory and semiempirical methods of quantum chemistry. The largest clusters correspond to the minimal nanoparticle size which are considered to be crystalline as determined experimentally. The clusters up to (H2O)72 were studied at the B3LYP/6-31++G(d,p) and B3LYP/6-311++G(2d,2p) levels. The larger clusters were studied using DFTBA and DFTB+ methods. Several adsorption complexes for the (H2O)270 water ice cluster were optimized at the RI-BLYP/6-31+G(d) theory level to verify the DFTB+ results. Trace gas molecules were coordinated on different sites of the nanoparticles corresponding to different ice Ih crystal planes: (0001), (10-10), (11-20). As atmospheric trace gases we have chosen CO, CO2, HCO*, HCOH*, HCHO, HCOOH and (HCO)2. which are the possible products and intermediates of the UV photolysis of organic molecules such as HCHCHO adsorbed on the ice surface. The structures of the corresponding coordination

  8. Quantum coherence-driven self-organized criticality and nonequilibrium light localization. (United States)

    Tsakmakidis, Kosmas L; Jha, Pankaj K; Wang, Yuan; Zhang, Xiang


    Self-organized criticality emerges in dynamical complex systems driven out of equilibrium and characterizes a wide range of classical phenomena in physics, geology, and biology. We report on a quantum coherence-controlled self-organized critical transition observed in the light localization behavior of a coherence-driven nanophotonic configuration. Our system is composed of a gain-enhanced plasmonic heterostructure controlled by a coherent drive, in which photons close to the stopped-light regime interact in the presence of the active nonlinearities, eventually synchronizing their dynamics. In this system, on the basis of analytical and corroborating full-wave Maxwell-Bloch computations, we observe quantum coherence-controlled self-organized criticality in the emergence of light localization arising from the synchronization of the photons. It is associated with two first-order phase transitions: one pertaining to the synchronization of the dynamics of the photons and the second pertaining to an inversionless lasing transition by the coherent drive. The so-attained light localization, which is robust to dissipation, fluctuations, and many-body interactions, exhibits scale-invariant power laws and absence of finely tuned control parameters. We also found that, in this nonequilibrium dynamical system, the effective critical "temperature" of the system drops to zero, whereupon one enters the quantum self-organized critical regime.

  9. Quantum coherence–driven self-organized criticality and nonequilibrium light localization (United States)

    Tsakmakidis, Kosmas L.; Jha, Pankaj K.; Wang, Yuan; Zhang, Xiang


    Self-organized criticality emerges in dynamical complex systems driven out of equilibrium and characterizes a wide range of classical phenomena in physics, geology, and biology. We report on a quantum coherence–controlled self-organized critical transition observed in the light localization behavior of a coherence-driven nanophotonic configuration. Our system is composed of a gain-enhanced plasmonic heterostructure controlled by a coherent drive, in which photons close to the stopped-light regime interact in the presence of the active nonlinearities, eventually synchronizing their dynamics. In this system, on the basis of analytical and corroborating full-wave Maxwell-Bloch computations, we observe quantum coherence–controlled self-organized criticality in the emergence of light localization arising from the synchronization of the photons. It is associated with two first-order phase transitions: one pertaining to the synchronization of the dynamics of the photons and the second pertaining to an inversionless lasing transition by the coherent drive. The so-attained light localization, which is robust to dissipation, fluctuations, and many-body interactions, exhibits scale-invariant power laws and absence of finely tuned control parameters. We also found that, in this nonequilibrium dynamical system, the effective critical “temperature” of the system drops to zero, whereupon one enters the quantum self-organized critical regime. PMID:29556531

  10. Quantum criticality and nodal superconductivity in the FeAs-based superconductor KFe2As2. (United States)

    Dong, J K; Zhou, S Y; Guan, T Y; Zhang, H; Dai, Y F; Qiu, X; Wang, X F; He, Y; Chen, X H; Li, S Y


    The in-plane resistivity rho and thermal conductivity kappa of the FeAs-based superconductor KFe2As2 single crystal were measured down to 50 mK. We observe non-Fermi-liquid behavior rho(T) approximately T{1.5} at H{c{2}}=5 T, and the development of a Fermi liquid state with rho(T) approximately T{2} when further increasing the field. This suggests a field-induced quantum critical point, occurring at the superconducting upper critical field H{c{2}}. In zero field, there is a large residual linear term kappa{0}/T, and the field dependence of kappa_{0}/T mimics that in d-wave cuprate superconductors. This indicates that the superconducting gaps in KFe2As2 have nodes, likely d-wave symmetry. Such a nodal superconductivity is attributed to the antiferromagnetic spin fluctuations near the quantum critical point.

  11. Coherent inflationary dynamics for Bose-Einstein condensates crossing a quantum critical point (United States)

    Feng, Lei; Clark, Logan W.; Gaj, Anita; Chin, Cheng


    Quantum phase transitions, transitions between many-body ground states, are of extensive interest in research ranging from condensed-matter physics to cosmology1-4. Key features of the phase transitions include a stage with rapidly growing new order, called inflation in cosmology5, followed by the formation of topological defects6-8. How inflation is initiated and evolves into topological defects remains a hot topic of debate. Ultracold atomic gas offers a pristine and tunable platform to investigate quantum critical dynamics9-21. We report the observation of coherent inflationary dynamics across a quantum critical point in driven Bose-Einstein condensates. The inflation manifests in the exponential growth of density waves and populations in well-resolved momentum states. After the inflation stage, extended coherent dynamics is evident in both real and momentum space. We present an intuitive description of the quantum critical dynamics in our system and demonstrate the essential role of phase fluctuations in the formation of topological defects.

  12. Critical behavior of the quantum spin- {1}/{2} anisotropic Heisenberg model (United States)

    Sousa, J. Ricardo de

    A two-step renormalization group approach - a decimation followed by an effective field renormalization group (EFRG) - is proposed in this work to study the critical behavior of the quantum spin- {1}/{2} anisotropic Heisenberg model. The new method is illustrated by employing approximations in which clusters with one, two and three spins are used. The values of the critical parameter and critical exponent, in two- and three-dimensional lattices, for the Ising and isotropic Heisenberg limits are calculated and compared with other renormalization group approaches and exact (or series) results.

  13. Absence of quantum criticality and bulk 3D magnetism in green dioptase (United States)

    Berlie, Adam; Terry, Ian


    Green dioptase is a naturally occurring antiferromagnetic mineral that in recent years has been suggested as a candidate to exhibit quantum fluctuations at both above and below T N. Our work uses muon spectroscopy to study the dynamic and static properties of the magnetism in zero applied field. We observe the antiferromagnetic transition through tracking out the evolution of the muon spin precession frequency as a function of temperature. T N is calculated to be 15 K and the critical exponent of the transition matches with that of a 3D Heisenberg system. We also note that no evidence for any quantum magnetic fluctuations is observed either above or below T N.

  14. Some critical considerations on the present epistemological and scientific debate on quantum mechanics

    International Nuclear Information System (INIS)

    Ghirardi, G.C.


    Some general methodological considerations aimed to guarantee the necessary logical rigor to the present debate on quantum mechanics are presented. In particular some misunderstandings about the implications of the critical analysis put forward by Einstein, Podolsky and Rosen (EPR) which can be found in the literature, are discussed. These misunderstandings are shown to arise from possible underestimates, overestimates and misinterpretations of the EPR argument. It is argued that the difficulties pointed out by EPR are, in a sense that will be defined precisely, unavoidable. A model which tries to solve the difficulties arising from quantum non separability effects when macroscopic systems are involved, is briefly sketched. (author)

  15. Regularity and chaos at critical points of first-order quantum phase transitions

    International Nuclear Information System (INIS)

    Macek, M.; Leviatan, A.


    We study the interplay between regular and chaotic dynamics at the critical point of a generic first-order quantum phase transition in an interacting boson model of nuclei. A classical analysis reveals a distinct behavior of the coexisting phases in a broad energy range. The dynamics is completely regular in the deformed phase and, simultaneously, strongly chaotic in the spherical phase. A quantum analysis of the spectra separates the regular states from the irregular ones, assigns them to particular phases, and discloses persisting regular rotational bands in the deformed region.

  16. Quantum chemical aided prediction of the thermal decomposition mechanisms and temperatures of ionic liquids

    International Nuclear Information System (INIS)

    Kroon, Maaike C.; Buijs, Wim; Peters, Cor J.; Witkamp, Geert-Jan


    The long-term thermal stability of ionic liquids is of utmost importance for their industrial application. Although the thermal decomposition temperatures of various ionic liquids have been measured previously, experimental data on the thermal decomposition mechanisms and kinetics are scarce. It is desirable to develop quantitative chemical tools that can predict thermal decomposition mechanisms and temperatures (kinetics) of ionic liquids. In this work ab initio quantum chemical calculations (DFT-B3LYP) have been used to predict thermal decomposition mechanisms, temperatures and the activation energies of the thermal breakdown reactions. These quantum chemical calculations proved to be an excellent method to predict the thermal stability of various ionic liquids

  17. Universal Scaling and Critical Exponents of the Anisotropic Quantum Rabi Model (United States)

    Liu, Maoxin; Chesi, Stefano; Ying, Zu-Jian; Chen, Xiaosong; Luo, Hong-Gang; Lin, Hai-Qing


    We investigate the quantum phase transition of the anisotropic quantum Rabi model, in which the rotating and counterrotating terms are allowed to have different coupling strengths. The model interpolates between two known limits with distinct universal properties. Through a combination of analytic and numerical approaches, we extract the phase diagram, scaling functions, and critical exponents, which determine the universality class at finite anisotropy (identical to the isotropic limit). We also reveal other interesting features, including a superradiance-induced freezing of the effective mass and discontinuous scaling functions in the Jaynes-Cummings limit. Our findings are extended to the few-body quantum phase transitions with N >1 spins, where we expose the same effective parameters, scaling properties, and phase diagram. Thus, a stronger form of universality is established, valid from N =1 up to the thermodynamic limit.

  18. Quantum critical behavior in three-dimensional one-band Hubbard model at half-filling

    International Nuclear Information System (INIS)

    Karchev, Naoum


    A one-band Hubbard model with hopping parameter t and Coulomb repulsion U is considered at half-filling. By means of the Schwinger bosons and slave fermions representation of the electron operators and integrating out the spin–singlet Fermi fields an effective Heisenberg model with antiferromagnetic exchange constant is obtained for vectors which identifies the local orientation of the spin of the itinerant electrons. The amplitude of the spin vectors is an effective spin of the itinerant electrons accounting for the fact that some sites, in the ground state, are doubly occupied or empty. Accounting adequately for the magnon–magnon interaction the Néel temperature is calculated. When the ratio t/U is small enough (t/U ≤0.09) the effective model describes a system of localized electrons. Increasing the ratio increases the density of doubly occupied states which in turn decreases the effective spin and Néel temperature. The phase diagram in the plane of temperature (T N )/U and parameter t/U is presented. The quantum critical point (T N =0) is reached at t/U =0.9. The magnons in the paramagnetic phase are studied and the contribution of the magnons’ fluctuations to the heat capacity is calculated. At the Néel temperature the heat capacity has a peak which is suppressed when the system approaches a quantum critical point. It is important to stress that, at half-filling, the ground state, determined by fermions, is antiferromagnetic. The magnon fluctuations drive the system to quantum criticality and when the effective spin is critically small these fluctuations suppress the magnetic order. -- Highlights: •Technique of calculation is introduced which permits us to study the magnons’ fluctuations. •Quantum critical point is obtained in the one-band 3D Hubbard model at half-filling. •The present analytical results supplement the numerical ones (see Fig. 7)

  19. Evolution of Quantum Fluctuations Near the Quantum Critical Point of the Transverse Field Ising Chain System CoNb_{2}O_{6}

    Directory of Open Access Journals (Sweden)

    A. W. Kinross


    Full Text Available The transverse field Ising chain model is ideally suited for testing the fundamental ideas of quantum phase transitions because its well-known T=0 ground state can be extrapolated to finite temperatures. Nonetheless, the lack of appropriate model materials hindered the past effort to test the theoretical predictions. Here, we map the evolution of quantum fluctuations in the transverse field Ising chain based on nuclear magnetic resonance measurements of CoNb_{2}O_{6}, and we demonstrate the finite-temperature effects on quantum criticality for the first time. From the temperature dependence of the ^{93}Nb longitudinal relaxation rate 1/T_{1}, we identify the renormalized classical, quantum critical, and quantum disordered scaling regimes in the temperature (T vs transverse magnetic field (h_{⊥} phase diagram. Precisely at the critical field h_{⊥}^{c}=5.25±0.15  T, we observe a power-law behavior, 1/T_{1}∼T^{−3/4}, as predicted by quantum critical scaling. Our parameter-free comparison between the data and theory reveals that quantum fluctuations persist up to as high as T∼0.4J, where the intrachain exchange interaction J is the only energy scale of the problem.

  20. Superconductivity mediated by quantum critical antiferromagnetic fluctuations: The rise and fall of hot spots (United States)

    Wang, Xiaoyu; Schattner, Yoni; Berg, Erez; Fernandes, Rafael M.


    In several unconventional superconductors, the highest superconducting transition temperature Tc is found in a region of the phase diagram where the antiferromagnetic transition temperature extrapolates to zero, signaling a putative quantum critical point. The elucidation of the interplay between these two phenomena—high-Tc superconductivity and magnetic quantum criticality—remains an important piece of the complex puzzle of unconventional superconductivity. In this paper, we combine sign-problem-free quantum Monte Carlo simulations and field-theoretical analytical calculations to unveil the microscopic mechanism responsible for the superconducting instability of a general low-energy model, called the spin-fermion model. In this approach, low-energy electronic states interact with each other via the exchange of quantum critical magnetic fluctuations. We find that even in the regime of moderately strong interactions, both the superconducting transition temperature and the pairing susceptibility are governed not by the properties of the entire Fermi surface, but instead by the properties of small portions of the Fermi surface called hot spots. Moreover, Tc increases with increasing interaction strength, until it starts to saturate at the crossover from hot-spots-dominated to Fermi-surface-dominated pairing. Our work provides not only invaluable insights into the system parameters that most strongly affect Tc, but also important benchmarks to assess the origin of superconductivity in both microscopic models and actual materials.

  1. Quantum chemical analysis of potential anti-Parkinson agents

    Indian Academy of Sciences (India)

    3-arylcoumarin MAO-B inhibitors (1–9) have been elucidated via molecular docking and density functional theory (DFT) calculations. Intermolecular binding energy components could not be analyzed by docking and due to this limitation, quantum mechanical (QM) calculations including functional B3LYP in association with.

  2. Tuning electronic properties in graphene quantum dots by chemical functionalization: Density functional theory calculations (United States)

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


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

  3. Scaling behavior of quantum critical relaxation dynamics of a system in a heat bath (United States)

    Yin, Shuai; Lo, Chung-Yu; Chen, Pochung


    We study the scaling behavior of the relaxation dynamics to thermal equilibrium when a quantum system is near the quantum critical point. In particular, we investigate systems whose relaxation dynamics is described by a Lindblad master equation. We find that the universal scaling behavior not only appears in the equilibrium stage at the long-time limit but also manifests in the nonequilibrium relaxation process. While the critical behavior is dictated by the low-lying energy levels of the Hamiltonian, the dissipative part in the Lindblad equation also plays important roles in two aspects: First, the dissipative part makes the high-energy levels decay fast, after which the universal behavior controlled by the low-lying modes emerges. Second, the dissipation rate gives rise to a time scale that affects the scaling behavior. We confirm our theory by solving the Lindblad equation for the one-dimensional transverse-field Ising model.

  4. Decofinement, dimensional crossover and quantum criticality in coupled correlated chains with frustration

    International Nuclear Information System (INIS)

    Lal, Siddhartha; Laad, Mukul S.


    The dynamics of the charge sector of a one-dimensional quarter-filled electronic system with extended Hubbard interactions were recently mapped onto that of an effective pseudospin transverse-field Ising model (TFIM) in the strong coupling limit. Motivated by studying the effects of inter-chain couplings, we investigate the phase diagram for the case of a system of many coupled effective (TFIM) chains. A random phase approximation analysis reveals a phase diagram with an ordered phase existing at finite temperatures. The phase boundary ends at a zero temperature quantum critical point. Critical quantum fluctuations are found to drive a zero temperature deconfinement transition, as well as enhance the dispersion of excitations in the transverse directions, leading to a dimensional crossover at finite temperatures. Our work is potentially relevant for a unified description of a class of strongly correlated, quarter-filled chain and ladder systems. (author)

  5. A DMFT+CTQMC Investigation of Strange Metallicity in Local Quantum Critical Scenario (United States)

    Acharya, Swagata; Laad, M. S.; Taraphder, A.


    “Strange” metallicity is now a pseudonym for a novel metallic state exhibiting anomalous infra-red (branch-cut) continuum features in one- and two-particle responses. Here, we employ dynamical mean-field theory (DMFT) using low-temperature continuous-time- quantum Monte-Carlo (CTQMC) solver for an extended periodic Anderson model (EPAM) model to investigate unusual magnetic fluctuations in the strange metal. We show how extinction of Landau quasiparticles in the orbital selective Mott phase (OSMP) leads to (i) qualitative explication of strange transport features and (ii) anomalous quantum critical magnetic fluctuations due to critical liquid-like features in dynamical spin fluctuations, in excellent accord with data in some f-electron systems.

  6. Critical fluctuations and the rates of interstate switching near the excitation threshold of a quantum parametric oscillator. (United States)

    Lin, Z R; Nakamura, Y; Dykman, M I


    We study the dynamics of a nonlinear oscillator near the critical point where period-two vibrations are first excited with the increasing amplitude of parametric driving. Above the threshold, quantum fluctuations induce transitions between the period-two states over the quasienergy barrier. We find the effective quantum activation energies for such transitions and their scaling with the difference of the driving amplitude from its critical value. We also find the scaling of the fluctuation correlation time with the quantum noise parameters in the critical region near the threshold. The results are extended to oscillators with nonlinear friction.

  7. Relative criterion for validity of a semiclassical approach to the dynamics near quantum critical points. (United States)

    Wang, Qian; Qin, Pinquan; Wang, Wen-ge


    Based on an analysis of Feynman's path integral formulation of the propagator, a relative criterion is proposed for validity of a semiclassical approach to the dynamics near critical points in a class of systems undergoing quantum phase transitions. It is given by an effective Planck constant, in the relative sense that a smaller effective Planck constant implies better performance of the semiclassical approach. Numerical tests of this relative criterion are given in the XY model and in the Dicke model.

  8. Quantum chemical investigation of levofloxacin-boron complexes: A computational approach (United States)

    Sayin, Koray; Karakaş, Duran


    Quantum chemical calculations are performed over some boron complexes with levofloxacin. Boron complex with fluorine atoms are optimized at three different methods (HF, B3LYP and M062X) with 6-31 + G(d) basis set. The best level is determined as M062X/6-31 + G(d) by comparison of experimental and calculated results of complex (1). The other complexes are optimized by using the best level. Structural properties, IR and NMR spectrum are examined in detail. Biological activities of mentioned complexes are investigated by some quantum chemical descriptors and molecular docking analyses. As a result, biological activities of complex (2) and (4) are close to each other and higher than those of other complexes. Additionally, NLO properties of mentioned complexes are investigated by some quantum chemical parameters. It is found that complex (3) is the best candidate for NLO applications.

  9. Quantum critical point and entanglement in a matrix-product ground state (United States)

    Tribedi, Amit; Bose, Indrani


    In this paper, we study the entanglement properties of a spin-1 model, the exact ground state of which is given by a matrix product (MP) state. The model exhibits a critical point transition at a parameter value a=0 . The longitudinal and transverse correlation lengths are known to diverge as a→0 . We use three different entanglement measures S(i) (the one-site von Neumann entropy), S(i,j) (the two-body entanglement), and G(2,n) (the generalized global entanglement) to determine the entanglement content of the MP ground state as the parameter a is varied. The entanglement length, associated with S(i,j) , is found to diverge in the vicinity of the quantum critical point a=0 . The first derivative of the entanglement measure E [=S(i),S(i,j)] with respect to the parameter a also diverges. The first derivative of G(2,n) with respect to a does not diverge as a→0 but attains a maximum value at a=0 . At the quantum critical point itself all three entanglement measures become zero. We further show that multipartite correlations are involved in the quantum phase transitions at a=0 .

  10. Non-critical string theory formulation of microtubule dynamics and quantum aspects of brain function

    CERN Document Server

    Mavromatos, Nikolaos E


    Microtubule (MT) networks, subneural paracrystalline cytosceletal structures, seem to play a fundamental role in the neurons. We cast here the complicated MT dynamics in the form of a 1+1-dimensional non-critical string theory, thus enabling us to provide a consistent quantum treatment of MTs, including enviromental {\\em friction} effects. We suggest, thus, that the MTs are the microsites, in the brain, for the emergence of stable, macroscopic quantum coherent states, identifiable with the {\\em preconscious states}. Quantum space-time effects, as described by non-critical string theory, trigger then an {\\em organized collapse} of the coherent states down to a specific or {\\em conscious state}. The whole process we estimate to take {\\cal O}(1\\,{\\rm sec}), in excellent agreement with a plethora of experimental/observational findings. The {\\em microscopic arrow of time}, endemic in non-critical string theory, and apparent here in the self-collapse process, provides a satisfactory and simple resolution to the age...

  11. Soliton phase near antiferromagnetic quantum critical point in Q1D conductors (United States)

    Gor'kov, L. P.; Grigoriev, P. D.


    In frameworks of a nesting model for Q1D organic conductors at the antiferromagnetic (SDW) quantum critical point, the first-order transition separates the metallic state from the soliton phase having periodic domain structure. The low-temperature phase diagram also displays a 2nd-order transition line between the soliton and the uniformly gapped SDW phases. The results agree with the phase diagram of (TMTSF)2PF6 near critical pressure (Vuletic T. et al., Eur. Phys. J. B 25 (2002) 319). The detection of the 2nd-order transition line is discussed. We comment on superconductivity at low temperature.

  12. Protein structure refinement using a quantum mechanics-based chemical shielding predictor

    DEFF Research Database (Denmark)

    Bratholm, Lars Andersen; Jensen, Jan Halborg


    The accurate prediction of protein chemical shifts using a quantum mechanics (QM)-based method has been the subject of intense research for more than 20 years but so far empirical methods for chemical shift prediction have proven more accurate. In this paper we show that a QM-based predictor...... of a protein backbone and CB chemical shifts (ProCS15, PeerJ, 2016, 3, e1344) is of comparable accuracy to empirical chemical shift predictors after chemical shift-based structural refinement that removes small structural errors. We present a method by which quantum chemistry based predictions of isotropic...... geometry optimized X-ray structures as starting points: simulated annealing of the starting structure and constant temperature MCMC simulation followed by simulated annealing of a representative ensemble structure. Annealing of the CHARMM structure changes the CA-RMSD by an average of 0.4 Å but lowers...

  13. Singularity of the London penetration depth at quantum critical points in superconductors. (United States)

    Chowdhury, Debanjan; Swingle, Brian; Berg, Erez; Sachdev, Subir


    We present a general theory of the singularity in the London penetration depth at symmetry-breaking and topological quantum critical points within a superconducting phase. While the critical exponents and ratios of amplitudes on the two sides of the transition are universal, an overall sign depends upon the interplay between the critical theory and the underlying Fermi surface. We determine these features for critical points to spin density wave and nematic ordering, and for a topological transition between a superconductor with Z2 fractionalization and a conventional superconductor. We note implications for recent measurements of the London penetration depth in BaFe2(As(1-x)P(x))2 [K. Hashimoto et al., Science 336, 1554 (2012)].

  14. Conductivity of Weakly Disordered Metals Close to a "Ferromagnetic" Quantum Critical Point (United States)

    Kastrinakis, George


    We calculate analytically the conductivity of weakly disordered metals close to a "ferromagnetic" quantum critical point in the low-temperature regime. Ferromagnetic in the sense that the effective carrier potential V(q,ω ) , due to critical fluctuations, is peaked at zero momentum q=0 . Vertex corrections, due to both critical fluctuations and impurity scattering, are explicitly considered. We find that only the vertex corrections due to impurity scattering, combined with the self-energy, generate appreciable effects as a function of the temperature T and the control parameter a, which measures the proximity to the critical point. Our results are consistent with resistivity experiments in several materials displaying typical Fermi liquid behaviour, but with a diverging prefactor of the T^2 term for small a.

  15. Quantum criticality and emergence of the T/B scaling in strongly correlated metals

    International Nuclear Information System (INIS)

    Watanabe, Shinji; Miyake, Kazumasa


    A new type of scaling observed in heavy-electron metal β-YbAlB 4 , where the magnetic susceptibility is expressed as a single scaling function of the ratio of temperature T and magnetic field B over four decades, is examined theoretically. We develop the mode-coupling theory for critical Yb-valence fluctuations under a magnetic field, verifying that the T/B scaling behavior appears near the QCP of the valence transition. Emergence of the T/B scaling indicates the presence of the small characteristic temperature of the critical Yb-valence fluctuation due to the strong local correlation effect. It is discussed that the T/B scaling as well as the unconventional criticality is explained from the viewpoint of the quantum valence criticality in a unified way.

  16. Modeling the role of microplastics in Bioaccumulation of organic chemicals to marine aquatic organisms. Critical Review

    NARCIS (Netherlands)

    Koelmans, A.A.


    It has been shown that ingestion of microplastics may increase bioaccumulation of organic chemicals by aquatic organisms. This paper critically reviews the literature on the effects of plastic ingestion on the bioaccumulation of organic chemicals, emphasizing quantitative approaches and mechanistic

  17. Critical temperature and the transition from quantum to classical order parameter fluctuations in the three-dimensional Heisenberg antiferromagnet


    Sandvik, A. W.


    We present results of extensive quantum Monte Carlo simulations of the three-dimensional (3D) S=1/2 Heisenberg antiferromagnet. Finite-size scaling of the spin stiffness and the sublattice magnetization gives the critical temperature Tc/J = 0.946 +/- 0.001. The critical behavior is consistent with the classical 3D Heisenberg universality class, as expected. We discuss the general nature of the transition from quantum mechanical to classical (thermal) order parameter fluctuations at a continuo...

  18. Non-Fermi Liquid Behavior Close to a Quantum Critical Point in a Ferromagnetic State without Local Moments

    Directory of Open Access Journals (Sweden)

    E. Svanidze


    Full Text Available A quantum critical point (QCP occurs upon chemical doping of the weak itinerant ferromagnet Sc_{3.1}In. Remarkable for a system with no local moments, the QCP is accompanied by non-Fermi liquid behavior, manifested in the logarithmic divergence of the specific heat both in the ferro-and the paramagnetic states, as well as linear temperature dependence of the low-temperature resistivity. With doping, critical scaling is observed close to the QCP, as the critical exponents δ, γ, and β have weak composition dependence, with δ nearly twice and β almost half of their respective mean-field values. The unusually large paramagnetic moment μ_{PM}∼1.3μ_{B}/F.U. is nearly composition independent. Evidence for strong spin fluctuations, accompanying the QCP at x_{c}=0.035±0.005, may be ascribed to the reduced dimensionality of Sc_{3.1}In, associated with the nearly one-dimensional Sc-In chains.

  19. Magnetic-field control of quantum critical points of valence transition. (United States)

    Watanabe, Shinji; Tsuruta, Atsushi; Miyake, Kazumasa; Flouquet, Jacques


    We study the mechanism of how critical end points of first-order valence transitions are controlled by a magnetic field. We show that the critical temperature is suppressed to be a quantum critical point (QCP) by a magnetic field, and unexpectedly, the QCP exhibits nonmonotonic field dependence in the ground-state phase diagram, giving rise to the emergence of metamagnetism even in the intermediate valence-crossover regime. The driving force of the field-induced QCP is clarified to be cooperative phenomena of the Zeeman and Kondo effects, which create a distinct energy scale from the Kondo temperature. This mechanism explains the peculiar magnetic response in CeIrIn(5) and the metamagnetic transition in YbXCu(4) for X=In as well as the sharp contrast between X=Ag and Cd.

  20. Dimensional reduction at the BEC quantum critical point in BaCuSi2O6. (United States)

    Sebastian, Suchitra; Fisher, Ian; Harrison, Neil; Jaime, Marcelo; Sharma, Peter; Batista, Cristian; Balicas, Luis; Kawashima, Naoki


    We present results on the magnetic spin dimer system BaCuSi2O6, which can be tuned across a Bose-Einstein condensation (BEC) quantum critical point (QCP) to an ordered BEC of spins by applying an external magnetic field. Experimental results reveal a continuous crossover in critical scaling behaviour near the QCP from 3d to 2d BEC universality, indicating that dimensionality itself is an emergent property at the QCP of this particle density-tuneable BEC. Geometrical frustration leading to inter-layer decoupling is identified as the mechanism responsible for this unique manifestation of a lower dimensional QCP in the 3d BaCuSi2O6 spin system. While the theoretical concept of dimensional reduction has been extensively discussed in many different contexts as a route to low dimensionality in bulk materials, this is the first experimental realisation of dimensionally reduced criticality.

  1. Inhomogeneous quasi-adiabatic driving of quantum critical dynamics in weakly disordered spin chains

    International Nuclear Information System (INIS)

    Rams, Marek M; Mohseni, Masoud; Campo, Adolfo del


    We introduce an inhomogeneous protocol to drive a weakly disordered quantum spin chain quasi-adiabatically across a quantum phase transition and minimize the residual energy of the final state. The number of spins that simultaneously reach the critical point is controlled by the length scale in which the magnetic field is modulated, introducing an effective size that favors adiabatic dynamics. The dependence of the residual energy on this length scale and the velocity at which the magnetic field sweeps out the chain is shown to be nonmonotonic. We determine the conditions for an optimal suppression of the residual energy of the final state and show that inhomogeneous driving can outperform conventional adiabatic schemes based on homogeneous control fields by several orders of magnitude. (paper)

  2. Avoided Quantum Criticality and Magnetoelastic Coupling in BaFe2-xNixAs2

    DEFF Research Database (Denmark)

    Lu, Xingye; Gretarsson, H.; Zhang, Rui


    suppressed and separated, resulting in sNT>T with increasing x, as was previously observed. However, the temperature separation between sT and NT decreases with increasing x for x≥0.065, tending toward a quantum bicritical point near optimal superconductivity at x≈0.1. The zero-temperature transition...... is preempted by the formation of a secondary incommensurate magnetic phase in the region 0.088≲x≲0.104, resulting in a finite value of NT≈cT+10 K above the superconducting dome around x≈0.1. Our results imply an avoided quantum critical point, which is expected to strongly influence the properties of both...

  3. Normal coordinate analysis and quantum chemical study of tris(p ...

    Indian Academy of Sciences (India)

    Department of Chemistry, Lucknow University, Lucknow 226 007, India. *. Corresponding author. B-981 ... matrix method and the semi-empirical quantum chemical molecular orbital PM3 method. Thus the ..... [20] J J P Stewart, MOPAC 2007, Stewart Computational Chemistry, version 7.075W. [21] N B Colthup, L H Daly and ...

  4. Green wet chemical route to synthesize capped CdSe quantum dots

    Indian Academy of Sciences (India)

    cadmium selenide quantum dots (CdSe QDs) employing chemical bath deposition (CBD) method. The mechanism of capping using ... more, the process can be operated under open atmosphere. (Chang and Lee 2007). Here, we report ... kept in bath at 65. ◦. C for. 1 h. In order to control the pH further, appropriate amount of.


    Czech Academy of Sciences Publication Activity Database

    Záliš, Stanislav; Kvapilová, Hana; Kratochvílová, Irena; Šebera, Jakub; Vlček, Antonín; Winter, R. F.


    Roč. 2011, č. 1 (2011), P1299 ISSN 1708-5284 R&D Projects: GA AV ČR KAN100400702; GA MŠk LD11086 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z10100520 Keywords : quantum chemical modeling * electron transfer Subject RIV: CF - Physical ; Theoretical Chemistry

  6. Complementing high-throughput X-ray powder diffraction data with quantum-chemical calculations

    DEFF Research Database (Denmark)

    Naelapaa, Kaisa; van de Streek, Jacco; Rantanen, Jukka


    of piroxicam form III. These combined experimental/quantum-chemical methods can provide access to reliable structural information in the course of an intensive experimentally based solid-form screening activity or in other circumstances wherein single crystals might never be viable, for example, for polymorphs...

  7. Quantum chemical investigations of AlN-doped C 60 for use as a ...

    Indian Academy of Sciences (India)

    Quantum chemical calculations were carried out to study the electronic structure and stability of adenine–thymine and the rare tautomer of adenine–thymine base pairs along with their Cu2+ complexes and their interactions with AlN-modified fullerene (C58AlN) using Density Functional Theory (B3LYP method). Since, these ...

  8. Electrochemical and Quantum Chemical Study of Reactivity of Orthophthalaldehyde with Aliphatic Primary Amines

    Czech Academy of Sciences Publication Activity Database

    Donkeng Dazie, Joel; Liška, Alan; Ludvík, Jiří


    Roč. 163, č. 9 (2016), G127-G132 ISSN 0013-4651 R&D Projects: GA ČR GA13-21704S Institutional support: RVO:61388955 Keywords : electrochemistry * quantum chemical study * amines Subject RIV: CG - Electrochemistry Impact factor: 3.259, year: 2016

  9. Green wet chemical route to synthesize capped CdSe quantum dots

    Indian Academy of Sciences (India)

    In the present work, we report green synthesis of tartaric acid (TA) and triethanolamine (TEA) capped cadmium selenide quantum dots (CdSe QDs) employing chemical bath deposition (CBD) method. The mechanism of capping using non-toxic binary capping agents is also discussed. Stable QDs of various sizes were ...

  10. Protein structure validation and refinement using amide proton chemical shifts derived from quantum mechanics

    DEFF Research Database (Denmark)

    Christensen, Anders Steen; Linnet, Troels Emtekær; Borg, Mikael


    We present the ProCS method for the rapid and accurate prediction of protein backbone amide proton chemical shifts - sensitive probes of the geometry of key hydrogen bonds that determine protein structure. ProCS is parameterized against quantum mechanical (QM) calculations and reproduces high level...

  11. Green wet chemical route to synthesize capped CdSe quantum dots

    Indian Academy of Sciences (India)

    Green wet chemical route to synthesize capped CdSe quantum dots. A OUDHIA and P BICHPURIA. ∗. Department of Physics, Government VYT PG Autonomous College, Durg 491 001, India. MS received 25 November 2012; revised 13 February 2013. Abstract. In the present work, we report green synthesis of tartaric acid ...

  12. Anomalous properties and coexistence of antiferromagnetism and superconductivity near a quantum critical point in rare-earth intermetallides

    International Nuclear Information System (INIS)

    Val’kov, V. V.; Zlotnikov, A. O.


    Mechanisms of the appearance of anomalous properties experimentally observed at the transition through the quantum critical point in rare-earth intermetallides have been studied. Quantum phase transitions are induced by the external pressure and are manifested as the destruction of the long-range antiferromagnetic order at zero temperature. The suppression of the long-range order is accompanied by an increase in the area of the Fermi surface, and the effective electron mass is strongly renormalized near the quantum critical point. It has been shown that such a renormalization is due to the reconstruction of the quasiparticle band, which is responsible for the formation of heavy fermions. It has been established that these features hold when the coexistence phase of antiferromagnetism and superconductivity is implemented near the quantum critical point.

  13. Photosensitization and phototherapy with furocoumarins: A quantum-chemical study

    International Nuclear Information System (INIS)

    Serrano-Perez, Juan Jose; Serrano-Andres, Luis; Merchan, Manuela


    The effect of electromagnetic radiation on biological objects extends from heating to complex photochemistry, and includes DNA alteration, that properly modified in damaged cells may entail beneficial effects. In this regard, psoralen + UV-A (PUVA) therapy, in which furocoumarins, psoralen-like chromophores, are used as photosensitizers and photoreactants with DNA bases, is one of the most promising strategies against a plethora of diseases. Understanding the underlying photochemical mechanisms is crucial to design effective drugs without undesired side effects. We have undertaken a quantum-mechanical study on the photophysics and photochemistry of furocoumarins, analyzing firstly the most efficient way in which the lowest excited triplet state, as protagonist of the photosensitizing action, is populated from the initially promoted singlet states, and secondly the basics of the formation of furocoumarin-DNA photoadducts

  14. Origin of quantum criticality in Yb-Al-Au approximant crystal and quasicrystal

    International Nuclear Information System (INIS)

    Watanabe, Shinji; Miyake, Kazumasa


    To get insight into the mechanism of emergence of unconventional quantum criticality observed in quasicrystal Yb 15 Al 34 Au 51 , the approximant crystal Yb 14 Al 35 Au 51 is analyzed theoretically. By constructing a minimal model for the approximant crystal, the heavy quasiparticle band is shown to emerge near the Fermi level because of strong correlation of 4f electrons at Yb. We find that charge-transfer mode between 4f electron at Yb on the 3rd shell and 3p electron at Al on the 4th shell in Tsai-type cluster is considerably enhanced with almost flat momentum dependence. The mode-coupling theory shows that magnetic as well as valence susceptibility exhibits χ ∼ T -0.5 for zero-field limit and is expressed as a single scaling function of the ratio of temperature to magnetic field T/B over four decades even in the approximant crystal when some condition is satisfied by varying parameters, e.g., by applying pressure. The key origin is clarified to be due to strong locality of the critical Yb-valence fluctuation and small Brillouin zone reflecting the large unit cell, giving rise to the extremely-small characteristic energy scale. This also gives a natural explanation for the quantum criticality in the quasicrystal corresponding to the infinite limit of the unit-cell size. (author)

  15. Quantum chemical investigation on structures and energetics of ...

    Indian Academy of Sciences (India)

    The present work deals with a systematic study on WF species using ab initio density functional method. The geometrical features related to the equilibrium structures of WF species up to = 5 are highlighted and the effect of addition as well as removal of an electron is discussed. The chemical stability of these species ...

  16. Theory of critical phenomena in finite-size systems scaling and quantum effects

    CERN Document Server

    Brankov, Jordan G; Tonchev, Nicholai S


    The aim of this book is to familiarise the reader with the rich collection of ideas, methods and results available in the theory of critical phenomena in systems with confined geometry. The existence of universal features of the finite-size effects arising due to highly correlated classical or quantum fluctuations is explained by the finite-size scaling theory. This theory (1) offers an interpretation of experimental results on finite-size effects in real systems; (2) gives the most reliable tool for extrapolation to the thermodynamic limit of data obtained by computer simulations; (3) reveals

  17. Finite-dimensional effects and critical indices of one-dimensional quantum models

    International Nuclear Information System (INIS)

    Bogolyubov, N.M.; Izergin, A.G.; Reshetikhin, N.Yu.


    Critical indices, depending on continuous parameters in Bose-gas quantum models and Heisenberg 1/2 spin antiferromagnetic in two-dimensional space-time at zero temperature, have been calculated by means of finite-dimensional effects. In this case the long-wave asymptotics of the correlation functions is of a power character. Derivation of man asymptotics terms is reduced to the determination of a central charge in the appropriate Virassoro algebra representation and the anomalous dimension-operator spectrum in this representation. The finite-dimensional effects allow to find these values

  18. Extraction of conformal data in critical quantum spin chains using the Koo-Saleur formula (United States)

    Milsted, Ashley; Vidal, Guifre


    We study the emergence of two-dimensional conformal symmetry in critical quantum spin chains on the finite circle. Our goal is to characterize the conformal field theory (CFT) describing the universality class of the corresponding quantum phase transition. As a means to this end, we propose and demonstrate automated procedures which, using only the lattice Hamiltonian H =∑jhj as an input, systematically identify the low-energy eigenstates corresponding to Virasoro primary and quasiprimary operators, and assign the remaining low-energy eigenstates to conformal towers. The energies and momenta of the primary operator states are needed to determine the primary operator scaling dimensions and conformal spins, an essential part of the conformal data that specifies the CFT. Our techniques use the action, on the low-energy eigenstates of H , of the Fourier modes Hn of the Hamiltonian density hj. The Hn were introduced as lattice representations of the Virasoro generators by Koo and Saleur [Nucl. Phys. B 426, 459 (1994), 10.1016/0550-3213(94)90018-3]. In this paper, we demonstrate that these operators can be used to extract conformal data in a nonintegrable quantum spin chain.

  19. A quantum chemical study on the formation of phosphorus mononitride

    International Nuclear Information System (INIS)

    Viana, Rommel B.; Pereira, Priscila S.S.; Macedo, Luiz G.M.; Pimentel, Andre S.


    The chemical mechanism of the 1 PN formation was successfully studied by using the CCSD(T)/6-311++G(3df,3pd) level of theory. The 1 NH 3 + 3 PH and 4 P + NH 3 reaction paths are not energetically favorable to form the 1 PN molecule. However, the 3 NH + 3 PH, 4 N + 3 PH 3 , 4 N + 3 PH, 4 P + 3 NH, and 4 P + 2 NH 2 reaction paths to form the 1 PN molecule are only energetically favorable by taking place through specific transition states to form the 1 PN molecule. The NH 3 + 3 PH, 4 N + 1 PH 3 , NH 3 + 4 P, and 4 N + 2 PH 2 reactions are spin-forbidden and the probability of hopping for these reactions was estimated to be 0 by the Landau-Zener theory. This is the first detailed study on the chemical mechanism for the 1 PN formation.

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

    International Nuclear Information System (INIS)

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


    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 C 7 H 10 O 2 , 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

  1. Quantum chemical simulation of methane production by coal hydrogenation pyrolysis (United States)

    Yang, Zhiyuan; Xue, Wenying; He, Xiaoxiao; Meng, Zhuoyue


    In this work, molecular mechanics, molecular dynamics and semi-empirical quantum chemistry of the Wiser molecular structure model of bituminous coal were studied by molecular simulation. The molecular structure model was optimized and the geometrical configuration of the structural model was analyzed. The bond length and bond cleavage energy of different types of bonds were obtained, and the weak bonds and possible fragments were revealed by a series of simulation. The reaction mechanism of methane production from debris of hydrogenation pyrolysis was studied by transition state theory. The results showed that the energy of the optimal structure of Wiser molecular model of bituminous coal was 704.517 kcal/mol, and the arrangement of aromatic layers was approximately parallel. The initial cleavage of the Wiser model mainly occurs in the coal structure of the relatively high degree of cross-linking and the C-C bond connected to carbonyl carbon. The three-dimensional structure of Wiser model was broken and then generated a large number of debris, the groups of methyl were removed from debris molecules under hydrogen atmosphere, and then methyl radicals and hydrogen radicals combined to form methane.

  2. Kondo hybridization and quantum criticality in β -YbAlB4 by laser ARPES (United States)

    Bareille, Cédric; Suzuki, Shintaro; Nakayama, Mitsuhiro; Kuroda, Kenta; Nevidomskyy, Andriy H.; Matsumoto, Yosuke; Nakatsuji, Satoru; Kondo, Takeshi; Shin, Shik


    We report an angle-resolved photoemission (ARPES) study of β -YbAlB4 , which is known to harbor unconventional quantum criticality (QC) without any tuning. We directly observe a quasiparticle peak (QP) emerging from hybridization, characterized by a binding energy and an onset of coherence both at about 4 meV. This value conforms with a previously observed reduced Kondo scale at about 40 K. Consistency with an earlier study of carriers in β -YbAlB4 via the Hall effect strongly suggests that this QP is responsible for the QC in β -YbAlB4 . A comparison with the sister polymorph α -YbAlB4 , which is not quantum critical at ambient pressure, further supports this result. Indeed, within the limitation of our instrumental resolution, our ARPES measurements do not show tangible sign of hybridization in this locally isomorphic system, while the conduction band we observe is essentially the same as in β -YbAlB4 . We therefore claim that we identified by ARPES the carriers responsible for the QC in β -YbAlB4 . The observed dispersion and the underlying hybridization of this QP are discussed in the context of existing theoretical models.

  3. Adiabatic Perturbation Theory: From Landau-Zener Problem to Quenching Through a Quantum Critical Point (United States)

    De Grandi, C.; Polkovnikov, A.

    Dynamics in closed systems recently attracted a lot of theoretical interest largely following experimental developments in cold atom systems (see e.g., [1] for a review). Several spectacular experiments already explored different aspects of non-equilibrium dynamics in interacting many-particle systems [2-8]. Recent theoretical works in this context focused on various topics, for instance: connection of dynamics and thermodynamics [9-11 M. Rigol, unpublished], dynamics following a sudden quench in low dimensional systems [11-23, L. Mathey and A. Polkovnikov, unpublished; A. Iucci and M.A. Cazalilla,unpublished], adiabatic dynamics near quantum critical points [24-37, D. Chowdhury et al., unpublished; K. Sengupta and D. Sen, unpublished; A.P. Itin and P. Törmä, unpublished; F. Pollmann et al., unpublished] and others. Though there is still very limited understanding of the generic aspects of non-equilibrium quantum dynamics, it has been recognized that such issues as integrability, dimensionality, universality (near critical points) can be explored to understand the non-equilibrium behavior of many-particle systems in various specific situations.

  4. A quantum chemical study on the formation of phosphorus mononitride

    Energy Technology Data Exchange (ETDEWEB)

    Viana, Rommel B. [Departamento de Quimica e Fisica Molecular, Instituto de Quimica de Sao Carlos, Universidade de Sao Paulo, Av. Trabalhador Sao Carlense, 400 CP 780, 13560-970 Sao Carlos, SP (Brazil); Pereira, Priscila S.S. [Departamento de Quimica, Pontificia Universidade Catolica do Rio de Janeiro, Rua Marques de Sao Vicente 225, Gavea, 22453-900 Rio de Janeiro, RJ (Brazil); Macedo, Luiz G.M. [Laboratorio de Simulacao Computacional, Departamento de Quimica, Universidade Estadual Paulista (UNESP), Bauru, SP 17033-360 Brazil (Brazil); Pimentel, Andre S., E-mail: [Departamento de Quimica, Pontificia Universidade Catolica do Rio de Janeiro, Rua Marques de Sao Vicente 225, Gavea, 22453-900 Rio de Janeiro, RJ (Brazil)


    The chemical mechanism of the {sup 1}PN formation was successfully studied by using the CCSD(T)/6-311++G(3df,3pd) level of theory. The {sup 1}NH{sub 3} + {sup 3}PH and {sup 4}P + NH{sub 3} reaction paths are not energetically favorable to form the {sup 1}PN molecule. However, the {sup 3}NH + {sup 3}PH, {sup 4}N + {sup 3}PH{sub 3}, {sup 4}N + {sup 3}PH, {sup 4}P + {sup 3}NH, and {sup 4}P + {sup 2}NH{sub 2} reaction paths to form the {sup 1}PN molecule are only energetically favorable by taking place through specific transition states to form the {sup 1}PN molecule. The NH{sub 3} + {sup 3}PH, {sup 4}N + {sup 1}PH{sub 3}, NH{sub 3} + {sup 4}P, and {sup 4}N + {sup 2}PH{sub 2} reactions are spin-forbidden and the probability of hopping for these reactions was estimated to be 0 by the Landau-Zener theory. This is the first detailed study on the chemical mechanism for the {sup 1}PN formation.

  5. Quantum confinement of lead titanate nanocrystals by wet chemical method

    Energy Technology Data Exchange (ETDEWEB)

    Kaviyarasu, K., E-mail: [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Muckleneuk Ridge, P O Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa); Manikandan, E., E-mail: [Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa); Central Research Laboratory, Sree Balaji Medical College & Hospital, Bharath University, Chrompet, Chennai, Tamil Nadu (India); Nuru, Z.Y. [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Muckleneuk Ridge, P O Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa); Maaza, M., E-mail: [UNESCO-UNISA Africa Chair in Nanosciences/Nanotechnology Laboratories, College of Graduate Studies, University of South Africa (UNISA), Muckleneuk Ridge, P O Box 392, Pretoria (South Africa); Nanosciences African Network (NANOAFNET), Materials Research Department (MSD), iThemba LABS-National Research Foundation - NRF, 1 Old Faure Road, 7129, P O Box 722, Somerset West, Western Cape Province (South Africa)


    Lead Titanate (PbTiO{sub 3)} is a category of the practical semiconductor metal oxides, which is widely applied in various scientific and industrial fields because of its catalytic, optical, and electrical properties. PbTiO{sub 3} nanocrystalline materials have attracted a wide attention due to their unique properties. PbTiO{sub 3} nanocrystals were investigated by X-ray diffraction (XRD) to identify the PbTiO{sub 3} nanocrystals were composed a tetragonal structure. The diameter of a single sphere was around 20 nm and the diameter reached up to 3 μm. The chemical composition of the samples and the valence states of elements were determined by X-ray photoelectron spectroscopy (XPS) in detail. - Highlights: • Single crystalline NSs of PbTiO{sub 3} fabricated by wet chemical method. • PbTiO{sub 3} NSs were uniform and continuous along the long axis. • Tetragonal perovskite structure with the diameter 20 nm and length 3 μm. • XPS spectrum was fitted with Lorentzian function respectively. • The size of the images is also 10 μm × 10 μm.

  6. Uncertainty quantification for quantum chemical models of complex reaction networks. (United States)

    Proppe, Jonny; Husch, Tamara; Simm, Gregor N; Reiher, Markus


    For the quantitative understanding of complex chemical reaction mechanisms, it is, in general, necessary to accurately determine the corresponding free energy surface and to solve the resulting continuous-time reaction rate equations for a continuous state space. For a general (complex) reaction network, it is computationally hard to fulfill these two requirements. However, it is possible to approximately address these challenges in a physically consistent way. On the one hand, it may be sufficient to consider approximate free energies if a reliable uncertainty measure can be provided. On the other hand, a highly resolved time evolution may not be necessary to still determine quantitative fluxes in a reaction network if one is interested in specific time scales. In this paper, we present discrete-time kinetic simulations in discrete state space taking free energy uncertainties into account. The method builds upon thermo-chemical data obtained from electronic structure calculations in a condensed-phase model. Our kinetic approach supports the analysis of general reaction networks spanning multiple time scales, which is here demonstrated for the example of the formose reaction. An important application of our approach is the detection of regions in a reaction network which require further investigation, given the uncertainties introduced by both approximate electronic structure methods and kinetic models. Such cases can then be studied in greater detail with more sophisticated first-principles calculations and kinetic simulations.

  7. Helping Students Develop a Critical Attitude towards Chemical Process Calculations. (United States)

    de Nevers, Noel; Seader, J. D.


    Discusses the use of computer-assisted programs that allow chemical engineering students to study textbook thermodynamics problems from different perspectives, including the classical graphical method, while utilizing more than one property correlation and/or operation model so that comparisons can be made and sensitivities determined more…

  8. Progress in chemical luminescence-based biosensors: A critical review. (United States)

    Roda, Aldo; Mirasoli, Mara; Michelini, Elisa; Di Fusco, Massimo; Zangheri, Martina; Cevenini, Luca; Roda, Barbara; Simoni, Patrizia


    Biosensors are a very active research field. They have the potential to lead to low-cost, rapid, sensitive, reproducible, and miniaturized bioanalytical devices, which exploit the high binding avidity and selectivity of biospecific binding molecules together with highly sensitive detection principles. Of the optical biosensors, those based on chemical luminescence detection (including chemiluminescence, bioluminescence, electrogenerated chemiluminescence, and thermochemiluminescence) are particularly attractive, due to their high-to-signal ratio and the simplicity of the required measurement equipment. Several biosensors based on chemical luminescence have been described for quantitative, and in some cases multiplex, analysis of organic molecules (such as hormones, drugs, pollutants), proteins, and nucleic acids. These exploit a variety of miniaturized analytical formats, such as microfluidics, microarrays, paper-based analytical devices, and whole-cell biosensors. Nevertheless, despite the high analytical performances described in the literature, the field of chemical luminescence biosensors has yet to demonstrate commercial success. This review presents the main recent advances in the field and discusses the approaches, challenges, and open issues, with the aim of stimulating a broader interest in developing chemical luminescence biosensors and improving their commercial exploitation. Copyright © 2015 Elsevier B.V. All rights reserved.

  9. Pressure induced superconductor quantum critical point in multi-band systems

    Energy Technology Data Exchange (ETDEWEB)

    Padilha, Igor T. [Instituto de Fisica, Universidade Federal Fluminense, Campus da Praia Vermelha, 24210-346 Niteroi, RJ (Brazil); Continentino, Mucio A. [Centro Brasileiro de Pesquisas Fisicas, Rua Dr. Xavier Sigaud 150, Rio de Janeiro, RJ, 22290-180 (Brazil)], E-mail:


    In multi-band superconductors as inter-metallic systems and heavy fermions, external pressure can reduce the critical temperature and eventually destroy superconductivity driving these systems to the normal state. In many cases this transition is continuous and is associated with a superconducting quantum critical point (SQCP). In this work we study a two-band superconductor in the presence of hybridization V. This one-body mixing term is due to the overlap of the different wave-functions. It can be tuned by external pressure and turns out as an important control parameter to study the phase diagram and the nature of the phase transitions. We use a BCS approximation and include both inter- and intra-band attractive interactions. For negligible inter-band interactions, as hybridization (pressure) increases we find a SQCP separating a superconductor from a normal state at a critical value of the hybridization V{sub c}. We obtain the behavior of the electronic specific heat close to the SQCP and the shape of the critical line as V approaches V{sub c}.

  10. Quantum criticality in He3 bi-layers and heavy fermion compounds

    International Nuclear Information System (INIS)

    Benlagra, A.


    Despite intense experimental as well as theoretical efforts the understanding of physical phenomena peculiar to heavy fermion compounds remains one of the major problems in condensed matter physics; this research thesis considers the recently proposed theoretical approaches to describe the critical regime properties. This approach is based on the following idea: critical modes which are responsible for this regime are non-magnetic and are associated to the destruction of the Kondo effect between localized magnetic impurities and travelling conduction electrons at the quantum critical point. The author derives an analytic expression for the free energy within this model by using the Luttinger-Ward functional approach within the frame of the Eliashberg theory. The obtained expressions are transparently including the effect of critical fluctuations, integrated in a self-coherent way. The behaviour of different thermodynamic quantities is then deduced from these expressions. The result is compared with recent experiments on heavy fermion compounds as well as on a Helium-3 bilayer system adsorbed on graphite substrate in order to test the validity of such a model. Strengths and drawbacks of the model are outlined

  11. Application of quantum dots as analytical tools in automated chemical analysis: A review

    International Nuclear Information System (INIS)

    Frigerio, Christian; Ribeiro, David S.M.; Rodrigues, S. Sofia M.; Abreu, Vera L.R.G.; Barbosa, João A.C.; Prior, João A.V.; Marques, Karine L.; Santos, João L.M.


    Highlights: ► Review on quantum dots application in automated chemical analysis. ► Automation by using flow-based techniques. ► Quantum dots in liquid chromatography and capillary electrophoresis. ► Detection by fluorescence and chemiluminescence. ► Electrochemiluminescence and radical generation. - Abstract: Colloidal semiconductor nanocrystals or quantum dots (QDs) are one of the most relevant developments in the fast-growing world of nanotechnology. Initially proposed as luminescent biological labels, they are finding new important fields of application in analytical chemistry, where their photoluminescent properties have been exploited in environmental monitoring, pharmaceutical and clinical analysis and food quality control. Despite the enormous variety of applications that have been developed, the automation of QDs-based analytical methodologies by resorting to automation tools such as continuous flow analysis and related techniques, which would allow to take advantage of particular features of the nanocrystals such as the versatile surface chemistry and ligand binding ability, the aptitude to generate reactive species, the possibility of encapsulation in different materials while retaining native luminescence providing the means for the implementation of renewable chemosensors or even the utilisation of more drastic and even stability impairing reaction conditions, is hitherto very limited. In this review, we provide insights into the analytical potential of quantum dots focusing on prospects of their utilisation in automated flow-based and flow-related approaches and the future outlook of QDs applications in chemical analysis.

  12. In Vivo Anti-Leukemia, Quantum Chemical Calculations and ADMET Investigations of Some Quaternary and Isothiouronium Surfactants

    Directory of Open Access Journals (Sweden)

    Ahmed A. El-Henawy


    Full Text Available Anti-leukemia screening of previously prepared isothiouronium and quaternary salts was performed, and some salts exhibited promising activity as anticancer agents. Quantum chemical calculations were utilized to explore the electronic structure and stability of these compounds. Computational studies have been carried out at the PM3 semiempirical molecular orbitals level, to establish the HOMO-LUMO, IP and ESP mapping of these compounds. The ADMET properties were also studied to gain a clear view of the potential oral bioavailability of these compounds. The surface properties calculated included critical micelle concentration (CMC, maximum surface excess (Γmax, minimum surface area (Amin, free energy of micellization (ΔGomic and adsorption (ΔGoads.

  13. Spectroscopic and chemical reactivity analysis of D-Myo-Inositol using quantum chemical approach and its experimental verification (United States)

    Mishra, Devendra P.; Srivastava, Anchal; Shukla, R. K.


    This paper describes the spectroscopic (^1H and ^{13}C NMR, FT-IR and UV-Visible), chemical, nonlinear optical and thermodynamic properties of D-Myo-Inositol using quantum chemical technique and its experimental verification. The structural parameters of the compound are determined from the optimized geometry by B3LYP method with 6 {-}311{+}{+}G(d,p) basis set. It was found that the optimized parameters thus obtained are almost in agreement with the experimental ones. A detailed interpretation of the infrared spectra of D-Myo-Inositol is also reported in the present work. After optimization, the proton and carbon NMR chemical shifts of the studied compound are calculated using GIAO and 6 {-}311{+}{+}G(d,p) basis set. The search of organic materials with improved charge transfer properties requires precise quantum chemical calculations of space-charge density distribution, state and transition dipole moments and HOMO-LUMO states. The nature of the transitions in the observed UV-Visible spectrum of the compound has been studied by the time-dependent density functional theory (TD-DFT). The global reactivity descriptors like chemical potential, electronegativity, hardness, softness and electrophilicity index, have been calculated using DFT. The thermodynamic calculation related to the title compound was also performed at B3LYP/ 6 {-}311{+}{+}G(d,p) level of theory. The standard statistical thermodynamic functions like heat capacity at constant pressure, entropy and enthalpy change were obtained from the theoretical harmonic frequencies of the optimized molecule. It is observed that the values of heat capacity, entropy and enthalpy increase with increase in temperature from 100 to 1000 K, which is attributed to the enhancement of molecular vibration with the increase in temperature.

  14. Understanding the potency of competitive CDK2 inhibitors using quantum chemical scoring

    Czech Academy of Sciences Publication Activity Database

    Deepa, Palanisamy; Fanfrlík, Jindřich; Brahmkshatriya, Pathik; Brynda, Jiří; Cankař, P.; Kryštof, V.; Řezáč, Jan; Lepšík, Martin; Hobza, Pavel


    Roč. 156, Suppl. 1 (2012), S75-S75 ISSN 1213-8118. [International Congress Natural Anticancer Drugs. 30.06.2012-04.07.2012, Olomouc] R&D Projects: GA ČR GBP208/12/G016 Grant - others:European Science Foundation(XE) CZ.1.05/2.1.00/03.0058 Institutional support: RVO:61388963 Keywords : cyclin -dependent kinases * CDK2 * quantum chemical scoring Subject RIV: CF - Physical ; Theoretical Chemistry

  15. Molecular interactions of nucleic acid bases. A review of quantum-chemical studies

    Czech Academy of Sciences Publication Activity Database

    Šponer, Jiří; Hobza, Pavel


    Roč. 68, č. 12 (2003), s. 2231-2282 ISSN 0010-0765 R&D Projects: GA MŠk LN00A032; GA AV ČR IAA4040904 Grant - others:Wellcome Trust(GB) GR067507MF Institutional research plan: CEZ:AV0Z5004920; CEZ:AV0Z4040901 Keywords : DNA base pairs * initio quantum-chemical calculations * electron correlation Subject RIV: BO - Biophysics Impact factor: 1.041, year: 2003

  16. Protein structure refinement using a quantum mechanics-based chemical shielding predictor. (United States)

    Bratholm, Lars A; Jensen, Jan H


    The accurate prediction of protein chemical shifts using a quantum mechanics (QM)-based method has been the subject of intense research for more than 20 years but so far empirical methods for chemical shift prediction have proven more accurate. In this paper we show that a QM-based predictor of a protein backbone and CB chemical shifts (ProCS15, PeerJ , 2016, 3, e1344) is of comparable accuracy to empirical chemical shift predictors after chemical shift-based structural refinement that removes small structural errors. We present a method by which quantum chemistry based predictions of isotropic chemical shielding values (ProCS15) can be used to refine protein structures using Markov Chain Monte Carlo (MCMC) simulations, relating the chemical shielding values to the experimental chemical shifts probabilistically. Two kinds of MCMC structural refinement simulations were performed using force field geometry optimized X-ray structures as starting points: simulated annealing of the starting structure and constant temperature MCMC simulation followed by simulated annealing of a representative ensemble structure. Annealing of the CHARMM structure changes the CA-RMSD by an average of 0.4 Å but lowers the chemical shift RMSD by 1.0 and 0.7 ppm for CA and N. Conformational averaging has a relatively small effect (0.1-0.2 ppm) on the overall agreement with carbon chemical shifts but lowers the error for nitrogen chemical shifts by 0.4 ppm. If an amino acid specific offset is included the ProCS15 predicted chemical shifts have RMSD values relative to experiments that are comparable to popular empirical chemical shift predictors. The annealed representative ensemble structures differ in CA-RMSD relative to the initial structures by an average of 2.0 Å, with >2.0 Å difference for six proteins. In four of the cases, the largest structural differences arise in structurally flexible regions of the protein as determined by NMR, and in the remaining two cases, the large structural

  17. Quantum critical fluctuations due to nested Fermi surface: The case of spinless fermions

    International Nuclear Information System (INIS)

    Schlottmann, P.


    A quantum critical point (QCP) can be obtained by tuning the critical temperature of a second-order phase transition to zero. A simple model of spinless fermions with nested Fermi surface leading to a charge density wave is considered. The QCP is obtained by tuning the nesting mismatch of the Fermi surface, which has the following consequences: (i) For the tuned QCP, the specific heat over T and the effective mass increase with the logarithm of the temperature as T is lowered. (ii) For the tuned QCP the linewidth of the quasi-particles is sublinear in T and ω. (iii) The specific heat and the linewidth display a crossover from non-Fermi liquid (∼T) to Fermi liquid (∼T 2 ) behavior with increasing nesting mismatch and decreasing temperature. (iv) For the tuned QCP, the dynamical charge susceptibility has a quasi-elastic peak with a linewidth proportional to T. (v) For non-critical Fermi vector mismatch the peak is inelastic. (vi) While the specific heat and the quasi-particle linewidth are only weakly dependent on the geometry of the nested Fermi surfaces, the momentum-dependent dynamical susceptibility is expected to be affected by the shape of the Fermi surface

  18. Hilbert-Glass Transition: New Universality of Temperature-Tuned Many-Body Dynamical Quantum Criticality

    Directory of Open Access Journals (Sweden)

    David Pekker


    Full Text Available We study a new class of unconventional critical phenomena that is characterized by singularities only in dynamical quantities and has no thermodynamic signatures. One example of such a transition is the recently proposed many-body localization-delocalization transition, in which transport coefficients vanish at a critical temperature with no singularities in thermodynamic observables. Describing this purely dynamical quantum criticality is technically challenging as understanding the finite-temperature dynamics necessarily requires averaging over a large number of matrix elements between many-body eigenstates. Here, we develop a real-space renormalization group method for excited states that allows us to overcome this challenge in a large class of models. We characterize a specific example: the 1 D disordered transverse-field Ising model with generic interactions. While thermodynamic phase transitions are generally forbidden in this model, using the real-space renormalization group method for excited states we find a finite-temperature dynamical transition between two localized phases. The transition is characterized by nonanalyticities in the low-frequency heat conductivity and in the long-time (dynamic spin correlation function. The latter is a consequence of an up-down spin symmetry that results in the appearance of an Edwards-Anderson-like order parameter in one of the localized phases.

  19. Quantum Hall criticality and localization in graphene with short-range impurities at the Dirac point. (United States)

    Gattenlöhner, S; Hannes, W-R; Ostrovsky, P M; Gornyi, I V; Mirlin, A D; Titov, M


    We explore the longitudinal conductivity of graphene at the Dirac point in a strong magnetic field with two types of short-range scatterers: adatoms that mix the valleys and "scalar" impurities that do not mix them. A scattering theory for the Dirac equation is employed to express the conductance of a graphene sample as a function of impurity coordinates; an averaging over impurity positions is then performed numerically. The conductivity σ is equal to the ballistic value 4e2/πh for each disorder realization, provided the number of flux quanta considerably exceeds the number of impurities. For weaker fields, the conductivity in the presence of scalar impurities scales to the quantum-Hall critical point with σ≃4×0.4e2/h at half filling or to zero away from half filling due to the onset of Anderson localization. For adatoms, the localization behavior is also obtained at half filling due to splitting of the critical energy by intervalley scattering. Our results reveal a complex scaling flow governed by fixed points of different symmetry classes: remarkably, all key manifestations of Anderson localization and criticality in two dimensions are observed numerically in a single setup.

  20. Weakly interacting topological insulators: Quantum criticality and the renormalization group approach (United States)

    Chen, Wei


    For D -dimensional weakly interacting topological insulators in certain symmetry classes, the topological invariant can be calculated from a D - or (D +1 ) -dimensional integration over a certain curvature function that is expressed in terms of single-particle Green's functions. Based on the divergence of curvature function at the topological phase transition, we demonstrate how a renormalization group approach circumvents these integrations and reduces the necessary calculation to that for the Green's function alone, rendering a numerically efficient tool to identify topological phase transitions in a large parameter space. The method further unveils a number of statistical aspects related to the quantum criticality in weakly interacting topological insulators, including correlation function, critical exponents, and scaling laws, that can be used to characterize the topological phase transitions driven by either interacting or noninteracting parameters. We use 1D class BDI and 2D class A Dirac models with electron-electron and electron-phonon interactions to demonstrate these principles and find that interactions may change the critical exponents of the topological insulators.

  1. Landau-Ginzburg Limit of Black Hole's Quantum Portrait: Self Similarity and Critical Exponent

    CERN Document Server

    Dvali, Gia


    Recently we have suggested that the microscopic quantum description of a black hole is an overpacked self-sustained Bose-condensate of N weakly-interacting soft gravitons, which obeys the rules of 't Hooft's large-N physics. In this note we derive an effective Landau-Ginzburg Lagrangian for the condensate and show that it becomes an exact description in a semi-classical limit that serves as the black hole analog of 't Hooft's planar limit. The role of a weakly-coupled Landau-Ginzburg order parameter is played by N. This description consistently reproduces the known properties of black holes in semi-classical limit. Hawking radiation, as the quantum depletion of the condensate, is described by the slow-roll of the field N. In the semiclassical limit, where black holes of arbitrarily small size are allowed, the equation of depletion is self similar leading to a scaling law for the black hole size with critical exponent 1/3.

  2. Anomalous transport phenomena in CeCoIn{sub 5} close to quantum critical point

    Energy Technology Data Exchange (ETDEWEB)

    Onari, S. [Department of Applied Physics, Nagoya University, Nagoya 464-8603 (Japan)]. E-mail:; Kontani, H. [Department of Physics, Nagoya University, Nagoya 464-8602 (Japan); Tanaka, Y. [Department of Applied Physics, Nagoya University, Nagoya 464-8603 (Japan)


    Various transport coefficients show striking deviations from conventional Fermi-liquid behaviors in many electron systems which are close to antiferromagnetic (AF) quantum critical points (QCP). For example, Hall coefficients and Nernst coefficients in three-dimensional heavy fermion CeCoIn{sub 5} and CeCu{sub 6-x}Au{sub x} increase remarkably at low temperatures. These temperature dependences are too strong to explain in terms of the relaxation time approximation. To elucidate the origin of these anomalous transport phenomena in three-dimensional systems, we study the role of current vertex corrections (CVC) based on the fluctuation exchange (FLEX) approximation. We find that the Hall coefficient and the Nernst coefficient strongly increase due to the CVC in the vicinity of the AF QCP, even in three-dimensional systems.

  3. Critical strain region evaluation of self-assembled semiconductor quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Sales, D L [Departamento de Ciencia de los Materiales e I. M. y Q. I., Universidad de Cadiz, Puerto Real, Cadiz (Spain); Pizarro, J [Departamento de Lenguajes y Sistemas Informaticos, Universidad de Cadiz, Puerto Real, Cadiz (Spain); Galindo, P L [Departamento de Lenguajes y Sistemas Informaticos, Universidad de Cadiz, Puerto Real, Cadiz (Spain); Garcia, R [Departamento de Ciencia de los Materiales e I. M. y Q. I., Universidad de Cadiz, Puerto Real, Cadiz (Spain); Trevisi, G [CNR-IMEM Institute, Parco delle Scienze 37a, 43100, Parma (Italy); Frigeri, P [CNR-IMEM Institute, Parco delle Scienze 37a, 43100, Parma (Italy); Nasi, L [CNR-IMEM Institute, Parco delle Scienze 37a, 43100, Parma (Italy); Franchi, S [CNR-IMEM Institute, Parco delle Scienze 37a, 43100, Parma (Italy); Molina, S I [Departamento de Ciencia de los Materiales e I. M. y Q. I., Universidad de Cadiz, Puerto Real, Cadiz (Spain)


    A novel peak finding method to map the strain from high resolution transmission electron micrographs, known as the Peak Pairs method, has been applied to In(Ga)As/AlGaAs quantum dot (QD) samples, which present stacking faults emerging from the QD edges. Moreover, strain distribution has been simulated by the finite element method applying the elastic theory on a 3D QD model. The agreement existing between determined and simulated strain values reveals that these techniques are consistent enough to qualitatively characterize the strain distribution of nanostructured materials. The correct application of both methods allows the localization of critical strain zones in semiconductor QDs, predicting the nucleation of defects, and being a very useful tool for the design of semiconductor devices.

  4. At the Limits of Criticality-Based Quantum Metrology: Apparent Super-Heisenberg Scaling Revisited (United States)

    Rams, Marek M.; Sierant, Piotr; Dutta, Omyoti; Horodecki, Paweł; Zakrzewski, Jakub


    We address the question of whether the super-Heisenberg scaling for quantum estimation is indeed realizable. We unify the results of two approaches. In the first one, the original system is compared with its copy rotated by the parameter-dependent dynamics. If the parameter is coupled to the one-body part of the Hamiltonian, the precision of its estimation is known to scale at most as N-1 (Heisenberg scaling) in terms of the number of elementary subsystems used N . The second approach compares the overlap between the ground states of the parameter-dependent Hamiltonian in critical systems, often leading to an apparent super-Heisenberg scaling. However, we point out that if one takes into account the scaling of time needed to perform the necessary operations, i.e., ensuring adiabaticity of the evolution, the Heisenberg limit given by the rotation scenario is recovered. We illustrate the general theory on a ferromagnetic Heisenberg spin chain example and show that it exhibits such super-Heisenberg scaling of ground-state fidelity around the critical value of the parameter (magnetic field) governing the one-body part of the Hamiltonian. Even an elementary estimator represented by a single-site magnetization already outperforms the Heisenberg behavior providing the N-1.5 scaling. In this case, Fisher information sets the ultimate scaling as N-1.75, which can be saturated by measuring magnetization on all sites simultaneously. We discuss universal scaling predictions of the estimation precision offered by such observables, both at zero and finite temperatures, and support them with numerical simulations in the model. We provide an experimental proposal of realization of the considered model via mapping the system to ultracold bosons in a periodically shaken optical lattice. We explicitly derive that the Heisenberg limit is recovered when the time needed for preparation of quantum states involved is taken into account.

  5. THz spectroscopy of one-dimensional Ising chain compound CoNb2O6 near the quantum critical point (United States)

    Viirok, Johan; Hüvonen, D.; Rõõm, T.; Nagel, U.; Morris, C. M.; Koohpayeh, S. M.; McQueen, T. M.; Armitage, N. P.; Krizan, J.; Cava, R. J.

    One-dimensional Ising spin chain is a novel example of an interacting quantum many body system. The Ising chain in a transverse field is a good candidate to study quantum phase transitions because its low dimensionality increases its tendency to exhibit interesting quantum effects. We studied the one-dimensional ferromagnetic Ising chain material CoNb2O6 using far infrared spectroscopy in high magnetic fields up to 17 T and down to 0.3 K using a dilution refrigerator. Special attention is paid to the spectral region near the quantum critical point near 5.5 T. Research sponsored by the Estonian Ministry of Education and Research (IUT23-3) and Estonian Ministry of Education and Research and the European Regional Development Fund project TK134.

  6. Rhorix: An interface between quantum chemical topology and the 3D graphics program blender. (United States)

    Mills, Matthew J L; Sale, Kenneth L; Simmons, Blake A; Popelier, Paul L A


    Chemical research is assisted by the creation of visual representations that map concepts (such as atoms and bonds) to 3D objects. These concepts are rooted in chemical theory that predates routine solution of the Schrödinger equation for systems of interesting size. The method of Quantum Chemical Topology (QCT) provides an alternative, parameter-free means to understand chemical phenomena directly from quantum mechanical principles. Representation of the topological elements of QCT has lagged behind the best tools available. Here, we describe a general abstraction (and corresponding file format) that permits the definition of mappings between topological objects and their 3D representations. Possible mappings are discussed and a canonical example is suggested, which has been implemented as a Python "Add-On" named Rhorix for the state-of-the-art 3D modeling program Blender. This allows chemists to use modern drawing tools and artists to access QCT data in a familiar context. A number of examples are discussed. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc.

  7. Degradation of di(2-ethyl hexyl) phthalate by Fusarium culmorum: Kinetics, enzymatic activities and biodegradation pathway based on quantum chemical modelingpathway based on quantum chemical modeling

    Energy Technology Data Exchange (ETDEWEB)

    Ahuactzin-Pérez, Miriam [Doctorado en Biología Experimental, Universidad Autónoma Metropolitana-Iztapalapa (UAM-I) (Mexico); Facultad de Agrobiología, Universidad Autónoma de Tlaxcala, Ixtacuixtla, Tlaxcala (Mexico); Tlecuitl-Beristain, Saúl; García-Dávila, Jorge [Universidad Politécnica de Tlaxcala, San Pedro Xalcatzinco, Tepeyanco, Tlaxcala CP 90180 (Mexico); González-Pérez, Manuel [Universidad Popular Autónoma del Estado de Puebla, Puebla CP 72410 (Mexico); Gutiérrez-Ruíz, María Concepción [Departamento de Ciencias de la Salud, Universidad Autónoma Metropolitana-Iztapalapa, D.F (Mexico); Sánchez, Carmen, E-mail: [Laboratory of Biotechnology, Research Centre for Biological Sciences, Universidad Autónoma de Tlaxcala, Ixtacuixtla, Tlaxcala CP. 90062 (Mexico)


    Di(2-ethylhexyl) phthalate (DEHP) is a plasticizer widely used in the manufacture of plastics, and it is an environmental contaminant. The specific growth rate (μ), maximum biomass (X{sub max}), biodegradation constant of DEHP (k), half-life (t{sub 1/2}) of DEHP biodegradation and removal efficiency of DEHP, esterase and laccase specific activities, and enzymatic yield parameters were evaluated for Fusarium culmorum grown on media containing glucose and different concentrations of DEHP (0, 500 and 1000 mg/L). The greatest μ and the largest X{sub max} occurred in media supplemented with 1000 mg of DEHP/L. F. culmorum degraded 95% of the highest amount of DEHP tested (1000 mg/L) within 60 h of growth. The k and t{sub 1/2} were 0.024 h{sup −1} and 28 h, respectively, for both DEHP concentrations. The removal efficiency of DEHP was 99.8% and 99.9% for 1000 and 500 mg/L, respectively. Much higher specific esterase activity than specific laccase activity was observed in all media tested. The compounds of biodegradation of DEHP were identified by GC–MS. A DEHP biodegradation pathway by F. culmorum was proposed on the basis of the intermolecular flow of electrons of the identified intermediate compounds using quantum chemical modeling. DEHP was fully metabolized by F. culmorum with butanediol as the final product. This fungus offers great potential in bioremediation of environments polluted with DEHP. - Highlights: • F. culmorum degraded 95% of DEHP (1000 mg/L) within 60 h. • Removal efficiency of DEHP was 99.8% and 99.9% for 1000 and 500 mg/L, respectively. • DEHP was fully metabolized by F. culmorum, with butanediol as the final product. • A DEHP biodegradation pathway was proposed using on quantum chemical modeling.

  8. The Radical Pair Mechanism and the Avian Chemical Compass: Quantum Coherence and Entanglement

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Yiteng [Purdue Univ., West Lafayette, IN (United States); Kais, Sabre [Purdue Univ., West Lafayette, IN (United States); Berman, Gennady Petrovich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    We review the spin radical pair mechanism which is a promising explanation of avian navigation. This mechanism is based on the dependence of product yields on 1) the hyperfine interaction involving electron spins and neighboring nuclear spins and 2) the intensity and orientation of the geomagnetic field. One surprising result is that even at ambient conditions quantum entanglement of electron spins can play an important role in avian magnetoreception. This review describes the general scheme of chemical reactions involving radical pairs generated from singlet and triplet precursors; the spin dynamics of the radical pairs; and the magnetic field dependence of product yields caused by the radical pair mechanism. The main part of the review includes a description of the chemical compass in birds. We review: the general properties of the avian compass; the basic scheme of the radical pair mechanism; the reaction kinetics in cryptochrome; quantum coherence and entanglement in the avian compass; and the effects of noise. We believe that the quantum avian compass can play an important role in avian navigation and can also provide the foundation for a new generation of sensitive and selective magnetic-sensing nano-devices.

  9. Applications of Canonical transformations and nontrivial vacuum solutions to flavor mixing and critical phenomena in quantum field theory

    Energy Technology Data Exchange (ETDEWEB)

    Mishchenko, Yuriy [North Carolina State Univ., Raleigh, NC (United States)


    MISHCHENKO, YURIY. Applications of Canonical Transformations and Nontrivial Vacuum Solutions to flavor mixing and critical phenomena in Quantum Field Theory. (Under the direction of Chueng-Ryong Ji.) In this dissertation we consider two recent applications of Bogoliubov Transformation to the phenomenology of quantum mixing and the theory of critical phenomena. In recent years quantum mixing got in the focus of the searches for New Physics due to its unparalleled sensitivity to SM parameters and indications of neutrino mixing. It was recently suggested that Bogoliubov Transformation may be important in proper definition of the flavor states that otherwise results in problems in perturbative treatment. As first part of this dissertation we investigate this conjecture and develop a complete formulation of such a mixing field theory involving introduction of general formalism, analysis of space-time conversion and phenomenological implications. As second part of this dissertati

  10. Uniformity of quantum well heterostructure GaAlAs lasers grown by metalorganic chemical vapor deposition

    Energy Technology Data Exchange (ETDEWEB)

    Scifres, D.R.; Burnham, R.D.; Bernstein, M.; Chung, H.; Endicott, F.; Mosby, W.; Tramontana, J.; Walker, J.; Yingling, R.D. Jr.


    The threshold current density, laser wavelength, grown layer thickness, reverse breakdown voltage, and far-field radiation pattern as a function of position on the grown wafer are reported for broad area multiple quantum well GaAlAs heterostructure lasers grown by metalorganic chemical vapor deposition. It is found that the layer thickness varies across a 1.5-in. sample by as much as 20% at the outer edges of the water, leading to a lasing wavelength shift of as much as 150 A owing to the quantum size effect. It is shown that this thickness variation has only a small effect on the threshold current density across the water such that the uniformity of threshold current density is comparable to that reported previously for molecular beam epitaxy-grown conventional double heterostructure lasers.

  11. Quantum-chemical investigations of spectroscopic properties of a fluorescence probe (United States)

    Titova, T. Yu.; Morozova, Yu. P.; Zharkova, O. M.; Artyukhov, V. Ya.; Korolev, B. V.


    The prodan molecule (6-propionyl-2-dimethylamino naphthalene) - fluorescence probe - is investigated by quantum-chemical methods of intermediate neglect of differential overlap (INDO) and molecular electrostatic potential (MEP). The dipole moments of the ground and excited states, the nature and position of energy levels, the centers of specific solvation, the rate constants of photoprocesses, and the fluorescence quantum yield are estimated. To elucidate the role of the dimethylamino group in the formation of bands and spectral characteristics, the molecule only with the propionyl group (pron) is investigated. The long-wavelength absorption bands of prodan and pron molecules are interpreted. The results obtained for the prodan molecule by the INDO method with original spectroscopic parameterization are compared with the literature data obtained by the DFT/CIS, ZINDO/S, and AM1/CISD methods.

  12. Spectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases (United States)

    Tokatli, A.; Ucun, F.; Sütçü, K.; Osmanoğlu, Y. E.; Osmanoğlu, Ş.


    In this study the conformational behavior of cycloheximide in the gas and solution (CHCl3) phases has theoretically been investigated by spectroscopic and quantum chemical properties using density functional theory (wB97X-D) method with 6-31++G(d,p) basis set, for the first time. The calculated IR results reveal that in the ground state the molecule exits as a mixture of the chair and twist-boat conformers in the gas phase, while the calculated NMR results reveal that it only exits as the chair conformer in the solution phase. In order to obtain the contributions coming from intramolecular interactions to the stability of the conformers in the gas and solution phases, the quantum theory of atoms in molecules (QTAIM), noncovalent interactions (NCI) method, and natural bond orbital analysis (NBO) have been employed. The QTAIM and NCI methods indicated that by intramolecular interactions with bond critical point (BCP) the twist-boat conformer is more stabilized than the chair conformer, while by steric interactions it is more destabilized. Considering that these interactions balance each other, the stabilities of the conformers are understood to be dictated by the van der Waals interactions. The NBO analyses show that the hyperconjugative and steric effects play an important role in the stabilization in the gas and solution phases. Furthermore, to get a better understanding of the chemical behavior of this important antibiotic drug we have evaluated and, commented the global and local reactivity descriptors of the both conformers. Finally, the EPR analysis of γ-irradiated cycloheximide has been done. The comparison of the experimental and calculated data have showed the inducement of a radical structure of (CH2)2ĊCH2 in the molecule. The experimental EPR spectrum has also confirmed that the molecule simultaneously exists in the chair and twist-boat conformers in the solid phase.

  13. Reassigning the Structures of Natural Products Using NMR Chemical Shifts Computed with Quantum Mechanics: A Laboratory Exercise (United States)

    Palazzo, Teresa A.; Truong, Tiana T.; Wong, Shirley M. T.; Mack, Emma T.; Lodewyk, Michael W.; Harrison, Jason G.; Gamage, R. Alan; Siegel, Justin B.; Kurth, Mark J.; Tantillo, Dean J.


    An applied computational chemistry laboratory exercise is described in which students use modern quantum chemical calculations of chemical shifts to assign the structure of a recently isolated natural product. A pre/post assessment was used to measure student learning gains and verify that students demonstrated proficiency of key learning…

  14. Quantum

    CERN Document Server

    Al-Khalili, Jim


    In this lively look at quantum science, a physicist takes you on an entertaining and enlightening journey through the basics of subatomic physics. Along the way, he examines the paradox of quantum mechanics--beautifully mathematical in theory but confoundingly unpredictable in the real world. Marvel at the Dual Slit experiment as a tiny atom passes through two separate openings at the same time. Ponder the peculiar communication of quantum particles, which can remain in touch no matter how far apart. Join the genius jewel thief as he carries out a quantum measurement on a diamond without ever touching the object in question. Baffle yourself with the bizzareness of quantum tunneling, the equivalent of traveling partway up a hill, only to disappear then reappear traveling down the opposite side. With its clean, colorful layout and conversational tone, this text will hook you into the conundrum that is quantum mechanics.

  15. Dynamical Quantum Phase Transitions in Spin Chains with Long-Range Interactions: Merging Different Concepts of Nonequilibrium Criticality (United States)

    Žunkovič, Bojan; Heyl, Markus; Knap, Michael; Silva, Alessandro


    We theoretically study the dynamics of a transverse-field Ising chain with power-law decaying interactions characterized by an exponent α , which can be experimentally realized in ion traps. We focus on two classes of emergent dynamical critical phenomena following a quantum quench from a ferromagnetic initial state: The first one manifests in the time-averaged order parameter, which vanishes at a critical transverse field. We argue that such a transition occurs only for long-range interactions α ≤2 . The second class corresponds to the emergence of time-periodic singularities in the return probability to the ground-state manifold which is obtained for all values of α and agrees with the order parameter transition for α ≤2 . We characterize how the two classes of nonequilibrium criticality correspond to each other and give a physical interpretation based on the symmetry of the time-evolved quantum states.

  16. Microwave, High-Resolution Infrared, and Quantum Chemical Investigations of CHBrF2

    DEFF Research Database (Denmark)

    Cazzoli, Gabriele; Cludi, Lino; Puzzarini, Cristina


    analysis by high-level quantum chemical calculations at the coupled-cluster level. In this context, the importance of relativistic effects, which are of the order of 6.5% and included in the present work using second-order direct perturbation theory, needs to be emphasized for accurate predictions...... of the bromine quadrupole-coupling constants. The infrared measurements focused on the v(4) fundamental band of (CHBrF2)-Br-79. Fourier transform investigations using a synchrotron radiation source provided the necessary resolution for the observation and analysis of the rotational structure. The spectroscopic...

  17. Compensation effects in molecular interactions and the quantum chemical le Chatelier principle. (United States)

    Mezey, Paul G


    Components of molecular interactions and various changes in the components of total energy changes during molecular processes typically exhibit some degrees of compensation. This may be as prominent as the over 90% compensation of the electronic energy and nuclear repulsion energy components of the total energy in some conformational changes. Some of these compensations are enhanced by solvent effects. For various arrangements of ions in a solvent, however, not only compensation but also a formal, mutual enhancement between the electronic energy and nuclear repulsion energy components of the total energy may also occur, when the tools of nuclear charge variation are applied to establish quantum chemically rigorous energy inequalities.

  18. Quantum Chemical Prediction of Equilibrium Acidities of Ureas, Deltamides, Squaramides, and Croconamides. (United States)

    Ho, Junming; Zwicker, Vincent E; Yuen, Karen K Y; Jolliffe, Katrina A


    Robust quantum chemical methods are employed to predict the pK a 's of several families of dual hydrogen-bonding organocatalysts/anion receptors, including deltamides and croconamides as well as their thio derivatives. The average accuracy of these predictions is ∼1 pK a unit and allows for a comparison of the acidity between classes of receptors and for quantitative studies of substituent effects. These computational insights further explain the relationship between pK a and chloride anion affinity of these receptors that will be important for designing future anion receptors and organocatalysts.

  19. Relation of Certain Quantum Chemical Parameters to Lubrication Behavior of Solid Oxides

    Directory of Open Access Journals (Sweden)

    Yuansheng Jin


    Full Text Available Abstract: It is well-documented that certain oxides (such as Re2O7, B2O3, MoO3, V2O5, etc. can provide friction coefficients of 0.1-0.3 to sliding surfaces at elevated temperatures and thus they are often referred to as lubricious oxides in the tribology literature. In a recently proposed crystal chemical model, Erdemir was able to establish a close correlation between the reported friction coefficients of such oxides and their ionic potentials [1]. In the present paper, we expand on this original concept and explore the relevance of two other quantum chemical parameters, electronegativity and chemical hardness, to the lubricity of solid oxides. These parameters have already been used by scientists to explain the nature of tribochemical interactions between various oil additives and sliding surfaces. It is conceivable that electronegativity and chemical hardness may also be strongly related to the extent of adhesive interactions and shear rheology of solid oxides and hence to their lubricity. The new results have confirmed that electronegativity, like ionic potential, is indeed a valid quantum chemistry parameter that can be used in predicting the lubrication behavior of solid oxides. Generally, the higher the electronegativity of the solid oxides is, the lower the friction coefficients will be. However, chemical hardness did not yield a similar trend. In light of these new findings, we propose some guidelines for the formulation of novel oxide or alloy systems that can lead to the formation of lubricious oxides at elevated temperatures. The findings of this study may pave the way for designer-based tribosystems in general and smart tribochemical systems in particular in future tribological applications such as dry machining.

  20. Deconfined quantum criticality of the O(3) nonlinear σ model in two spatial dimensions: A renormalization-group study

    International Nuclear Information System (INIS)

    Kim, Ki-Seok


    We investigate the quantum phase transition of the O(3) nonlinear σ model without Berry phase in two spatial dimensions. Utilizing the CP 1 representation of the nonlinear σ model, we obtain an effective action in terms of bosonic spinons interacting via compact U(1) gauge fields. Based on the effective field theory, we find that the bosonic spinons are deconfined to emerge at the quantum critical point of the nonlinear σ model. It is emphasized that the deconfinement of spinons is realized in the absence of Berry phase. This is in contrast to the previous study of Senthil et al. [Science 303, 1490 (2004)], where the Berry phase plays a crucial role, resulting in the deconfinement of spinons. It is the reason why the deconfinement is obtained even in the absence of the Berry phase effect that the quantum critical point is described by the XY ('neutral') fixed point, not the IXY ('charged') fixed point. The IXY fixed point is shown to be unstable against instanton excitations and the instanton excitations are proliferated. At the IXY fixed point it is the Berry phase effect that suppresses the instanton excitations, causing the deconfinement of spinons. On the other hand, the XY fixed point is found to be stable against instanton excitations because an effective internal charge is zero at the neutral XY fixed point. As a result the deconfinement of spinons occurs at the quantum critical point of the O(3) nonlinear σ model in two dimensions

  1. Influence of wet chemical cleaning on quantum efficiency of GaN photocathode (United States)

    Wang, Xiao-Hui; Gao, Pin; Wang, Hong-Gang; Li, Biao; Chang, Ben-Kang


    GaN samples 1-3 are cleaned by a 2:2:1 solution of sulfuric acid (98%) to hydrogen peroxide (30%) to de-ionized water; hydrochloric acid (37%); or a 4:1 solution of sulfuric acid (98%) to hydrogen peroxide (30%). The samples are activated by Cs/O after the same annealing process. X-ray photoelectron spectroscopy after the different ways of wet chemical cleaning shows: sample 1 has the largest proportion of Ga, N, and O among the three samples, while its C content is the lowest. After activation the quantum efficiency curves show sample 1 has the best photocathode performance. We think the wet chemical cleaning method is a process which will mainly remove C contamination.

  2. Influence of wet chemical cleaning on quantum efficiency of GaN photocathode

    International Nuclear Information System (INIS)

    Wang Xiao-Hui; Gao Pin; Wang Hong-Gang; Li Biao; Chang Ben-Kang


    GaN samples 1–3 are cleaned by a 2:2:1 solution of sulfuric acid (98%) to hydrogen peroxide (30%) to de-ionized water; hydrochloric acid (37%); or a 4:1 solution of sulfuric acid (98%) to hydrogen peroxide (30%). The samples are activated by Cs/O after the same annealing process. X-ray photoelectron spectroscopy after the different ways of wet chemical cleaning shows: sample 1 has the largest proportion of Ga, N, and O among the three samples, while its C content is the lowest. After activation the quantum efficiency curves show sample 1 has the best photocathode performance. We think the wet chemical cleaning method is a process which will mainly remove C contamination. (condensed matter: electronic structure, electrical, magnetic, and optical properties)

  3. Influence of GaAs Substrate Orientation on InAs Quantum Dots: Surface Morphology, Critical Thickness, and Optical Properties

    Directory of Open Access Journals (Sweden)

    Liang BL


    Full Text Available AbstractInAs/GaAs heterostructures have been simultaneously grown by molecular beam epitaxy on GaAs (100, GaAs (100 with a 2° misorientation angle towards [01−1], and GaAs (n11B (n = 9, 7, 5 substrates. While the substrate misorientation angle increased from 0° to 15.8°, a clear evolution from quantum dots to quantum well was evident by the surface morphology, the photoluminescence, and the time-resolved photoluminescence, respectively. This evolution revealed an increased critical thickness and a delayed formation of InAs quantum dots as the surface orientation departed from GaAs (100, which was explained by the thermal-equilibrium model due to the less efficient of strain relaxation on misoriented substrate surfaces.

  4. Coherent chemical kinetics as quantum walks. I. Reaction operators for radical pairs. (United States)

    Chia, A; Tan, K C; Pawela, Ł; Kurzyński, P; Paterek, T; Kaszlikowski, D


    Classical chemical kinetics uses rate-equation models to describe how a reaction proceeds in time. Such models are sufficient for describing state transitions in a reaction where coherences between different states do not arise, in other words, a reaction that contains only incoherent transitions. A prominent example of a reaction containing coherent transitions is the radical-pair model. The kinetics of such reactions is defined by the so-called reaction operator that determines the radical-pair state as a function of intermediate transition rates. We argue that the well-known concept of quantum walks from quantum information theory is a natural and apt framework for describing multisite chemical reactions. By composing Kraus maps that act only on two sites at a time, we show how the quantum-walk formalism can be applied to derive a reaction operator for the standard avian radical-pair reaction. Our reaction operator predicts the same recombination dephasing rate as the conventional Haberkorn model, which is consistent with recent experiments [K. Maeda et al., J. Chem. Phys. 139, 234309 (2013)], in contrast to previous work by Jones and Hore [J. A. Jones and P. J. Hore, Chem. Phys. Lett. 488, 90 (2010)]. The standard radical-pair reaction has conventionally been described by either a normalized density operator incorporating both the radical pair and reaction products or a trace-decreasing density operator that considers only the radical pair. We demonstrate a density operator that is both normalized and refers only to radical-pair states. Generalizations to include additional dephasing processes and an arbitrary number of sites are also discussed.

  5. TG-FTIR, DSC and quantum chemical studies of the thermal decomposition of quaternary methylammonium halides

    International Nuclear Information System (INIS)

    Sawicka, Marlena; Storoniak, Piotr; Skurski, Piotr; Blazejowski, Jerzy; Rak, Janusz


    The thermal decomposition of quaternary methylammonium halides was studied using thermogravimetry coupled to FTIR (TG-FTIR) and differential scanning calorimetry (DSC) as well as the DFT, MP2 and G2 quantum chemical methods. There is almost perfect agreement between the experimental IR spectra and those predicted at the B3LYP/6-311G(d,p) level: this has demonstrated for the first time that an equimolar mixture of trimethylamine and a methyl halide is produced as a result of decomposition. The experimental enthalpies of dissociation are 153.4, 171.2, and 186.7 kJ/mol for chloride, bromide and iodide, respectively, values that correlate well with the calculated enthalpies of dissociation based on crystal lattice energies and quantum chemical thermodynamic barriers. The experimental activation barriers estimated from the least-squares fit of the F1 kinetic model (first-order process) to thermogravimetric traces - 283, 244 and 204 kJ/mol for chloride, bromide and iodide, respectively - agree very well with theoretically calculated values. The theoretical approach assumed in this work has been shown capable of predicting the relevant characteristics of the thermal decomposition of solids with experimental accuracy

  6. IR spectroscopic and quantum-chemical manifestation of flavin mononucleotide’s isoalloxazine ring protonation

    Directory of Open Access Journals (Sweden)

    Ю. Н. Близнюк


    Full Text Available Flavin mononucleotide (FMN is the prosthetic group of many oxidoreductases performing redox function in cells. The coenzyme reversible reduction reaction involvs isoalloxazine ring which may take two electrons and two protons upon reduction. The spectra of dried films of flavin mononucleotide grown from neutral (pH=7,0 and weakly acidic (pH=6,0 solutions were obtained in absorption region of C=C, C=N atoms of isoalloxazine ring (1450–1650 cm-1 using infrared (IR spectroscopic method. The high-frequency shifts of absorption bands of intra-ring vibrations in films grown from weakly acidic (pH=6,0 solution were found. These high-frequency shifts were explained by the protonation of N1 and N5 nitrogen atoms of the ring. The performed quantum-chemical calculation using the density functional theory (DFT confirmed that the N1 and N5 atoms have significant negative charges. The obtained quantum-chemical data on the charges of the isoalloxazine ring atoms and its bond orders correlate with the frequency shifts of the absorption bands of protonated atoms of intra-ring vibrations.

  7. Quantum Chemical Methods for the Prediction of Energetic, Physical, and Spectroscopic Properties of Ionic Liquids. (United States)

    Izgorodina, Ekaterina I; Seeger, Zoe L; Scarborough, David L A; Tan, Samuel Y S


    The accurate prediction of physicochemical properties of condensed systems is a longstanding goal of theoretical (quantum) chemistry. Ionic liquids comprising entirely of ions provide a unique challenge in this respect due to the diverse chemical nature of available ions and the complex interplay of intermolecular interactions among them, thus resulting in the wide variability of physicochemical properties, such as thermodynamic, transport, and spectroscopic properties. It is well understood that intermolecular forces are directly linked to physicochemical properties of condensed systems, and therefore, an understanding of this relationship would greatly aid in the design and synthesis of functionalized materials with tailored properties for an application at hand. This review aims to give an overview of how electronic structure properties obtained from quantum chemical methods such as interaction/binding energy and its fundamental components, dipole moment, polarizability, and orbital energies, can help shed light on the energetic, physical, and spectroscopic properties of semi-Coulomb systems such as ionic liquids. Particular emphasis is given to the prediction of their thermodynamic, transport, spectroscopic, and solubilizing properties.

  8. Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes. (United States)

    Gao, Jiali; Major, Dan T; Fan, Yao; Lin, Yen-Lin; Ma, Shuhua; Wong, Kin-Yiu


    A method for incorporating quantum mechanics into enzyme kinetics modeling is presented. Three aspects are emphasized: 1) combined quantum mechanical and molecular mechanical methods are used to represent the potential energy surface for modeling bond forming and breaking processes, 2) instantaneous normal mode analyses are used to incorporate quantum vibrational free energies to the classical potential of mean force, and 3) multidimensional tunneling methods are used to estimate quantum effects on the reaction coordinate motion. Centroid path integral simulations are described to make quantum corrections to the classical potential of mean force. In this method, the nuclear quantum vibrational and tunneling contributions are not separable. An integrated centroid path integral-free energy perturbation and umbrella sampling (PI-FEP/UM) method along with a bisection sampling procedure was summarized, which provides an accurate, easily convergent method for computing kinetic isotope effects for chemical reactions in solution and in enzymes. In the ensemble-averaged variational transition state theory with multidimensional tunneling (EA-VTST/MT), these three aspects of quantum mechanical effects can be individually treated, providing useful insights into the mechanism of enzymatic reactions. These methods are illustrated by applications to a model process in the gas phase, the decarboxylation reaction of N-methyl picolinate in water, and the proton abstraction and reprotonation process catalyzed by alanine racemase. These examples show that the incorporation of quantum mechanical effects is essential for enzyme kinetics simulations.

  9. Development of a quantum chemical molecular dynamics tribochemical simulator and its application to tribochemical reaction dynamics of lubricant additives

    International Nuclear Information System (INIS)

    Onodera, T; Tsuboi, H; Hatakeyama, N; Endou, A; Miyamoto, A; Miura, R; Takaba, H; Suzuki, A; Kubo, M


    Tribology at the atomistic and molecular levels has been theoretically studied by a classical molecular dynamics (MD) method. However, this method inherently cannot simulate the tribochemical reaction dynamics because it does not consider the electrons in nature. Although the first-principles based MD method has recently been used for understanding the chemical reaction dynamics of several molecules in the tribology field, the method cannot simulate the tribochemical reaction dynamics of a large complex system including solid surfaces and interfaces due to its huge computation costs. On the other hand, we have developed a quantum chemical MD tribochemical simulator on the basis of a hybrid tight-binding quantum chemical/classical MD method. In the simulator, the central part of the chemical reaction dynamics is calculated by the tight-binding quantum chemical MD method, and the remaining part is calculated by the classical MD method. Therefore, the developed tribochemical simulator realizes the study on tribochemical reaction dynamics of a large complex system, which cannot be treated by using the conventional classical MD or the first-principles MD methods. In this paper, we review our developed quantum chemical MD tribochemical simulator and its application to the tribochemical reaction dynamics of a few lubricant additives

  10. Electronic in-plane symmetry breaking at field-tuned quantum criticality in CeRhIn5

    Energy Technology Data Exchange (ETDEWEB)

    Helm, T. [MPI-CPFS (Germany); Bachmann, M. [MPI-CPFS (Germany); Moll, P.J.W. [MPI-CPFS (Germany); Balicas, L. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). National High Magnetic Field Lab. (MagLab); Chan, Mun Keat [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Ramshaw, Brad [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Mcdonald, Ross David [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Balakirev, Fedor Fedorovich [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Bauer, Eric Dietzgen [Los Alamos National Lab. (LANL), Los Alamos, NM (United States); Ronning, Filip [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)


    Electronic nematicity appears in proximity to unconventional high-temperature superconductivity in the cuprates and iron-arsenides, yet whether they cooperate or compete is widely discussed. While many parallels are drawn between high-Tc and heavy fermion superconductors, electronic nematicity was not believed to be an important aspect in their superconductivity. We have found evidence for a field-induced strong electronic in-plane symmetry breaking in the tetragonal heavy fermion superconductor CeRhIn5. At ambient pressure and zero field, it hosts an anti-ferromagnetic order (AFM) of nominally localized 4f electrons at TN=3.8K(1). Moderate pressure of 17kBar suppresses the AFM order and a dome of superconductivity appears around the quantum critical point. Similarly, a density-wave-like correlated phase appears centered around the field-induced AFM quantum critical point. In this phase, we have now observed electronic nematic behavior.

  11. Controlling organic chemical hazards in food manufacturing: a hazard analysis critical control points (HACCP) approach. (United States)

    Ropkins, K; Beck, A J


    Hazard analysis by critical control points (HACCP) is a systematic approach to the identification, assessment and control of hazards. Effective HACCP requires the consideration of all hazards, i.e., chemical, microbiological and physical. However, to-date most 'in-place' HACCP procedures have tended to focus on the control of microbiological and physical food hazards. In general, the chemical component of HACCP procedures is either ignored or limited to applied chemicals, e.g., food additives and pesticides. In this paper we discuss the application of HACCP to a broader range of chemical hazards, using organic chemical contaminants as examples, and the problems that are likely to arise in the food manufacturing sector. Chemical HACCP procedures are likely to result in many of the advantages previously identified for microbiological HACCP procedures: more effective, efficient and economical than conventional end-point-testing methods. However, the high costs of analytical monitoring of chemical contaminants and a limited understanding of formulation and process optimisation as means of controlling chemical contamination of foods are likely to prevent chemical HACCP becoming as effective as microbiological HACCP.

  12. Chemical and explosive detections using photo-acoustic effect and quantum cascade lasers (United States)

    Choa, Fow-Sen


    Photoacoustic (PA) effect is a sensitive spectroscopic technique for chemical sensing. In recent years, with the development of quantum cascade lasers (QCLs), significant progress has been achieved for PA sensing applications. Using high-power, tunable mid-IR QCLs as laser sources, PA chemical sensor systems have demonstrated parts-pertrillion- level detection sensitivity. Many of these high sensitivity measurements were demonstrated locally in PA cells. Recently, we have demonstrated standoff PA detection of isopropanol vapor for more than 41 feet distance using a quantum cascade laser and a microphone with acoustic reflectors. We also further demonstrated solid phase TNT detections at a standoff distance of 8 feet. To further calibrate the detection sensitivity, we use nerve gas simulants that were generated and calibrated by a commercial vapor generator. Standoff detection of gas samples with calibrated concentration of 2.3 ppm was achieved at a detection distance of more than 2 feet. An extended detection distance up to 14 feet was observed for a higher gas concentration of 13.9 ppm. For field operations, array of microphones and microphone-reflector pairs can be utilized to achieve noise rejection and signal enhancement. We have experimentally demonstrated that the signal and noise spectra of the 4 microphone/4 reflector system with a combined SNR of 12.48 dB. For the 16-microphone and one reflector case, an SNR of 17.82 was achieved. These successful chemical sensing demonstrations will likely create new demands for widely tunable QCLs with ultralow threshold (for local fire-alarm size detection systems) and high-power (for standoff detection systems) performances.

  13. Spin-1/2 Heisenberg ladder: variation of entanglement and fidelity measures close to quantum critical points


    Tribedi, Amit; Bose, Indrani


    We consider a two-chain, spin-1/2 antiferromagnetic Heisenberg spin ladder in an external magnetic field H. The spin ladder is known to undergo second order quantum phase transitions (QPTs) at two critical values, Hc1 and Hc2, of the magnetic field. There are now known examples of strongly coupled (rung exchange interaction much stronger than nearest-neighbour intrachain exchange interaction) organic ladder compounds in which QPTs have been experimentally observed. In this paper, we investiga...

  14. On critical stability of three quantum charges interacting through delta potentials

    DEFF Research Database (Denmark)

    Cornean, Horia; Duclos, Pierre; Ricaud, Benjamin

    We consider three one dimensional quantum, charged and spinless particles interacting through delta potentials. We derive sufficient conditions which guarantee the existence of at least one bound state.......We consider three one dimensional quantum, charged and spinless particles interacting through delta potentials. We derive sufficient conditions which guarantee the existence of at least one bound state....

  15. On critical stability of three quantum charges interacting through delta potentials

    DEFF Research Database (Denmark)

    Cornean, Horia; Duclos, Pierre; Ricaud, Benjamin


    We consider three one-dimensional quantum, charged and spinless particles interacting through delta potentials. We derive sufficient conditions which guarantee the existence of at least one bound state.......We consider three one-dimensional quantum, charged and spinless particles interacting through delta potentials. We derive sufficient conditions which guarantee the existence of at least one bound state....

  16. Spin- (1)/(2) Heisenberg ladder: Variation of entanglement and fidelity measures close to quantum critical points (United States)

    Tribedi, Amit; Bose, Indrani


    We consider a two-chain, spin- (1)/(2) antiferromagnetic Heisenberg spin ladder in an external magnetic field H . The spin ladder is known to undergo second-order quantum phase transitions (QPTs) at two critical values Hc1 and Hc2 of the magnetic field. There are now known examples of strongly coupled (where the rung exchange interaction is much stronger than the nearest-neighbor intrachain exchange interaction) organic ladder compounds in which QPTs have been experimentally observed. In this paper, we investigate whether well-known bipartite entanglement meaures such as one-site von Neumann entropy, two-site von Neumann entropy, and concurrence develop special features close to the quantum critical points. As suggested by an earlier theorem, the first derivatives of the measures with respect to magnetic field are expected to diverge as H→Hc1 and H→Hc2 . Based on numerical diagonalization data and a mapping of the strongly coupled ladder Hamiltonian onto the XXZ chain Hamiltonian, for which several analytical results are known, we find that the derivatives of the entanglement measures diverge as H→Hc2 but remain finite as H→Hc1 . The reason for this discrepancy is analyzed. We further calculate two recently proposed quantum information theoretic measures, the reduced fidelity and reduced fidelity susceptibility, and show that these measures provide appropriate signatures of the QPTs occuring at the critical points H=Hc1 and H=Hc2 .

  17. Lévy flights and multifractality in quantum critical diffusion and in classical random walks on fractals. (United States)

    Kravtsov, V E; Yevtushenko, O M; Snajberk, P; Cuevas, E


    We employ the method of virial expansion to compute the retarded density correlation function (generalized diffusion propagator) in the critical random matrix ensemble in the limit of strong multifractality. We find that the long-range nature of the Hamiltonian is a common root of both multifractality and Lévy flights, which show up in the power-law intermediate- and long-distance behaviors, respectively, of the density correlation function. We review certain models of classical random walks on fractals and show the similarity of the density correlation function in them to that for the quantum problem described by the random critical long-range Hamiltonians.

  18. Genetic variation, inbreeding and chemical exposure—combined effects in wildlife and critical considerations for ecotoxicology (United States)

    Brown, A. Ross; Hosken, David J.; Balloux, François; Bickley, Lisa K.; LePage, Gareth; Owen, Stewart F.; Hetheridge, Malcolm J.; Tyler, Charles R.


    Exposure to environmental chemicals can have negative consequences for wildlife and even cause localized population extinctions. Resistance to chemical stress, however, can evolve and the mechanisms include desensitized target sites, reduced chemical uptake and increased metabolic detoxification and sequestration. Chemical resistance in wildlife populations can also arise independently of exposure and may be spread by gene flow between populations. Inbreeding—matings between closely related individuals—can have negative fitness consequences for natural populations, and there is evidence of inbreeding depression in many wildlife populations. In some cases, reduced fitness in inbred populations has been shown to be exacerbated under chemical stress. In chemical testing, both inbred and outbred laboratory animals are used and for human safety assessments, iso-genic strains (virtual clones) of mice and rats are often employed that reduce response variation, the number of animals used and associated costs. In contrast, for environmental risk assessment, strains of animals are often used that have been selectively bred to maintain heterozygosity, with the assumption that they are better able to predict adverse effects in wild, genetically variable, animals. This may not necessarily be the case however, as one outbred strain may not be representative of another or of a wild population. In this paper, we critically discuss relationships between genetic variation, inbreeding and chemical effects with the intention of seeking to support more effective chemical testing for the protection of wildlife. PMID:19833649

  19. Comparison of sugar molecule decomposition through glucose and fructose: a high-level quantum chemical study.

    Energy Technology Data Exchange (ETDEWEB)

    Assary, R. S.; Curtiss, L. A. (Center for Nanoscale Materials); ( MSD); (Northwestern Univ.)


    Efficient chemical conversion of biomass is essential to produce sustainable energy and industrial chemicals. Industrial level conversion of glucose to useful chemicals, such as furfural, hydroxymethylfurfural, and levulinic acid, is a major step in the biomass conversion but is difficult because of the formation of undesired products and side reactions. To understand the molecular level reaction mechanisms involved in the decomposition of glucose and fructose, we have carried out high-level quantum chemical calculations [Gaussian-4 (G4) theory]. Selective 1,2-dehydration, keto-enol tautomerization, isomerization, retro-aldol condensation, and hydride shifts of glucose and fructose molecules were investigated. Detailed kinetic and thermodynamic analyses indicate that, for acyclic glucose and fructose molecules, the dehydration and isomerization require larger activation barriers compared to the retro-aldol reaction at 298 K in neutral medium. The retro-aldol reaction results in the formation of C2 and C4 species from glucose and C3 species from fructose. The formation of the most stable C3 species, dihydroxyacetone from fructose, is thermodynamically downhill. The 1,3-hydride shift leads to the cleavage of the C-C bond in the acyclic species; however, the enthalpy of activation is significantly higher (50-55 kcal/mol) than that of the retro-aldol reaction (38 kcal/mol) mainly because of the sterically hindered distorted four-membered transition state compared to the hexa-membered transition state in the retro-aldol reaction. Both tautomerization and dehydration are catalyzed by a water molecule in aqueous medium; however, water has little effect on the retro-aldol reaction. Isomerization of glucose to fructose and glyceraldehyde to dihydroxyacetone proceeds through hydride shifts that require an activation enthalpy of about 40 kcal/mol at 298 K in water medium. This investigation maps out accurate energetics of the decomposition of glucose and fructose molecules

  20. Standoff detection of turbulent chemical mixture plumes using a swept external cavity quantum cascade laser

    Energy Technology Data Exchange (ETDEWEB)

    Phillips, Mark C. [Pacific Northwest National Laboratory, Richland, Washington; Brumfield, Brian E. [Pacific Northwest National Laboratory, Richland, Washington


    We demonstrate standoff detection of turbulent mixed-chemical plumes using a broadly-tunable external cavity quantum cascade laser (ECQCL). The ECQCL was directed through plumes of mixed methanol/ethanol vapor to a partially-reflective surface located 10 m away. The reflected power was measured as the ECQCL was swept over its tuning range of 930-1065 cm-1 (9.4-10.8 µm) at rates up to 200 Hz. Analysis of the transmission spectra though the plume was performed to determine chemical concentrations with time resolution of 0.005 s. Comparison of multiple spectral sweep rates of 2 Hz, 20 Hz, and 200 Hz shows that higher sweep rates reduce effects of atmospheric and source turbulence, resulting in lower detection noise and more accurate measurement of the rapidly-changing chemical concentrations. Detection sensitivities of 0.13 ppm*m for MeOH and 1.2 ppm*m for EtOH are demonstrated for a 200 Hz spectral sweep rate, normalized to 1 s detection time.

  1. Quantum correlation dynamics subjected to critical spin environment with short-range anisotropic interaction. (United States)

    Guo, J L; Zhang, X Z


    Short-range interaction among the spins can not only results in the rich phase diagram but also brings about fascinating phenomenon both in the contexts of quantum computing and information. In this paper, we investigate the quantum correlation of the system coupled to a surrounding environment with short-range anisotropic interaction. It is shown that the decay of quantum correlation of the central spins measured by pairwise entanglement and quantum discord can serve as a signature of quantum phase transition. In addition, we study the decoherence factor of the system when the environment is in the vicinity of the phase transition point. In the strong coupling regime, the decay of the decoherence factor exhibits Gaussian envelop in the time domain. However, in weak coupling limit, the quantum correlation of the system is robust against the disturbance of the magnetic field through optimal control of the anisotropic short-range interaction strength. Based on this, the effects of the short-range anisotropic interaction on the sudden transition from classical to quantum decoherence are also presented.

  2. Quantum chemical calculation of electron ionization mass spectra for general organic and inorganic molecules. (United States)

    Ásgeirsson, Vilhjálmur; Bauer, Christoph A; Grimme, Stefan


    We introduce a fully stand-alone version of the Quantum Chemistry Electron Ionization Mass Spectra (QCEIMS) program [S. Grimme, Angew. Chem. Int. Ed. , 2013, 52 , 6306] allowing efficient simulations for molecules composed of elements with atomic numbers up to Z = 86. The recently developed extended tight-binding semi-empirical method GFN-xTB has been combined with QCEIMS, thereby eliminating dependencies on third-party electronic structure software. Furthermore, for reasonable calculations of ionization potentials, as required by the method, a second tight-binding variant, IPEA-xTB, is introduced here. This novel combination of methods allows the automatic, fast and reasonably accurate computation of electron ionization mass spectra for structurally different molecules across the periodic table. In order to validate and inspect the transferability of the method, we perform large-scale simulations for some representative organic, organometallic, and main-group inorganic systems. Theoretical spectra for 23 molecules are compared directly to experimental data taken from standard databases. For the first time, realistic quantum chemistry based EI-MS for organometallic systems like ferrocene or copper(ii)acetylacetonate are presented. Compared to previously used semiempirical methods, GFN-xTB is faster, more robust, and yields overall higher quality spectra. The partially analysed theoretical reaction and fragmentation mechanisms are chemically reasonable and reveal in unprecedented detail the extreme complexity of high energy gas phase ion chemistry including complicated rearrangement reactions prior to dissociation.

  3. Application of quantum dots as analytical tools in automated chemical analysis: a review. (United States)

    Frigerio, Christian; Ribeiro, David S M; Rodrigues, S Sofia M; Abreu, Vera L R G; Barbosa, João A C; Prior, João A V; Marques, Karine L; Santos, João L M


    Colloidal semiconductor nanocrystals or quantum dots (QDs) are one of the most relevant developments in the fast-growing world of nanotechnology. Initially proposed as luminescent biological labels, they are finding new important fields of application in analytical chemistry, where their photoluminescent properties have been exploited in environmental monitoring, pharmaceutical and clinical analysis and food quality control. Despite the enormous variety of applications that have been developed, the automation of QDs-based analytical methodologies by resorting to automation tools such as continuous flow analysis and related techniques, which would allow to take advantage of particular features of the nanocrystals such as the versatile surface chemistry and ligand binding ability, the aptitude to generate reactive species, the possibility of encapsulation in different materials while retaining native luminescence providing the means for the implementation of renewable chemosensors or even the utilisation of more drastic and even stability impairing reaction conditions, is hitherto very limited. In this review, we provide insights into the analytical potential of quantum dots focusing on prospects of their utilisation in automated flow-based and flow-related approaches and the future outlook of QDs applications in chemical analysis. Copyright © 2012 Elsevier B.V. All rights reserved.

  4. Recovery from chemical, biological, and radiological incidents. Critical infrastructure and economic impact considerations

    Energy Technology Data Exchange (ETDEWEB)

    Franco, David Oliver [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Yang, Lynn I. [Sandia National Lab. (SNL-CA), Livermore, CA (United States); Hammer, Ann E. [Sandia National Lab. (SNL-CA), Livermore, CA (United States)


    To restore regional lifeline services and economic activity as quickly as possible after a chemical, biological or radiological incident, emergency planners and managers will need to prioritize critical infrastructure across many sectors for restoration. In parallel, state and local governments will need to identify and implement measures to promote reoccupation and economy recovery in the region. This document provides guidance on predisaster planning for two of the National Disaster Recovery Framework Recovery Support Functions: Infrastructure Systems and Economic Recovery. It identifies key considerations for infrastructure restoration, outlines a process for prioritizing critical infrastructure for restoration, and identifies critical considerations for promoting regional economic recovery following a widearea disaster. Its goal is to equip members of the emergency preparedness community to systematically prioritize critical infrastructure for restoration, and to develop effective economic recovery plans in preparation for a widearea CBR disaster.

  5. Semiempirical Quantum Chemical Calculations Accelerated on a Hybrid Multicore CPU-GPU Computing Platform. (United States)

    Wu, Xin; Koslowski, Axel; Thiel, Walter


    In this work, we demonstrate that semiempirical quantum chemical calculations can be accelerated significantly by leveraging the graphics processing unit (GPU) as a coprocessor on a hybrid multicore CPU-GPU computing platform. Semiempirical calculations using the MNDO, AM1, PM3, OM1, OM2, and OM3 model Hamiltonians were systematically profiled for three types of test systems (fullerenes, water clusters, and solvated crambin) to identify the most time-consuming sections of the code. The corresponding routines were ported to the GPU and optimized employing both existing library functions and a GPU kernel that carries out a sequence of noniterative Jacobi transformations during pseudodiagonalization. The overall computation times for single-point energy calculations and geometry optimizations of large molecules were reduced by one order of magnitude for all methods, as compared to runs on a single CPU core.

  6. Quantum chemical simulation of hydrogen like states in silicon and diamond

    International Nuclear Information System (INIS)

    Gel'fand, R.B.; Gordeev, V.A.; Gorelkinskij, Yu.V.


    The quantum-chemical methods of the complete neglect of differential overlap (CNDO) and intermediate neglect of differential overlap (INDO) are used to calculate the electronic structure of atomic hydrogen (muonium) located at different interstital sites of the silicon and diamond crystal lattices. The electronic g- and hyperfine interaction tensors of the impure atom are determined.The results obtained are compared with the experimental data on the 'normal' (Mu') and 'anomalous' (Mu * ) muonium centers as well as on the hydrogen-bearing Si-AA9 EPR center which is a hydrogen-bearing analogue of (Mu * ). The most likely localization sites for hydrogen (muonium) atoms in silicon and diamond crystals are established. 22 refs

  7. Structural and quantum chemical analysis of exciton coupling in homo- and heteroaggregate stacks of merocyanines (United States)

    Bialas, David; Zitzler-Kunkel, André; Kirchner, Eva; Schmidt, David; Würthner, Frank


    Exciton coupling is of fundamental importance and determines functional properties of organic dyes in (opto-)electronic and photovoltaic devices. Here we show that strong exciton coupling is not limited to the situation of equal chromophores as often assumed. Quadruple dye stacks were obtained from two bis(merocyanine) dyes with same or different chromophores, respectively, which dimerize in less-polar solvents resulting in the respective homo- and heteroaggregates. The structures of the quadruple dye stacks were assigned by NMR techniques and unambiguously confirmed by single-crystal X-ray analysis. The heteroaggregate stack formed from the bis(merocyanine) bearing two different chromophores exhibits remarkably different ultraviolet/vis absorption bands compared with those of the homoaggregate of the bis(merocyanine) comprising two identical chromophores. Quantum chemical analysis based on an extension of Kasha's exciton theory appropriately describes the absorption properties of both types of stacks revealing strong exciton coupling also between different chromophores within the heteroaggregate. PMID:27680284

  8. QSAR analysis of salicylamide isosteres with the use of quantum chemical molecular descriptors. (United States)

    Dolezal, R; Van Damme, S; Bultinck, P; Waisser, K


    Quantitative relationships between the molecular structure and the biological activity of 49 isosteric salicylamide derivatives as potential antituberculotics with a new mechanism of action against three Mycobacterial strains were investigated. The molecular structures were represented by quantum chemical B3LYP/6-31G( *) based molecular descriptors. A resulting set of 220 molecular descriptors, including especially electronic properties, was statistically analyzed using multiple linear regression, resulting in acceptable and robust QSAR models. The best QSAR model was found for Mycobacterium tuberculosis (r(2)=0.92; q(2)=0.89), and somewhat less good QSAR models were found for Mycobacterium avium (r(2)=0.84; q(2)=0.78) and Mycobacterium kansasii (r(2)=0.80; q(2)=0.56). All QSAR models were cross-validated using the leave-10-out procedure.

  9. Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling (United States)

    Slaby, Scott M.; Ewing, David W.; Zehe, Michael J.


    The AM1 semiempirical quantum chemical method was used to model the interaction of perfluoroethers with aluminum surfaces. Perfluorodimethoxymethane and perfluorodimethyl ether were studied interacting with aluminum surfaces, which were modeled by a five-atom cluster and a nine-atom cluster. Interactions were studied for edge (high index) sites and top (low index) sites of the clusters. Both dissociative binding and nondissociative binding were found, with dissociative binding being stronger. The two different ethers bound and dissociated on the clusters in different ways: perfluorodimethoxymethane through its oxygen atoms, but perfluorodimethyl ether through its fluorine atoms. The acetal linkage of perfluorodimeth-oxymethane was the key structural feature of this molecule in its binding and dissociation on the aluminum surface models. The high-index sites of the clusters caused the dissociation of both ethers. These results are consistent with the experimental observation that perfluorinated ethers decompose in contact with sputtered aluminum surfaces.

  10. Random Forest Approach to QSPR Study of Fluorescence Properties Combining Quantum Chemical Descriptors and Solvent Conditions. (United States)

    Chen, Chia-Hsiu; Tanaka, Kenichi; Funatsu, Kimito


    The Quantitative Structure - Property Relationship (QSPR) approach was performed to study the fluorescence absorption wavelengths and emission wavelengths of 413 fluorescent dyes in different solvent conditions. The dyes included the chromophore derivatives of cyanine, xanthene, coumarin, pyrene, naphthalene, anthracene and etc., with the wavelength ranging from 250 nm to 800 nm. An ensemble method, random forest (RF), was employed to construct nonlinear prediction models compared with the results of linear partial least squares and nonlinear support vector machine regression models. Quantum chemical descriptors derived from density functional theory method and solvent information were also used by constructing models. The best prediction results were obtained from RF model, with the squared correlation coefficients [Formula: see text] of 0.940 and 0.905 for λ abs and λ em , respectively. The descriptors used in the models were discussed in detail in this report by comparing the feature importance of RF.

  11. A theoretical quantum chemical study of alanine formation in interstellar medium (United States)

    Shivani; Pandey, Parmanad; Misra, Alka; Tandon, Poonam


    The interstellar medium, the vast space between the stars, is a rich reservoir of molecular material ranging from simple diatomic molecules to more complex, astrobiologically important molecules such as amino acids, nucleobases, and other organic species. Radical-radical and radical-neutral interaction schemes are very important for the formation of comparatively complex molecules in low temperature chemistry. An attempt has been made to explore the possibility of formation of complex organic molecules in interstellar medium, through detected interstellar molecules like CH3CN and HCOOH. The gas phase reactions are theoretically studied using quantum chemical techniques. We used the density functional theory (DFT) at the B3LYP/6-311G( d, p) level. The reaction energies, potential barrier and optimized structures of all the geometries, involved in the reaction path, has been discussed. We report the potential energy surfaces for the reactions considered in this work.

  12. Quantum chemical approach for condensed-phase thermochemistry: proposal of a harmonic solvation model. (United States)

    Nakai, Hiromi; Ishikawa, Atsushi


    We propose a novel quantum chemical method, called the harmonic solvation model (HSM), for calculating thermochemical parameters in the condensed phase, particularly in the liquid phase. The HSM represents translational and rotational motions of a solute as vibrations interacting with a cavity wall of solvent molecules. As examples, the HSM and the ideal-gas model (IGM) were used for the standard formation reaction of liquid water, combustion reactions of liquid formic acid, methanol, and ethanol, vapor-liquid equilibration of water and ethanol, and dissolution of gaseous CO2 in water. The numerical results confirmed the reliability and applicability of the HSM. In particular, the temperature dependence of the Gibbs energy of liquid molecules was accurately reproduced by the HSM; for example, the boiling point of water was reasonably determined using the HSM, whereas the conventional IGM treatment failed to obtain a crossing of the two Gibbs energy curves for gaseous and liquid water.

  13. Quantum mechanics of chemical reactions: Recent developments in reactive scattering and in reaction path Hamiltonians

    International Nuclear Information System (INIS)

    Miller, W.H.


    Two recent developments in the theory of chemical reaction dynamics are reviewed. First, it has recently been discovered that the S- matrix version of the Kohn variational principle is free of the ''Kohn anomalies'' that have plagued other versions and prevented its general use. This has considerably simplified quantum mechanical reactive scattering calculations, which provide the rigorous characterizations of bimolecular reactions. Second, a new kind of reaction path Hamiltonian has been developed, one based on the ''least motion'' path that interpolates linearly between the reactant and product geometry of the molecule (rather than the previously used minimum energy, or ''intrinsic'' reaction path). The form of Hamiltonian which results is much simpler than the original reaction path Hamiltonian, but more important is the fact that it provides a more physically correct description of hydrogen atom transfer reactions. 44 refs., 4 figs

  14. Molecular simulation, quantum chemical calculations and electrochemical studies for inhibition of mild steel by triazoles

    International Nuclear Information System (INIS)

    Khaled, K.F.


    The inhibition performance of three triazole derivatives on mild steel in 1 M HCl were tested by weight loss, potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The adsorption behavior of these molecules at the Fe surface was studied by the molecular dynamics simulation method and the quantum chemical calculations. Results showed that these compounds inhibit the corrosion of mild steel in 1 M HCl solution significantly. Molecular simulation studies were applied to optimize the adsorption structures of triazole derivatives. The iron/inhibitor/solvent interfaces were simulated and the charges on the inhibitor molecules as well as their structural parameters were calculated in presence of solvent effects. Aminotriazole was the best inhibitor among the three triazole derivatives (triazole, aminotriazole and benzotriazole). The adsorption of the inhibitors on the mild steel surface in the acid solution was found to obey Langmuir's adsorption isotherm

  15. Prediction of monomer reactivity in radical copolymerizations from transition state quantum chemical descriptors

    Directory of Open Access Journals (Sweden)

    Zhengde Tan


    Full Text Available In comparison with the Q-e scheme, the Revised Patterns Scheme: the U, V Version (the U-V scheme has greatly improved both its accessibility and its accuracy in interpreting and predicting the reactivity of a monomer in free-radical copolymerizations. Quantitative structure-activity relationship (QSAR models were developed to predict the reactivity parameters u and v of the U-V scheme, by applying genetic algorithm (GA and support vector machine (SVM techniques. Quantum chemical descriptors used for QSAR models were calculated from transition state species with structures C¹H3 - C²HR³• or •C¹H2 - C²H2R³ (formed from vinyl monomers C¹H²=C²HR³ + H•, using density functional theory (DFT, at the UB3LYP level of theory with 6-31G(d basis set. The optimum support vector regression (SVR model of the reactivity parameter u based on Gaussian radial basis function (RBF kernel (C = 10, ε = 10- 5 and γ = 1.0 produced root-mean-square (rms errors for the training, validation and prediction sets being 0.220, 0.326 and 0.345, respectively. The optimal SVR model for v with the RBF kernel (C = 20, ε = 10- 4 and γ = 1.2 produced rms errors for the training set of 0.123, the validation set of 0.206 and the prediction set of 0.238. The feasibility of applying the transition state quantum chemical descriptors to develop SVM models for reactivity parameters u and v in the U-V scheme has been demonstrated.

  16. Proton exchange between oxymethyl radical and acids and bases: semiempirical quantum-chemical study

    Directory of Open Access Journals (Sweden)

    Irina Pustolaikina


    Full Text Available The reactions with proton participation are widely represented in the analytical, technological and biological chemistry. Quantum-chemical study of the exchange processes in hydrogen bonding complexes will allow us to achieve progress in the understanding of the elementary act mechanism of proton transfer in hydrogen bonding chain as well as the essence of the acid-base interactions. Oxymethyl radical •CH2ОН is small in size and comfortable as a model particle that well transmits protolytic properties of paramagnetic acids having more complex structure. Quantum-chemical modeling of proton exchange reaction oxymethyl radical ∙CH2OH and its diamagnetic analog CH3OH with amines, carboxylic acids and water was carried out using UAM1 method with the help of Gaussian-2009 program. QST2 method was used for the search of transition state, IRC procedure was applied for the calculation of descents along the reaction coordinate. The difference in the structure of transition states of ∙CH2OH/ CH3OH with bases and acids has been shown. It has been confirmed that in the case of bases, consecutive proton exchange mechanism was fixed, and in the case of complexes with carboxylic acids parallel proton exchange mechanism was fixed. The similarity in the reaction behavior of paramagnetic and diamagnetic systems in the proton exchange has been found. It was suggested that the mechanism of proton exchange reaction is determined by the structure of the hydrogen bonding cyclic complex, which is, in turn, depends from the nature of the acid-base interactions partners.

  17. Quantum chemical studies of the physics around the metal-insulator transition in (EDO-TTF)2PF6

    NARCIS (Netherlands)

    Linker, Gerrit-Jan


    In this thesis, the physics of molecular charge transfer crystals is studied by using quantum chemical methods. We looked in detail at the metal insulator phase transition in the (EDO TTF)2PF6 molecular crystal and also into related geometrical reorganisations and charge ordering phenomena. Unlike

  18. Chemical processing of three-dimensional graphene networks on transparent conducting electrodes for depleted-heterojunction quantum dot solar cells. (United States)

    Tavakoli, Mohammad Mahdi; Simchi, Abdolreza; Fan, Zhiyong; Aashuri, Hossein


    We present a novel chemical procedure to prepare three-dimensional graphene networks (3DGNs) as a transparent conductive film to enhance the photovoltaic performance of PbS quantum-dot (QD) solar cells. It is shown that 3DGN electrodes enhance electron extraction, yielding a 30% improvement in performance compared with the conventional device.

  19. Chemical Potential for the Interacting Classical Gas and the Ideal Quantum Gas Obeying a Generalized Exclusion Principle (United States)

    Sevilla, F. J.; Olivares-Quiroz, L.


    In this work, we address the concept of the chemical potential [mu] in classical and quantum gases towards the calculation of the equation of state [mu] = [mu](n, T) where n is the particle density and "T" the absolute temperature using the methods of equilibrium statistical mechanics. Two cases seldom discussed in elementary textbooks are…

  20. Evaluation of the catalytic mechanism of AICAR transformylase by pH-dependent kinetics, mutagenesis, and quantum chemical calculations. (United States)

    Shim, J H; Wall, M; Benkovic, S J; Díaz, N; Suárez, D; Merz, K M


    The catalytic mechanism of 5-aminoimidazole-4-carboxamide ribonucleotide transformylase (AICAR Tfase) is evaluated with pH dependent kinetics, site-directed mutagenesis, and quantum chemical calculations. The chemistry step, represented by the burst rates, was not pH-dependent, which is consistent with our proposed mechanism that the 4-carboxamide of AICAR assists proton shuttling. Quantum chemical calculations on a model system of 5-amino-4-carboxamide imidazole (AICA) and formamide using the B3LYP/6-31G level of theory confirmed that the 4-carboxamide participated in the proton-shuttling mechanism. The result also indicated that the amide-assisted mechanism is concerted such that the proton transfers from the 5-amino group to the formamide are simultaneous with nucleophilic attack by the 5-amino group. Because the process does not lead to a kinetically stable intermediate, the intramolecular proton transfer from the 5-amino group through the 4-carboxamide to the formamide proceeds in the same transition state. Interestingly, the calculations predicted that protonation of the N3 of the imidazole of AICA would reduce the energy barrier significantly. However, the pK(a) of the imidazole of AICAR was determined to be 3.23 +/- 0.01 by NMR titration, and AICAR is likely to bind to the enzyme with its imidazole in the free base form. An alternative pathway was suggested by modeling Lys266 to have a hydrogen-bonding interaction with the N3 of the imidazole of AICAR. Lys266 has been implicated in catalysis based on mutagenesis studies and the recent X-ray structure of AICAR Tfase. The quantum chemical calculations on a model system that contains AICA complexed with CH3NH3+ as a mimic of the Lys residue confirmed that such an interaction lowered the activation energy of the reaction and likewise implicated the 4-carboxamide. To experimentally verify this hypothesis, we prepared the K266R mutant and found that its kcat is reduced by 150-fold from that of the wild type

  1. Logarithmic terms in entanglement entropies of 2D quantum critical points and Shannon entropies of spin chains. (United States)

    Zaletel, Michael P; Bardarson, Jens H; Moore, Joel E


    Universal logarithmic terms in the entanglement entropy appear at quantum critical points (QCPs) in one dimension (1D) and have been predicted in 2D at QCPs described by 2D conformal field theories. The entanglement entropy in a strip geometry at such QCPs can be obtained via the "Shannon entropy" of a 1D spin chain with open boundary conditions. The Shannon entropy of the XXZ chain is found to have a logarithmic term that implies, for the QCP of the square-lattice quantum dimer model, a logarithm with universal coefficient ±0.25. However, the logarithm in the Shannon entropy of the transverse-field Ising model, which corresponds to entanglement in the 2D Ising conformal QCP, is found to have a singular dependence on the replica or Rényi index resulting from flows to different boundary conditions at the entanglement cut.

  2. Ferromagnetic quantum criticality in the uranium-based ternary compounds URhSi, URhAl, and UCoAl

    International Nuclear Information System (INIS)

    Combier, Tristan


    In this thesis we explore the ferromagnetic quantum criticality in three uranium-based ternary compounds, by means of thermodynamical and transport measurements on single crystal samples, at low temperature and high pressure. URhSi and URhAl are itinerant ferromagnets, while UCoAl is a paramagnet being close to a ferromagnetic instability. All of them have Ising-type magnetic ordering. In the orthorhombic compound URhSi, we show that the Curie temperature decreases upon applying a magnetic field perpendicular to the easy magnetization axis, and a quantum phase transition is expected around 40 T. In the hexagonal system URhAl, we establish the pressure-temperature phase diagram for the first time, indicating a quantum phase transition around 5 GPa. In the isostructural compound UCoAl, we investigate the metamagnetic transition with measurements of magnetization, Hall effect, resistivity and X-ray magnetic circular dichroism. Some intriguing magnetic relaxation phenomena are observed, with step-like features. Hall effect and resistivity have been measured at dilution temperatures, under hydrostatic pressure up to 2.2 GPa and magnetic field up to 16 T. The metamagnetic transition terminates under pressure and magnetic field at a quantum critical endpoint. In this region, a strong effective mass enhancement occurs, and an intriguing difference between up and down field sweeps appears in transverse resistivity. This may be the signature of a new phase, supposedly linked to the relaxation phenomena observed in magnetic measurements, arising from frustration on the quasi-Kagome lattice of uranium atoms in this crystal structure. (author) [fr

  3. Quantum chemical study on the stability of honeybee queen pheromone against atmospheric factors. (United States)

    Shi, Rongwei; Liu, Fanglin


    The managed honeybee, Apis mellifera, has been experienced a puzzling event, termed as colony collapse disorder (CCD), in which worker bees abruptly disappear from their hives. Potential factors include parasites, pesticides, malnutrition, and environmental stresses. However, so far, no definitive relationship has been established between specific causal factors and CCD events. Here we theoretically test whether atmospheric environment could disturb the chemical communication between the queen and their workers in a colony. A quantum chemistry method has been used to investigate for the stability of the component of A. mellifera queen mandibular pheromone (QMP), (E)-9-keto-2-decenoic acid (9-ODA), against atmospheric water and free radicals. The results show that 9-ODA is less likely to react with water due to the high barrier heights (~36.5 kcal · mol(-1)) and very low reaction rates. However, it can easily react with triplet oxygen and hydroxyl radicals because of low or negative energy barriers. Thus, the atmospheric free radicals may disturb the chemical communication between the queen and their daughters in a colony. Our pilot study provides new insight for the cause of CCD, which has been reported throughout the world.

  4. Spectroscopic studies and quantum chemical investigations of (3,4-dimethoxybenzylidene) propanedinitrile. (United States)

    Gupta, Ujval; Kumar, Vinay; Singh, Vivek K; Kant, Rajni; Khajuria, Yugal


    The Fourier Transform Infrared (FTIR), Ultra-Violet Visible (UV-Vis) spectroscopy and Thermogravimetric (TG) analysis of (3,4-dimethoxybenzylidene) propanedinitrile have been carried out and investigated using quantum chemical calculations. The molecular geometry, harmonic vibrational frequencies, Mulliken charges, natural atomic charges and thermodynamic properties in the ground state have been investigated by using Hartree Fock Theory (HF) and Density Functional Theory (DFT) using B3LYP functional with 6-311G(d,p) basis set. Both HF and DFT methods yield good agreement with the experimental data. Vibrational modes are assigned with the help of Vibrational Energy Distribution Analysis (VEDA) program. UV-Visible spectrum was recorded in the spectral range of 190-800nm and the results are compared with the calculated values using TD-DFT approach. Stability of the molecule arising from hyperconjugative interactions, charge delocalization have been analyzed using natural bond orbital (NBO) analysis. The results obtained from the studies of Highest Occupied Molecular Orbital (HOMO) and Lowest Unoccupied Molecular Orbital (LUMO) are used to calculate molecular parameters like ionization potential, electron affinity, global hardness, electron chemical potential and global electrophilicity. Copyright © 2014 Elsevier B.V. All rights reserved.

  5. A general intermolecular force field based on tight-binding quantum chemical calculations (United States)

    Grimme, Stefan; Bannwarth, Christoph; Caldeweyher, Eike; Pisarek, Jana; Hansen, Andreas


    A black-box type procedure is presented for the generation of a molecule-specific, intermolecular potential energy function. The method uses quantum chemical (QC) information from our recently published extended tight-binding semi-empirical scheme (GFN-xTB) and can treat non-covalently bound complexes and aggregates with almost arbitrary chemical structure. The necessary QC information consists of the equilibrium structure, Mulliken atomic charges, charge centers of localized molecular orbitals, and also of frontier orbitals and orbital energies. The molecular pair potential includes model density dependent Pauli repulsion, penetration, as well as point charge electrostatics, the newly developed D4 dispersion energy model, Drude oscillators for polarization, and a charge-transfer term. Only one element-specific and about 20 global empirical parameters are needed to cover systems with nuclear charges up to radon (Z = 86). The method is tested for standard small molecule interaction energy benchmark sets where it provides accurate intermolecular energies and equilibrium distances. Examples for structures with a few hundred atoms including charged systems demonstrate the versatility of the approach. The method is implemented in a stand-alone computer code which enables rigid-body, global minimum energy searches for molecular aggregation or alignment.

  6. Uranium and thorium hydride complexes as multielectron reductants: a combined neutron diffraction and quantum chemical study. (United States)

    Grant, Daniel J; Stewart, Timothy J; Bau, Robert; Miller, Kevin A; Mason, Sax A; Gutmann, Matthias; McIntyre, Garry J; Gagliardi, Laura; Evans, William J


    The unusual uranium reaction system in which uranium(4+) and uranium(3+) hydrides interconvert by formal bimetallic reductive elimination and oxidative addition reactions, [(C(5)Me(5))(2)UH(2)](2) (1) ⇌ [(C(5)Me(5))(2)UH](2) (2) + H(2), was studied by employing multiconfigurational quantum chemical and density functional theory methods. 1 can act as a formal four-electron reductant, releasing H(2) gas as the byproduct of four H(2)/H(-) redox couples. The calculated structures for both reactants and products are in good agreement with the X-ray diffraction data on 2 and 1 and the neutron diffraction data on 1 obtained under H(2) pressure as part of this study. The interconversion of the uranium(4+) and uranium(3+) hydride species was calculated to be near thermoneutral (~-2 kcal/mol). Comparison with the unknown thorium analogue, [(C(5)Me(5))(2)ThH](2), shows that the thorium(4+) to thorium(3+) hydride interconversion reaction is endothermic by 26 kcal/mol. © 2012 American Chemical Society

  7. Chemical effects of alkali atoms on critical temperature in superconducting alkali-doped fullerides (United States)

    Hetfleisch, F.; Gunnarsson, O.; Srama, R.; Han, J. E.; Stepper, M.; Roeser, H.-P.; Bohr, A.; Lopez, J. S.; Mashmool, M.; Roth, S.


    Alkali metal doped fullerides (A3C60) are superconductors with critical temperatures, Tc, extending up to 38 K. Tc is known to depend strongly on the lattice parameter a, which can be adjusted by physical or chemical pressure. In the latter case an alkali atom is replaced by a different sized one, which changes a. We have collected an extensive data base of experimental data for Tc from very early up to recent measurements. We disentangle alkali atom chemical effects on Tc, beyond the well-known consequences of changing a. It is found that Tc, for a fixed a, is typically increased as smaller alkali atoms are replaced by larger ones, except for very large a. Possible reasons for these results are discussed. Although smaller in size than the lattice parameter contribution, the chemical effect is not negligible and should be considered in future physical model developments.

  8. A quantum-chemical perspective into low optical-gap polymers for highly-efficient organic solar cells

    KAUST Repository

    Risko, Chad


    The recent and rapid enhancement in power conversion efficiencies of organic-based, bulk heterojunction solar cells has been a consequence of both improved materials design and better understanding of the underlying physical processes involved in photocurrent generation. In this Perspective, we first present an overview of the application of quantum-chemical techniques to study the intrinsic material properties and molecular- and nano-scale processes involved in device operation. In the second part, these quantum-chemical tools are applied to an oligomer-based study on a collection of donor-acceptor copolymers that have been used in the highest-efficiency solar cell devices reported to date. The quantum-chemical results are found to be in good agreement with the empirical data related to the electronic and optical properties. In particular, they provide insight into the natures of the electronic excitations responsible for the near-infrared/visible absorption profiles, as well as into the energetics of the low-lying singlet and triplet states. These results lead to a better understanding of the inherent differences among the materials, and highlight the usefulness of quantum chemistry as an instrument for material design. Importantly, the results also point to the need to continue the development of integrated, multi scale modeling approaches to provide a thorough understanding of the materials properties. © The Royal Society of Chemistry 2011.

  9. Critical investigation of Jauch's approach to the quantum theory of measurement

    International Nuclear Information System (INIS)

    Herbut, Fedor


    To make Jauch's approach more realistic, his assumptions are modified in two ways: (1) On the quantum system plus the measuring apparatus (S + MA) after the measuring interaction has ceased, one can actually measure only operators of the form given. (2) Measurement is defined in the most general way (including, besides first-kind, also second-kind and third-kind or indirect measurements). It is shown that Jauch's basic result that the microstates (statistical operators) of S + MA before and after the collapse correspond to the same macrostate (belong to the same equivalence class of microstates) remains valid under the above modifications, and that the significance of this result goes beyond measurement theory. On the other hand, it is argued that taking the orthodox (i.e. uncompromisingly quantum) view of quantum mechanics, it is not the collapse, but the Jauch-type macrostates that are spurious in a Jauch-type theory. (author)

  10. Novel quantum criticality in CeRu2Si2 near absolute zero observed by thermal expansion and magnetostriction. (United States)

    Yoshida, J; Abe, S; Takahashi, D; Segawa, Y; Komai, Y; Tsujii, H; Matsumoto, K; Suzuki, H; Onuki, Y


    We report linear thermal expansion and magnetostriction measurements for CeRu2Si2 in magnetic fields up to 52.6 mT and at temperatures down to 1 mK. At high temperatures, this compound showed Landau-Fermi-liquid behavior: The linear thermal expansion coefficient and the magnetostriction coefficient were proportional to the temperature and magnetic field, respectively. In contrast, a pronounced non-Fermi-liquid effect was found below 50 mK. The negative contribution of thermal expansion and magnetostriction suggests the existence of an additional quantum critical point.

  11. Application of hazard analysis critical control points (HACCP) to organic chemical contaminants in food. (United States)

    Ropkins, K; Beck, A J


    Hazard Analysis Critical Control Points (HACCP) is a systematic approach to the identification, assessment, and control of hazards that was developed as an effective alternative to conventional end-point analysis to control food safety. It has been described as the most effective means of controlling foodborne diseases, and its application to the control of microbiological hazards has been accepted internationally. By contrast, relatively little has been reported relating to the potential use of HACCP, or HACCP-like procedures, to control chemical contaminants of food. This article presents an overview of the implementation of HACCP and discusses its application to the control of organic chemical contaminants in the food chain. Although this is likely to result in many of the advantages previously identified for microbiological HACCP, that is, more effective, efficient, and economical hazard management, a number of areas are identified that require further research and development. These include: (1) a need to refine the methods of chemical contaminant identification and risk assessment employed, (2) develop more cost-effective monitoring and control methods for routine chemical contaminant surveillance of food, and (3) improve the effectiveness of process optimization for the control of chemical contaminants in food.

  12. Magneto-acoustic study near the quantum critical point of the frustrated quantum antiferromagnet Cs{sub 2}CuCl{sub 4}

    Energy Technology Data Exchange (ETDEWEB)

    Cong, P. T., E-mail: [Dresden High Magnetic Field Laboratory, Helmholtz-Zentrum Dresden-Rossendorf, D-01314 Dresden (Germany); Physics Institute, Goethe University Frankfurt, D-60438 Frankfurt am Main (Germany); Postulka, L.; Wolf, B.; Ritter, F.; Assmus, W.; Krellner, C.; Lang, M., E-mail: [Physics Institute, Goethe University Frankfurt, D-60438 Frankfurt am Main (Germany); Well, N. van [Physics Institute, Goethe University Frankfurt, D-60438 Frankfurt am Main (Germany); Laboratory for Neutron Scattering and Imaging, Paul Scherrer Institute, CH-5232 Villigen (Switzerland)


    Magneto-acoustic investigations of the frustrated triangular-lattice antiferromagnet Cs{sub 2}CuCl{sub 4} were performed for the longitudinal modes c{sub 11} and c{sub 33} in magnetic fields along the a-axis. The temperature dependence of the sound velocity at zero field shows a mild softening at low temperature and displays a small kink-like anomaly at T{sub N}. Isothermal measurements at T < T{sub N} of the sound attenuation α reveal two closely spaced features of different characters on approaching the material's quantum-critical point (QCP) at B{sub s} ≈ 8.5 T for B || a. The peak at slightly lower fields remains sharp down to the lowest temperature and can be attributed to the ordering temperature T{sub N}(B). The second anomaly, which is rounded and which becomes reduced in size upon cooling, is assigned to the material's spin-liquid properties preceding the long-range antiferromagnetic ordering with decreasing temperature. These two features merge upon cooling suggesting a coincidence at the QCP. The elastic constant at lowest temperatures of our experiment at 32 mK can be well described by a Landau free energy model with a very small magnetoelastic coupling constant G/k{sub B} ≈ 2.8 K. The applicability of this classical model indicates the existence of a small gap in the magnetic excitation spectrum which drives the system away from quantum criticality.

  13. Theoretical study of the electronic structure of f-element complexes by quantum chemical methods

    International Nuclear Information System (INIS)

    Vetere, V.


    This thesis is related to comparative studies of the chemical properties of molecular complexes containing lanthanide or actinide trivalent cations, in the context of the nuclear waste disposal. More precisely, our aim was a quantum chemical analysis of the metal-ligand bonding in such species. Various theoretical approaches were compared, for the inclusion of correlation (density functional theory, multiconfigurational methods) and of relativistic effects (relativistic scalar and 2-component Hamiltonians, relativistic pseudopotentials). The performance of these methods were checked by comparing computed structural properties to published experimental data, on small model systems: lanthanide and actinide tri-halides and on X 3 M-L species (X=F, Cl; M=La, Nd, U; L = NH 3 , acetonitrile, CO). We have thus shown the good performance of density functionals combined with a quasi-relativistic method, as well as of gradient-corrected functionals associated with relativistic pseudopotentials. In contrast, functionals including some part of exact exchange are less reliable to reproduce experimental trends, and we have given a possible explanation for this result . Then, a detailed analysis of the bonding has allowed us to interpret the discrepancies observed in the structural properties of uranium and lanthanides complexes, based on a covalent contribution to the bonding, in the case of uranium(III), which does not exist in the lanthanide(III) homologues. Finally, we have examined more sizeable systems, closer to experimental species, to analyse the influence of the coordination number, of the counter-ions and of the oxidation state of uranium, on the metal-ligand bonding. (author)

  14. Structural and optical characteristics of InN/GaN multiple quantum wells grown by metalorganic chemical vapor deposition

    International Nuclear Information System (INIS)

    Kim, Je Won; Lee, Kyu Han; Hong, Sangsu


    The structural and electrical properties of InN/GaN multiple quantum wells, which were grown by metalorganic chemical vapor deposition, were characterized by transmission electron microscopy (TEM) and electroluminescence measurements. From the TEM micrographs, it was shown that the well layer was grown like a quantum dot. The well layer is expected to be the nano-size structures in the InN multiple quantum well layers. The multi-photon confocal laser scanning microscopy was used to investigate the optical properties of the light emitting diode (LED) structures with InN active layers. It was found that the two-photon excitation was possible in InN system. The pit density was measured by using the far-field optical technique. In the varied current conditions, the blue LED with the InN multiple quantum well structures did not have the wavelength shift. With this result, we can expect that the white LEDs with the InN multiple quantum well structures do not show the color temperature changes with the variations of applied currents

  15. Growth of InAs Quantum Dots on Germanium Substrate Using Metal Organic Chemical Vapor Deposition Technique

    Directory of Open Access Journals (Sweden)

    Tyagi Renu


    Full Text Available Abstract Self-assembled InAs quantum dots (QDs were grown on germanium substrates by metal organic chemical vapor deposition technique. Effects of growth temperature and InAs coverage on the size, density, and height of quantum dots were investigated. Growth temperature was varied from 400 to 450 °C and InAs coverage was varied between 1.40 and 2.35 monolayers (MLs. The surface morphology and structural characteristics of the quantum dots analyzed by atomic force microscope revealed that the density of the InAs quantum dots first increased and then decreased with the amount of InAs coverage; whereas density decreased with increase in growth temperature. It was observed that the size and height of InAs quantum dots increased with increase in both temperature and InAs coverage. The density of QDs was effectively controlled by growth temperature and InAs coverage on GaAs buffer layer.

  16. The furan microsolvation blind challenge for quantum chemical methods: First steps (United States)

    Gottschalk, Hannes C.; Poblotzki, Anja; Suhm, Martin A.; Al-Mogren, Muneerah M.; Antony, Jens; Auer, Alexander A.; Baptista, Leonardo; Benoit, David M.; Bistoni, Giovanni; Bohle, Fabian; Dahmani, Rahma; Firaha, Dzmitry; Grimme, Stefan; Hansen, Andreas; Harding, Michael E.; Hochlaf, Majdi; Holzer, Christof; Jansen, Georg; Klopper, Wim; Kopp, Wassja A.; Kröger, Leif C.; Leonhard, Kai; Mouhib, Halima; Neese, Frank; Pereira, Max N.; Ulusoy, Inga S.; Wuttke, Axel; Mata, Ricardo A.


    Herein we present the results of a blind challenge to quantum chemical methods in the calculation of dimerization preferences in the low temperature gas phase. The target of study was the first step of the microsolvation of furan, 2-methylfuran and 2,5-dimethylfuran with methanol. The dimers were investigated through IR spectroscopy of a supersonic jet expansion. From the measured bands, it was possible to identify a persistent hydrogen bonding OH-O motif in the predominant species. From the presence of another band, which can be attributed to an OH-π interaction, we were able to assert that the energy gap between the two types of dimers should be less than or close to 1 kJ/mol across the series. These values served as a first evaluation ruler for the 12 entries featured in the challenge. A tentative stricter evaluation of the challenge results is also carried out, combining theoretical and experimental results in order to define a smaller error bar. The process was carried out in a double-blind fashion, with both theory and experimental groups unaware of the results on the other side, with the exception of the 2,5-dimethylfuran system which was featured in an earlier publication.

  17. ExcelAutomat: a tool for systematic processing of files as applied to quantum chemical calculations (United States)

    Laloo, Jalal Z. A.; Laloo, Nassirah; Rhyman, Lydia; Ramasami, Ponnadurai


    The processing of the input and output files of quantum chemical calculations often necessitates a spreadsheet as a key component of the workflow. Spreadsheet packages with a built-in programming language editor can automate the steps involved and thus provide a direct link between processing files and the spreadsheet. This helps to reduce user-interventions as well as the need to switch between different programs to carry out each step. The ExcelAutomat tool is the implementation of this method in Microsoft Excel (MS Excel) using the default Visual Basic for Application (VBA) programming language. The code in ExcelAutomat was adapted to work with the platform-independent open-source LibreOffice Calc, which also supports VBA. ExcelAutomat provides an interface through the spreadsheet to automate repetitive tasks such as merging input files, splitting, parsing and compiling data from output files, and generation of unique filenames. Selected extracted parameters can be retrieved as variables which can be included in custom codes for a tailored approach. ExcelAutomat works with Gaussian files and is adapted for use with other computational packages including the non-commercial GAMESS. ExcelAutomat is available as a downloadable MS Excel workbook or as a LibreOffice workbook.

  18. Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculations, and NMR analysis. (United States)

    Ruiz, Elia; Ferro, Victor R; Palomar, Jose; Ortega, Juan; Rodriguez, Juan Jose


    The interactions between ionic liquids (ILs) and acetone have been studied to obtain a further understanding of the behavior of their mixtures, which generally give place to an exothermic process, mutual miscibility, and negative deviation of Raoult's law. COSMO-RS was used as a suitable computational method to systematically analyze the excess enthalpy of IL-acetone systems (>300), in terms of the intermolecular interactions contributing to the mixture behavior. Spectroscopic and COSMO-RS results indicated that acetone, as a polar compound with strong hydrogen bond acceptor character, in most cases, establishes favorable hydrogen bonding with ILs. This interaction is strengthened by the presence of an acidic cation and an anion with dispersed charge and non-HB acceptor character in the IL. COSMO-RS predictions indicated that gas-liquid and vapor-liquid equilibrium data for IL-acetone systems can be finely tuned by the IL selection, that is, acting on the intermolecular interactions between the molecular and ionic species in the liquid phase. NMR measurements for IL-acetone mixtures at different concentrations were also carried out. Quantum-chemical calculations by using molecular clusters of acetone and IL species were finally performed. These results provided additional evidence of the main role played by hydrogen bonding in the behavior of systems containing ILs and HB acceptor compounds, such as acetone.

  19. An FT-Raman, FT-IR, and Quantum Chemical Investigation of Stanozolol and Oxandrolone

    Directory of Open Access Journals (Sweden)

    Tibebe Lemma


    Full Text Available We have studied the Fourier Transform Infrared (FT-IR and the Fourier transform Raman (FT-Raman spectra of stanozolol and oxandrolone, and we have performed quantum chemical calculations based on the density functional theory (DFT with a B3LYP/6-31G (d, p level of theory. The FT-IR and FT-Raman spectra were collected in a solid phase. The consistency between the calculated and experimental FT-IR and FT-Raman data indicates that the B3LYP/6-31G (d, p can generate reliable geometry and related properties of the title compounds. Selected experimental bands were assigned and characterized on the basis of the scaled theoretical wavenumbers by their total energy distribution. The good agreement between the experimental and theoretical spectra allowed positive assignment of the observed vibrational absorption bands. Finally, the calculation results were applied to simulate the Raman and IR spectra of the title compounds, which show agreement with the observed spectra.

  20. Quantum Monte Carlo for large chemical systems: implementing efficient strategies for peta scale platforms and beyond

    International Nuclear Information System (INIS)

    Scemama, Anthony; Caffarel, Michel; Oseret, Emmanuel; Jalby, William


    Various strategies to implement efficiently quantum Monte Carlo (QMC) simulations for large chemical systems are presented. These include: (i) the introduction of an efficient algorithm to calculate the computationally expensive Slater matrices. This novel scheme is based on the use of the highly localized character of atomic Gaussian basis functions (not the molecular orbitals as usually done), (ii) the possibility of keeping the memory footprint minimal, (iii) the important enhancement of single-core performance when efficient optimization tools are used, and (iv) the definition of a universal, dynamic, fault-tolerant, and load-balanced framework adapted to all kinds of computational platforms (massively parallel machines, clusters, or distributed grids). These strategies have been implemented in the QMC-Chem code developed at Toulouse and illustrated with numerical applications on small peptides of increasing sizes (158, 434, 1056, and 1731 electrons). Using 10-80 k computing cores of the Curie machine (GENCI-TGCC-CEA, France), QMC-Chem has been shown to be capable of running at the peta scale level, thus demonstrating that for this machine a large part of the peak performance can be achieved. Implementation of large-scale QMC simulations for future exa scale platforms with a comparable level of efficiency is expected to be feasible. (authors)

  1. Energetics and stability of azulene: From experimental thermochemistry to high-level quantum chemical calculations

    International Nuclear Information System (INIS)

    Sousa, Clara C.S.; Matos, M. Agostinha R.; Morais, Victor M.F.


    Highlights: • Experimental standard molar enthalpy of formation, sublimation azulene. • Mini-bomb combustion calorimetry, sublimation Calvet microcalorimetry. • High level composite ab initio calculations. • Computational estimate of the enthalpy of formation of azulene. • Discussion of stability and aromaticity of azulene. - Abstract: The standard (p 0 = 0.1 MPa) molar enthalpy of formation for crystalline azulene was derived from the standard molar enthalpy of combustion, in oxygen, at T = 298.15 K, measured in a mini-bomb combustion calorimeter (aneroid isoperibol calorimeter) and the standard molar enthalpy of sublimation, at T = 298.15 K, measured by Calvet microcalorimetry. From these experiments, the standard molar enthalpy of formation of azulene in the gaseous phase at T = 298.15 K was calculated. In addition, very accurate quantum chemical calculations at the G3 and G4 composite levels of calculation were conducted in order to corroborate our experimental findings and further clarify and establish the definitive standard enthalpy of formation of this interesting non-benzenoid hydrocarbon

  2. Humic acid metal cation interaction studied by spectromicroscopy techniques in combination with quantum chemical calculations. (United States)

    Plaschke, M; Rothe, J; Armbruster, M K; Denecke, M A; Naber, A; Geckeis, H


    Humic acids (HA) have a high binding capacity towards traces of toxic metal cations, thus affecting their transport in aquatic systems. Eu(III)-HA aggregates are studied by synchrotron-based scanning transmission X-ray microscopy (STXM) at the carbon K-edge and laser scanning luminescence microscopy (LSLM) at the (5)D(0) --> (7)F(1,2) fluorescence emission lines. Both methods provide the necessary spatial resolution in the sub-micrometre range to resolve characteristic aggregate morphologies: optically dense zones embedded in a matrix of less dense material in STXM images correspond to areas with increased Eu(III) luminescence yield in the LSLM micrographs. In the C 1s-NEXAFS of metal-loaded polyacrylic acid (PAA), used as a HA model compound, a distinct complexation effect is identified. This effect is similar to trends observed in the dense fraction of HA/metal cation aggregates. The strongest complexation effect is observed for the Zr(IV)-HA/PAA system. This effect is confirmed by quantum chemical calculations performed at the ab initio level for model complexes with different metal centres and complex geometries. Without the high spatial resolution of STXM and LSLM and without the combination of molecular modelling with experimental results, the different zones indicating a ;pseudo'-phase separation into strong complexing domains and weaker complexing domains of HA would never have been identified. This type of strategy can be used to study metal interaction with other organic material.

  3. Construction of environment states in quantum-chemical density-matrix renormalization group calculations. (United States)

    Moritz, Gerrit; Reiher, Markus


    The application of the quantum-chemical density-matrix renormalization group (DMRG) algorithm is cumbersome for complex electronic structures with many active orbitals. The high computational cost is mainly due to the poor convergence of standard DMRG calculations. A factor which affects the convergence behavior of the calculations is the choice of the start-up procedure. In this start-up step matrix representations of operators have to be calculated in a guessed many-electron basis of the DMRG environment block. Different possibilities for the construction of these basis states exist, and we first compare four procedures to approximate the environment states using Slater determinants explicitly. These start-up procedures are applied to DMRG calculations on a sophisticated test system: the chromium dimer. It is found that the converged energies and the rate of convergence depend significantly on the choice of the start-up procedure. However, since already the most simple start-up procedure, which uses only the Hartree-Fock determinant, is comparatively good, Slater determinants, in general, appear not to be a good choice as approximate environment basis states for convergence acceleration. Based on extensive test calculations it is demonstrated that the computational cost can be significantly reduced if the number of total states m is successively increased. This is done in such a way that the environment states are built up stepwise from system states of previous truncated DMRG sweeps for slowly increasing m values.

  4. Intramolecular hydrogen bonding in 5-nitrosalicylaldehyde: IR spectrum and quantum chemical calculations (United States)

    Moosavi-Tekyeh, Zainab; Taherian, Fatemeh; Tayyari, Sayyed Faramarz


    The structural parameters, and vibrational frequencies of 5-nitrosalicylaldehyde (5NSA) were studied by the FT-IR and Raman spectra and the quantum chemical calculations carried out at the B3LYP/6-311++G(d,p) level of theory in order to investigate the intramolecular hydrogen bonding (IHB) present in its structure. The strength and nature of IHB in the optimized structure of 5NSA were studied in detail by means of the atoms in molecules (AIM) and the natural bond orbital (NBO) approaches. The results obtained were then compared with the corresponding data for its parent molecule, salicylaldehyde (SA). Comparisons made between the geometrical structures for 5NSA and SA, their OH/OD stretching and out-of-plane bending modes, their enthalpies for the hydrogen bond, and their AIM parameters demonstrated a stronger H-bonding in 5NSA compared with that in SA. The calculated binding enthalpy (ΔHbind) for 5NSA was -10.92 kcal mol-1. The observed νOH and γOH appeared at about 3120 cm-1 and 786 cm-1 respectively. The stretching frequency shift of H-bond formation was 426 cm-1 which is consistent with ΔHbind and the strength of H-bond in 5NSA. The delocalization energies and electron delocalization indices derived by the NBO and AIM approaches indicate that the resonance effects were responsible for the stronger IHB in 5NSA than in SA.

  5. Silicon Oxysulfide, OSiS: Rotational Spectrum, Quantum-Chemical Calculations, and Equilibrium Structure. (United States)

    Thorwirth, Sven; Mück, Leonie Anna; Gauss, Jürgen; Tamassia, Filippo; Lattanzi, Valerio; McCarthy, Michael C


    Silicon oxysulfide, OSiS, and seven of its minor isotopic species have been characterized for the first time in the gas phase at high spectral resolution by means of Fourier transform microwave spectroscopy. The equilibrium structure of OSiS has been determined from the experimental data using calculated vibration-rotation interaction constants. The structural parameters (rO-Si = 1.5064 Å and rSi-S = 1.9133 Å) are in very good agreement with values from high-level quantum chemical calculations using coupled-cluster techniques together with sophisticated additivity and extrapolation schemes. The bond distances in OSiS are very short in comparison with those in SiO and SiS. This unexpected finding is explained by the partial charges calculated for OSiS via a natural population analysis. The results suggest that electrostatic effects rather than multiple bonding are the key factors in determining bonding in this triatomic molecule. The data presented provide the spectroscopic information needed for radio astronomical searches for OSiS.

  6. New solid forms of efavirenz: Synthesis, vibrational spectroscopy and quantum chemical calculations (United States)

    Marques, Marcelo M.; Rezende, Carlos A.; Lima, Gabriel C.; Marques, Andressa C. S.; Prado, Lívia D.; Leal, Kátia Z.; Rocha, Helvécio V. A.; Ferreira, Gláucio B.; Resende, Jackson A. L. C.


    Efavirenz,(S)-6-chloro-4-(cyclopropylethynyl)-1,4-dihydro-4-(trifluoromethyl)-2H-3,1-benzoxazin-2-one, is an anti HIV agent from the class of the non-nucleoside inhibitors of the HIV-1 virus reverse transcriptase. This paper describes the synthesis of two new solvatomorphs of efavirenz (EFV). The results through XRPD and DSC/TG indicate that the new forms undergo a solvent loss over the days, and then return to the original polymorph. Structural and spectral characteristics of EFV were studied by vibrational spectroscopy and quantum chemical methods. Density functional theory (DFT) calculations for the potential energy curve, optimized geometries and vibrational spectra were carried out using 6-311 + G** basis sets and CAM-B3LYP functional, solid state calculations were also performed using DFT-XGGA (PBE-D3) exchange-correlation functional with the option of mixtures of Gaussian and plane waves method (GPW). Based on these results, the paper discussed the correlation between the vibrational modes and the crystalline structure of the most stable form of EFV. A complete analysis of the experimental infrared and Raman spectra was reported on the basis of the wavenumbers of the vibrational bands and the potential energy distribution.

  7. Electronic and rovibrational quantum chemical analysis of C3P-: the next interstellar anion? (United States)

    Fortenberry, Ryan C.; Lukemire, Joseph A.


    C3P- is analogous to the known interstellar anion C3N- with phosphorus replacing nitrogen in a simple step down the periodic table. In this work, it is shown that C3P- is likely to possess a dipole-bound excited state. It has been hypothesized and observationally supported that dipole-bound excited states are an avenue through which anions could be formed in the interstellar medium. Additionally, C3P- has a valence excited state that may lead to further stabilization of this molecule, and C3P- has a larger dipole moment than neutral C3P (˜6 D versus ˜4 D). As such, C3P- is probably a more detectable astromolecule than even its corresponding neutral radical. Highly accurate quantum chemical quartic force fields are also applied to C3P- and its singly 13C substituted isotopologues in order to provide structures, vibrational frequencies, and spectroscopic constants that may aid in its detection.

  8. The pDynamo Program for Molecular Simulations using Hybrid Quantum Chemical and Molecular Mechanical Potentials. (United States)

    Field, Martin J


    The pDynamo program has been developed for the simulation of molecular systems using hybrid quantum chemical (QC) and molecular mechanical (MM) potentials. pDynamo is written in a mixture of the computer languages Python and C and is a successor to the previous version of Dynamo, now denoted fDynamo, that was written in Fortran 90 (J. Comput. Chem. 2000, 21, 1088). The current version of Dynamo has a similar range of functionality to the older one but extends it in some significant ways, including the addition of a density functional theory QC capability. This paper gives a general description of pDynamo and outlines some of the advantages and disadvantages that have been encountered in switching computer languages. Some technical aspects of the implementation of pDynamo's algorithms are also discussed and illustrated with the results of example calculations. pDynamo is available on the Web at the address and is released under the CeCILL license which is equivalent to the GNU general public license but conforms to the principles of French law.

  9. [Chemical risk assessment in the construction industry: principles and critical issues]. (United States)

    Manno, M


    Risk assessment (RA) represents the first step to ensure the protection of the workers' health in all work sectors, production and services included. For this reason RA has become a legal duty for the occupational physician in his/her professional activity. The basic concepts of RA have been developed as a formal procedure for the management of chemical risks but they are currently applied to protect human health against all types of occupational and environmental risk factors. In the construction industry, in particular, chemical risk assessment is specially difficult due to the complexity of the working condition, and the variability and multiplicity of exposure. The critical aspects of RA in the construction industry will be discussed here, in the attempt to highlight how the occupational physician, making use of traditional and new tools, including biological monitoring, can address and partly overcome them.

  10. Quantum chemical calculations predict biological function: The case of T cell receptor interaction with a peptide/MHC class I (United States)

    Antipas, Georgios S. E.; Germenis, Anastasios


    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.

  11. Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration. (United States)

    Kozuch, Sebastian; Shaik, Sason


    A combined kinetic-quantum chemical model is developed with the goal of estimating in a straightforward way the turnover frequency (TOF) of catalytic cycles, based on the state energies obtained by quantum chemical calculations. We describe how the apparent activation energy of the whole cycle, so-called energetic span (delta E), is influenced by the energy levels of two species: the TOF determining transition state (TDTS) and the TOF determining intermediate (TDI). Because these key species need not be adjoining states, we conclude that for catalysis there are no rate-determining steps, only rate determining states. In addition, we add here the influence of reactants concentrations. And, finally, the model is applied to the Haber-Bosch process of ammonia synthesis, for which we show how to calculate which catalyst will be the most effective under specific reagents conditions.

  12. A quantum chemical based toxicity study of estimated reduction potential and hydrophobicity in series of nitroaromatic compounds. (United States)

    Gooch, A; Sizochenko, N; Sviatenko, L; Gorb, L; Leszczynski, J


    Nitroaromatic compounds and the products of their degradation are toxic to bacteria, cells and animals. Various studies have been carried out to better understand the mechanism of toxicity of aromatic nitrocompounds and their relationship to humans and the environment. Recent data relate cytotoxicity of nitroaromatic compounds to their single- or two-electron enzymatic reduction. However, mechanisms of animal toxicity could be more complex. This work investigates the estimated reduction and oxidation potentials of 34 nitroaromatic compounds using quantum chemical approaches. All geometries were optimized with density functional theory (DFT) using the solvation model based on density (SMD) and polarizable continuum model (PCM) solvent model protocols. Quantitative structure-activity/property (QSAR/QSPR) models were developed using descriptors obtained from quantum chemical optimizations as well as the DRAGON software program. The QSAR/QSPR equations developed consist of two to four descriptors. Correlations have been identified between electron affinity (E LUMO ) and hydrophobicity (log P).

  13. Critical Investigation of Jauch's Approach to the Quantum Theory of Measurement (United States)

    Herbut, Fedor


    To make Jauch's approach more realistic, his assumptions are modified in two ways: (1) On the quantum system plus the measuring apparatus (S+MA) after the measuring interaction has ceased, one can actually measure only operators of the form A⊗∑ k b k Q k ,where A is any Hermitian operator for S, the resolution of the identity ∑kQk=1 defines MA as a classical system (following von Neumann), and the b k are real numbers (S and MA are distant). (2) Measurement is defined in the most general way (including, besides first-kind, also second-kind and third-kind or indirect measurements). It is shown that Jauch's basic result that the microstates (statistical operators) of S+MA before and after the collapse correspond to the same macrostate (belong to the same equivalence class of microstates) remains valid under the above modifications, and that the significance of this result goes beyond measurement theory. On the other hand, it is argued that taking the orthodox (i.e. uncompromisingly quantum) view of quantum mechanics, it is not the collapse, but the Jauch-type macrostates that are spurious in a Jauch-type theory.

  14. Planck's Quantum Theory of the First Two Decades: Historico-Critical Reflectiones (United States)

    Campogalliani, P.

    While the role played by Planck's theory of black body radiation in the birth of quantum physics is wellknown, on the contrary his continuous quantistic theoretical work during the first two decades of this century is still obscure. In order to correctly understand this theoretical work, it is necessary to insert some basic questions: a) what are the specific original features of this theoretical construction? b) is it reasonable to consider this quantistic theory as different from contemporary old quantum theory? c) what is its contribution to the birth of quantum mechanics? Here an attempt will be made to examine the first and partially the second question. The thesis is that some basic statements of his epistemology, specifically a strong realistic view about scientific knowledge and the conviction that evolution of phyisics has a unifying trend, strongly influenced his creative theoretical process. The principle of elementary disorder, with its ambiguous nature, allows this strong connection. Conclusively it is necessary to keep persistent positivistic historiography at a distance, in order to follow a different historiography attentive to the trasformative processes generated by ideas which are not completely translated in the formal apparatus.

  15. Dependence of the extraction capacity of neutral bidentate organophosphorus compounds on their structure: a quantum chemical study

    International Nuclear Information System (INIS)

    Sudarushkin, S.K.; Morgalyuk, V.P.; Tananaev, I.G.; Gribov, L.A.; Myasoedov, B.F.


    Correlations between the extraction capacities and molecular structures of organic phosphorus compounds (reagents for extraction of transplutonium elements from spent nuclear fuel) were studied using a quantum chemical approach. The results of calculations are in qualitative agreement with experimental data. The approach proposed can be used for analysis of the extraction properties of all classes of organic phosphorus compounds and also for prediction of the most efficient organic phosphorus extractants with preset properties [ru

  16. A quantum-chemical study of oxygen-vacancy defects in PbTiO{sub 3} crystals

    Energy Technology Data Exchange (ETDEWEB)

    Stashans, Arvids [Laboratorio de Fisica, Escuela de Electronica y Telecomunicaciones, Universidad Tecnica Particular de Loja, Apartado 11-01-608, Loja (Ecuador)]. E-mail:; Serrano, Sheyla [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador); Escuela de Ingenierias, Universidad Politecnica Salesiana, Campus Sur, Rumichaca s/n y Moran Valverde, Apartado 17-12-536, Quito (Ecuador); Medina, Paul [Centro de Investigacion en Fisica de Materia Condensada, Corporacion de Fisica Fundamental y Aplicada, Apartado 17-12-637, Quito (Ecuador)


    Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO{sub 3} crystals is done by means of quantum-chemical simulations. Displacements of defect-surrounding atoms, electronic and optical properties, lattice relaxation energies and some new effects due to the defects presence are reported and analyzed. A comparison with similar studies is made and conclusions are drawn on the basis of the obtained results.

  17. Spin-liquid Mott quantum criticality in two dimensions: Destabilization of a spinon Fermi surface and emergence of one-dimensional spin dynamics (United States)

    Han, Jae-Ho; Cho, Yong-Heum; Kim, Ki-Seok


    Resorting to a recently developed theoretical device called dimensional regularization for quantum criticality with a Fermi surface, we examine a metal-insulator quantum phase transition from a Landau's Fermi-liquid state to a U(1) spin-liquid phase with a spinon Fermi surface in two dimensions. Unfortunately, we fail to approach the spin-liquid Mott quantum critical point from the U(1) spin-liquid state within the dimensional regularization technique. Self-interactions between charge fluctuations called holons are not screened, which shows a run-away renormalization group flow, interpreted as holons remain gapped. This leads us to consider another fixed point, where the spinon Fermi surface can be destabilized across the Mott transition. Based on this conjecture, we reveal the nature of the spin-liquid Mott quantum critical point: Dimensional reduction to one dimension occurs for spin dynamics described by spinons. As a result, Landau damping for both spin and charge dynamics disappear in the vicinity of the Mott quantum critical point. When the flavor number of holons is over its critical value, an interacting fixed point appears to be identified with an inverted X Y universality class, controlled within the dimensional regularization technique. On the other hand, a fluctuation-driven first order metal-insulator transition results when it is below the critical number. We propose that the destabilization of a spinon Fermi surface and the emergence of one-dimensional spin dynamics near the spin-liquid Mott quantum critical point can be checked out by spin susceptibility with a 2 kF transfer momentum, where kF is a Fermi momentum in the U(1) spin-liquid state: The absence of Landau damping in U(1) gauge fluctuations gives rise to a divergent behavior at zero temperature while it vanishes in the presence of a spinon Fermi surface.

  18. Electrochemical and quantum chemical study of purines as corrosion inhibitors for mild steel in 1 M HCl solution

    International Nuclear Information System (INIS)

    Yan Ying; Li Weihua; Cai Lankun; Hou Baorong


    The purines and its derivatives, such as, guanine, adenine, 2,6-diaminopurine, 6-thioguanine and 2,6-dithiopurine, were investigated as corrosion inhibitors for mild steel in 1 M HCl solution by weight loss measurements, electrochemical tests and quantum chemical calculations. The polarization curves of mild steel in the hydrochloric acid solutions of the purines showed that both cathodic and anodic processes of steel corrosion were suppressed. The Nyquist plots of impedance expressed mainly as a depressed capacitive loop with different compounds and concentrations. For all these purines, the inhibition efficiency increased by increasing the inhibitor concentration, and the inhibition efficiency orders are 2,6-dithiopurine > 6-thioguanine > 2,6-diaminopurine > adenine > guanine with the highest inhibiting efficiency of 88.0% for 10 -3 M 2,6-dithiopurine. The optimized structures of purines, the Mulliken charges, molecular orbital densities and relevant parameters were calculated by quantum chemical calculations. The quantum chemical calculation results inferred that the adsorption belong to physical adsorption, which might arise from the π stacking between the π electron of the purines and the metal surface

  19. A QCD chiral critical point at small chemical potential: is it there or not?

    CERN Document Server

    de Forcrand, Philippe; Philipsen, Owe


    For a QCD chiral critical point to exist, the parameter region of small quark masses for which the finite temperature transition is first-order must expand when the chemical potential is turned on. This can be tested by a Taylor expansion of the critical surface (m_{u,d},m_s)_c(mu). We present a new method to perform this Taylor expansion numerically, which we first test on an effective model of QCD with static, dense quarks. We then present the results for QCD with 3 degenerate flavors. For a lattice with N_t=4 time-slices, the first-order region shrinks as the chemical potential is turned on. This implies that, for physical quark masses, the analytic crossover which occurs at mu=0 between the hadronic and the plasma regimes remains crossover in the mu-region where a Taylor expansion is reliable, i.e. mu less than or similar to T. We present preliminary results from finer lattices indicating that this situation persists, as does the discrepancy between the curvature of T_c(mu) and the experimentally observed...

  20. Complexation reactions in pyridine and 2,6-dimethylpyridine-water system: The quantum-chemical description and the path to liquid phase separation (United States)

    Chernia, Zelig; Tsori, Yoav


    Phase separation in substituted pyridines in water is usually described as an interplay between temperature-driven breakage of hydrogen bonds and the associating interaction of the van der Waals force. In previous quantum-chemical studies, the strength of hydrogen bonding between one water and one pyridine molecules (the 1:1 complex) was assigned a pivotal role. It was accepted that the disassembly of the 1:1 complex at a critical temperature leads to phase separation and formation of the miscibility gap. Yet, for over two decades, notable empirical data and theoretical arguments were presented against that view, thus revealing the need in a revised quantum-mechanical description. In the present study, pyridine-water and 2,6-dimethylpyridine-water systems at different complexation stages are calculated using high level Kohn-Sham theory. The hydrophobic-hydrophilic properties are accounted for by the polarizable continuum solvation model. Inclusion of solvation in free energy of formation calculations reveals that 1:1 complexes are abundant in the organically rich solvents but higher level oligomers (i.e., 2:1 dimers with two pyridines and one water molecule) are the only feasible stable products in the more polar media. At the critical temperature, the dissolution of the external hydrogen bonds between the 2:1 dimer and the surrounding water molecules induces the demixing process. The 1:1 complex acts as a precursor in the formation of the dimers but is not directly involved in the demixing mechanism. The existence of the miscibility gap in one pyridine-water system and the lack of it in another is explained by the ability of the former to maintain stable dimerization. Free energy of formation of several reaction paths producing the 2:1 dimers is calculated and critically analyzed.

  1. Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells. (United States)

    Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei; Xiong, Yan; Tsai, Fang-Chang


    A photoelectric conversion efficiency (PCE) of 4.9% was obtained under 100 mW cm -2 illumination by quantum-dot-sensitized solar cells (QDSSCs) using a CdS/Mn : CdSe sensitizer. CdS quantum dots (QDs) were deposited on a TiO 2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn 2+ doping into CdSe QDs is an innovative and simple method-chemical bath co-deposition, that is, mixing the Mn ion source with CdSe precursor solution for Mn : CdSe QD deposition. Compared with the CdS/CdSe sensitizer without Mn 2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn 2+ doping on the chemical, physical and photovoltaic properties of the QDSSCs were investigated by energy dispersive spectrometry, absorption spectroscopy, photocurrent density-voltage characteristics and electrochemical impedance spectroscopy. Mn-doped CdSe QDs in QDSSCs can obtain superior light absorption, faster electron transport and slower charge recombination than CdSe QDs.

  2. Human cost burden of exposure to endocrine disrupting chemicals. A critical review. (United States)

    Bond, Gregory G; Dietrich, Daniel R


    Recently published papers have alleged that exposures to endocrine disrupting chemicals (EDCs) are causing substantial disease burdens in the EU and US and are consequently costing society hundreds of billions of dollars annually. To date, these cost estimates have not undergone adequate scientific scrutiny, but nevertheless are being used aggressively in advocacy campaigns in an attempt to fundamentally change how chemicals are tested, evaluated and regulated. Consequently, we critically evaluated the underlying methodology and assumptions employed by the chief architects of the disease burden cost estimates. Since the vast majority of their assigned disease burden costs are driven by the assumption that "loss of IQ" and "increased prevalence of intellectual disability" are caused by exposures to organophosphate pesticides (OPPs) and brominated flame retardants (PBDEs), we have taken special care in describing and evaluating the underlying toxicology and epidemiology evidence that was relied upon. Unfortunately, our review uncovered substantial flaws in the approach taken and the conclusions that were drawn. Indeed, the authors of these papers assumed causal relationships between putative exposures to EDCs and selected diseases, i.e., "loss of IQ" and "increased prevalence of intellectual disability", despite not having established them via a thorough evaluation of the strengths and weaknesses of the underlying animal toxicology and human epidemiology evidence. Consequently, the assigned disease burden costs are highly speculative and should not be considered in the weight of evidence approach underlying any serious policy discussions serving to protect the public and regulate chemicals considered as EDCs.

  3. Prediction of aqueous solubility, vapor pressure and critical micelle concentration for aquatic partitioning of perfluorinated chemicals. (United States)

    Bhhatarai, Barun; Gramatica, Paola


    The majority of perfluorinated chemicals (PFCs) are of increasing risk to biota and environment due to their physicochemical stability, wide transport in the environment and difficulty in biodegradation. It is necessary to identify and prioritize these harmful PFCs and to characterize their physicochemical properties that govern the solubility, distribution and fate of these chemicals in an aquatic ecosystem. Therefore, available experimental data (10-35 compounds) of three important properties: aqueous solubility (AqS), vapor pressure (VP) and critical micelle concentration (CMC) on per- and polyfluorinated compounds were collected for quantitative structure-property relationship (QSPR) modeling. Simple and robust models based on theoretical molecular descriptors were developed and externally validated for predictivity. Model predictions on selected PFCs were compared with available experimental data and other published in silico predictions. The structural applicability domains (AD) of the models were verified on a bigger data set of 221 compounds. The predicted properties of the chemicals that are within the AD, are reliable, and they help to reduce the wide data gap that exists. Moreover, the predictions of AqS, VP, and CMC of most common PFCs were evaluated to understand the aquatic partitioning and to derive a relation with the available experimental data of bioconcentration factor (BCF).

  4. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology. (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi


    Quantum chemical techniques today are indispensable for the detailed mechanistic understanding of catalytic reactions. The development of modern density functional theory approaches combined with the enormous growth in computer power have made it possible to treat quite large systems at a reasonable level of accuracy. Accordingly, quantum chemistry has been applied extensively to a wide variety of catalytic systems. A huge number of problems have been solved successfully, and vast amounts of chemical insights have been gained. In this Account, we summarize some of our recent work in this field. A number of examples concerned with transition metal-catalyzed reactions are selected, with emphasis on reactions with various kinds of selectivities. The discussed cases are (1) copper-catalyzed C-H bond amidation of indoles, (2) iridium-catalyzed C(sp(3))-H borylation of chlorosilanes, (3) vanadium-catalyzed Meyer-Schuster rearrangement and its combination with aldol- and Mannich-type additions, (4) palladium-catalyzed propargylic substitution with phosphorus nucleophiles, (5) rhodium-catalyzed 1:2 coupling of aldehydes and allenes, and finally (6) copper-catalyzed coupling of nitrones and alkynes to produce β-lactams (Kinugasa reaction). First, the methodology adopted in these studies is presented briefly. The electronic structure method in the great majority of these kinds of mechanistic investigations has for the last two decades been based on density functional theory. In the cases discussed here, mainly the B3LYP functional has been employed in conjunction with Grimme's empirical dispersion correction, which has been shown to improve the calculated energies significantly. The effect of the surrounding solvent is described by implicit solvation techniques, and the thermochemical corrections are included using the rigid-rotor harmonic oscillator approximation. The reviewed examples are chosen to illustrate the usefulness and versatility of the adopted methodology in

  5. Quantum chemical investigation on photodegradation mechanisms of sulfamethoxypyridazine with dissolved inorganic matter and hydroxyl radical. (United States)

    Shah, Shaheen; Hao, Ce


    Sulfamethoxypyridazine (SMP) is one of the commonly used sulfonamide antibiotics (SAs). SAs are mainly studied to undergo triplet-sensitized photodegradation in water under natural sunlight with other coexisting aquatic environmental organic pollutants. In this work, SMP was selected as a representative of SAs. We studied the mechanisms of triplet-sensitized photodegradation of SMP and the influence of selected dissolved inorganic matter, i.e., anions (Br - , Cl - , and NO 3 - ) and cations ions (Ca 2+ , Mg 2+ , and Zn 2+ ) on SMP photodegradation mechanism by quantum chemical methods. In addition, the degradation mechanisms of SMP by hydroxyl radical (OH) were also investigated. The creation of SO 2 extrusion product was accessed with two different energy pathways (pathway-1 and pathway-2) by following two steps (step-I and step-II) in the triplet-sensitized photodegradation of SMP. Due to low activation energy, the pathway-1 was considered as the main pathway to obtain SO 2 extrusion product. Step-II of pathway-1 was measured to be the rate-limiting step (RLS) of SMP photodegradation mechanism and the effect of the selected anions and cations was estimated for this step. All selected anions and cations promoted photodegradation of SMP by dropping the activation energy of pathway-1. The estimated low activation energies of different degradation pathways of SMP with OH radical indicate that OH radical is a very powerful oxidizing agent for SMP degradation via attack through benzene derivative and pyridazine derivative ring. Copyright © 2016. Published by Elsevier B.V.

  6. Quantum Chemical Benchmarking, Validation, and Prediction of Acidity Constants for Substituted Pyridinium Ions and Pyridinyl Radicals. (United States)

    Keith, John A; Carter, Emily A


    Sensibly modeling (photo)electrocatalytic reactions involving proton and electron transfer with computational quantum chemistry requires accurate descriptions of protonated, deprotonated, and radical species in solution. Procedures to do this are generally nontrivial, especially in cases that involve radical anions that are unstable in the gas phase. Recently, pyridinium and the corresponding reduced neutral radical have been postulated as key catalysts in the reduction of CO2 to methanol. To assess practical methodologies to describe the acid/base chemistry of these species, we employed density functional theory (DFT) in tandem with implicit solvation models to calculate acidity constants for 22 substituted pyridinium cations and their corresponding pyridinyl radicals in water solvent. We first benchmarked our calculations against experimental pyridinium deprotonation energies in both gas and aqueous phases. DFT with hybrid exchange-correlation functionals provide chemical accuracy for gas-phase data and allow absolute prediction of experimental pKas with unsigned errors under 1 pKa unit. The accuracy of this economical pKa calculation approach was further verified by benchmarking against highly accurate (but very expensive) CCSD(T)-F12 calculations. We compare the relative importance and sensitivity of these energies to selection of solvation model, solvation energy definitions, implicit solvation cavity definition, basis sets, electron densities, model geometries, and mixed implicit/explicit models. After determining the most accurate model to reproduce experimentally-known pKas from first principles, we apply the same approach to predict pKas for radical pyridinyl species that have been proposed relevant under electrochemical conditions. This work provides considerable insight into the pitfalls using continuum solvation models, particularly when used for radical species.

  7. Quantum-chemical study of dispersion medium influence on the emulsifying ability of milk proteins

    Directory of Open Access Journals (Sweden)

    Borisenko A. A.


    Full Text Available Nowadays the products containing milk proteins are widely used in meat industry. Due to these substances application protein-fatty emulsions are stabilized, products consistency, succulence and appearance are made better. To investigate the influence of electrochemically activated water on the emulsifying ability of milk proteins computer molecular modeling and quantum chemical calculations of fragment molecules of αs1-casein in drinking water and catholyte in the presence of linoleic acid triacylglyceride has been conducted. It has been revealed that the negatively charged part of the test protein in the presence of fat molecules in the water is directed toward the polar component, and the nonpolar part is directed toward the hydrophobic component. It has been established that the dipole moment value of αs1-casein molecule fragment being studied in catholyte has been reduced by 10.55 D, the number of hydrogen bonds with molecules of the catholyte has increased by a factor of 1.3 and the number of intramolecular hydrogen bonds of the protein has increased by a factor of 1.7 comparing to the results of the system modeling on the basis of drinking water. On the fragment molecules of αs1-casein in the catholyte the strong electrostatic potential concentration with high electron density center displacement to the phosphoserine amino-acid residue area has been fixed; the protein emulsifying ability increase due to hydrophilic and hydrophobic properties strengthening at the corresponding sections of the peptide chain comparing to drinking water has been established. On the basis of the conducted researches it has been established that protein milk products hydrated with electrochemically activated water (catholyte are more effective as emulsifiers and water-binding components then when drinking water is used. This allows recommending them for the production of different meat products.

  8. Study of polymorphism in imatinib mesylate: A quantum chemical approach using electronic and vibrational spectra (United States)

    Srivastava, Anubha; Joshi, B. D.; Tandon, Poonam; Ayala, A. P.; Bansal, A. K.; Grillo, Damián


    Imatinib mesylate, 4-(4-methyl-piperazin-1-ylmethyl)-N-u[4-methyl-3-(4-pyridin-3-yl)pyrimidine-2-ylamino)phenyl]benzamide methanesulfonate is a therapeutic drug that is approved for the treatment of chronic myelogeneous leukemia (CML) and gastrointestinal stromal tumors (GIST). It is known that imatinib mesylate exists in two polymorphic forms α and β. However, β-form is more stable than the α-form. In this work, we present a detailed vibrational spectroscopic investigation of β-form by using FT-IR and FT-Raman spectra. These data are supported by quantum mechanical calculations using DFT employing 6-311G(d,p) basis set, which allow us to characterize completely the vibrational spectra of this compound. The FT-IR spectrum of α-form has also been discussed. The importance of hydrogen-bond formation in the molecular packing arrangements of both forms has been examined with the vibrational shifts observed due to polymorphic changes. The red shift of the NH stretching bands in the infrared spectrum from the computed wavenumber indicates the weakening of the NH bond. The UV-vis spectroscopic studies along with the HOMO-LUMO analysis of both polymorphs (α and β) were performed and their chemical activity has been discussed. The TD-DFT method was used to calculate the electronic absorption spectra in the gas phase as well as in the solvent environment using IEF-PCM model and 6-31G basis set. Finally, the results obtained complements to the experimental findings.

  9. Critical comparison of electrode models in density functional theory based quantum transport calculations. (United States)

    Jacob, D; Palacios, J J


    We study the performance of two different electrode models in quantum transport calculations based on density functional theory: parametrized Bethe lattices and quasi-one-dimensional wires or nanowires. A detailed account of implementation details in both the cases is given. From the systematic study of nanocontacts made of representative metallic elements, we can conclude that the parametrized electrode models represent an excellent compromise between computational cost and electronic structure definition as long as the aim is to compare with experiments where the precise atomic structure of the electrodes is not relevant or defined with precision. The results obtained using parametrized Bethe lattices are essentially similar to the ones obtained with quasi-one-dimensional electrodes for large enough cross-sections of these, adding a natural smearing to the transmission curves that mimics the true nature of polycrystalline electrodes. The latter are more demanding from the computational point of view, but present the advantage of expanding the range of applicability of transport calculations to situations where the electrodes have a well-defined atomic structure, as is the case for carbon nanotubes, graphene nanoribbons, or semiconducting nanowires. All the analysis is done with the help of codes developed by the authors which can be found in the quantum transport toolbox ALACANT and are publicly available.

  10. Advances in chemical physics

    CERN Document Server

    Rice, Stuart A


    The Advances in Chemical Physics series-the cutting edge of research in chemical physics The Advances in Chemical Physics series provides the chemical physics field with a forum for critical, authoritative evaluations of advances in every area of the discipline. Filled with cutting-edge research reported in a cohesive manner not found elsewhere in the literature, each volume of the Advances in Chemical Physics series serves as the perfect supplement to any advanced graduate class devoted to the study of chemical physics. This volume explores: Quantum Dynamical Resonances in Ch

  11. Unconventional and conventional quantum criticalities in CeRh0.58Ir0.42In5 (United States)

    Luo, Yongkang; Lu, Xin; Dioguardi, Adam P.; Rosa, Priscila S. F.; Bauer, Eric D.; Si, Qimiao; Thompson, Joe D.


    An appropriate description of the state of matter that appears as a second order phase transition is tuned toward zero temperature, viz. quantum-critical point (QCP), poses fundamental and still not fully answered questions. Experiments are needed both to test basic conclusions and to guide further refinement of theoretical models. Here, charge and entropy transport properties as well as AC specific heat of the heavy-fermion compound CeRh0.58Ir0.42In5, measured as a function of pressure, reveal two qualitatively different QCPs in a single material driven by a single non-symmetry-breaking tuning parameter. A discontinuous sign-change jump in thermopower suggests an unconventional QCP at pc1 accompanied by an abrupt Fermi-surface reconstruction that is followed by a conventional spin-density-wave critical point at pc2 across which the Fermi surface evolves smoothly to a heavy Fermi-liquid state. These experiments are consistent with some theoretical predictions, including the sequence of critical points and the temperature dependence of the thermopower in their vicinity.

  12. A Comparative Study of Two Quantum Chemical Descriptors in Predicting Toxicity of Aliphatic Compounds towards Tetrahymena pyriformis

    Directory of Open Access Journals (Sweden)

    Altaf Hussain Pandith


    Full Text Available Quantum chemical parameters such as LUMO energy, HOMO energy, ionization energy (I, electron affinity (A, chemical potential (μ, hardness (η electronegativity (χ, philicity (ωα, and electrophilicity (ω of a series of aliphatic compounds are calculated at the B3LYP/6-31G(d level of theory. Quantitative structure-activity relationship (QSAR models are developed for predicting the toxicity (pIGC50 of 13 classes of aliphatic compounds, including 171 electron acceptors and 81 electron donors, towards Tetrahymena pyriformis. The multiple linear regression modeling of toxicity of these compounds is performed by using the molecular descriptor log P (1-octanol/water partition coefficient in conjunction with two other quantum chemical descriptors, electrophilicity (ω and energy of the lowest unoccupied molecular orbital (ELUMO. A comparison is made towards the toxicity predicting the ability of electrophilicity (ω versus ELUMO as a global chemical reactivity descriptor in addition to log P. The former works marginally better in most cases. There is a slight improvement in the quality of regression by changing the unit of IGC50 from mg/L to molarity and by removing the racemates and the diastereoisomers from the data set.

  13. LaCu6−xAgx : A promising host of an elastic quantum critical point

    Energy Technology Data Exchange (ETDEWEB)

    Poudel, Lekh [ORNL; Dela Cruz, Clarina R. [ORNL; Koehler, Michael R. [University of Tennessee, Knoxville (UTK); McGuire, Michael A. [ORNL; Keppens, Veerle [University of Tennessee, Knoxville (UTK); Mandrus, David [ORNL; Christianson, Andrew D. [ORNL


    Structural properties of LaCu6−xAgx have been investigated using neutron and x-ray diffraction, and resonant ultrasound spectroscopy (RUS) measurements. Diffraction measurements indicate a continuous structural transition from orthorhombic (Pnma) to monoclinic (P2₁/C) structure. RUS measurements show softening of natural frequencies at the structural transition, consistent with the elastic nature of the structural ground state. The structural transition temperatures in LaCu6−xAgx decrease with Ag composition until the monoclinic phase is completely suppressed at xc=0.225. All of the evidence is consistent with the presence of an elastic quantum critical point in LaCu6−xAgx.

  14. The idealized quantum two-slit gedanken experiment revisited-Criticism and reinterpretation

    International Nuclear Information System (INIS)

    El Naschie, Mohamed Saladin


    An idealized two-slit experiment is envisaged in which the hypothetical experimental set-up is constructed in such a way as to resemble a toy model giving information about the structure of quantum space-time itself. Thus starting from a very simple equation which may be interpreted as a physical realization of Goedel's undecidability theorem, we proceed to show that space-time is very likely to be akin to a fuzzy Kaehler-like manifold on the quantum level. This remarkable manifold transforms gradually into a classical space-time as we decrease the resolution in a way reversibly analogous to the processes of recovering classical space-time from the Riemannian space of general relativity. The paper's main philosophy is to emphasize that the quintessence of the two-slit experiment as well as Feynman's path integral could be given a different interpretation by altering our classical concept of space-time geometry and topology. In turn this would be in keeping with the development in theoretical physics since special and subsequently general relativity. In the final analysis it would seem that we have two different yet, from a positivistic philosophy viewpoint, completely equivalent alternatives to view quantum physics. Either we insist on what we see in our daily experiences, namely, a smooth four-dimensional space-time, and then accept, whether we like it or not, things such as probability waves and complex probabilities. Alternatively, we could see behind the facade of classical space-time a far more elaborate and highly complex fuzzy space-time with infinite hierarchical dimensions such as the so-called Fuzzy K3 or E-Infinity space-time and as a reward for this imaginative picture we can return to real probabilities without a phase and an almost classical picture with the concept of a particle's path restored. We say almost classical because non-linear dynamics and deterministic chaos have long shown the central role of randomness in classical mechanics and this is

  15. Experimental studies of the quantum chromodynamics phase ...

    Indian Academy of Sciences (India)


    May 6, 2015 ... 200 GeV, permits an initial exploration of the phase diagram of quantum chromodynamics (QCD) matter. ... dynamics critical point; phase transition; chemical freeze-out; directed and elliptic flow; chiral magnetic effect .... The two main extracted parameters are chemical freeze-out temperature Tch and μB.

  16. Critical behavior in two-dimensional quantum gravity and equations of motion of the string

    International Nuclear Information System (INIS)

    Das, S.R.; Dhar, A.; Wadia, S.R.


    The authors show how consistent quantization determines the renormalization of couplings in a quantum field theory coupled to gravity in two dimensions. The special status of couplings corresponding to conformally invariant matter is discussed. In string theory, where the dynamical degree of freedom of the two-dimensional metric plays the role of time in target space, these renormalization group equations are themselves the classical equations of motion. Time independent solutions, like classical vacuua, correspond to the situation in which matter is conformally invariant. Time dependent solutions, like tunnelling configurations between vacuua, correspond to special trajectories in theory space. The authors discuss an example of such a trajectory in the space containing the c ≤ 1 minimal models. The authors also discuss the connection between this work and the recent attempts to construct non-pertubative string theories based on matrix models

  17. In situ synthesis, electrochemical and quantum chemical analysis of an amino acid-derived ionic liquid inhibitor for corrosion protection of mild steel in 1M HCl solution

    International Nuclear Information System (INIS)

    Kowsari, E.; Arman, S.Y.; Shahini, M.H.; Zandi, H.; Ehsani, A.; Naderi, R.; PourghasemiHanza, A.; Mehdipour, M.


    Highlights: • Electrochemical analysis of effectiveness of an amino acid-derived ionic liquid inhibitor. • Quantum chemical analysis of effectiveness of an amino acid-derived ionic liquid inhibitor. • Finding correlation between electrochemical analysis and quantum chemical analysis. - Abstract: In this study, an amino acid-derived ionic liquid inhibitor, namely tetra-n-butyl ammonium methioninate, was synthesized and the role this inhibitor for corrosion protection of mild steel exposed to 1.0 M HCl was investigated using electrochemical, quantum and surface analysis. By taking advantage of potentiodynamic polarization, the inhibitory action of tetra-n-butyl ammonium methioninate was found to be mainly mixed-type with dominant anodic inhibition. The effectiveness of the inhibitor was also indicated using electrochemical impedance spectroscopy (EIS). Moreover, to provide further insight into the mechanism of inhibition, electrochemical noise (EN) and quantum chemical calculations of the inhibitor were performed.

  18. Scaling behavior near the itinerant ferromagnetic quantum critical point (FQCP) of NiCoCrx for 0.8 (United States)

    Sales, Brian; Jin, Ke; Bei, Hongbin; Nichols, John; Chisholm, Matthew; May, Andrew; McGuire, Michael

    Low temperature magnetization, resistivity and heat capacity data are reported for the concentrated solid solution NiCoCrx as a function of temperature and magnetic field. In the quantum critical region the low field (0.001-0.01 T) magnetic susceptibility, Chi, diverges as T- 1 / 2 and the magnetization data exhibits T/B scaling from 0.001 2 Tesla, the crossover temperature from the QC to Fermi liquid regime is no longer linear in B, and is better described by B0.75. This scaling behavior is particularly accurate in describing the normalized magnetoresistance data [Rho(B,T)-Rho(0,T)]/T, which is equivalent to the ratio of relaxation rates associated with magnetic field and temperature TauT/TauB. The location of the QCP is sensitive to the composition x and the strain generated during synthesis. These medium-entropy alloys are interesting model systems to explore the role of chemical disorder at FQCP. Research supported by the DOE Office of Science, Materials Science and Engineering Division, and the Energy Dissipation to Defect Evolution EFRC.

  19. Quantum chemical calculation of the equilibrium structures of small metal atom clusters (United States)

    Kahn, L. R.


    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.

  20. The quantum phase-transitions of water (United States)

    Fillaux, François


    It is shown that hexagonal ices and steam are macroscopically quantum condensates, with continuous spacetime-translation symmetry, whereas liquid water is a quantum fluid with broken time-translation symmetry. Fusion and vaporization are quantum phase-transitions. The heat capacities, the latent heats, the phase-transition temperatures, the critical temperature, the molar volume expansion of ice relative to water, as well as neutron scattering data and dielectric measurements are explained. The phase-transition mechanisms along with the key role of quantum interferences and that of Hartley-Shannon's entropy are enlightened. The notions of chemical bond and force-field are questioned.

  1. Isolation, characterization, spectroscopic properties and quantum chemical computations of an important phytoalexin resveratrol as antioxidant component from Vitis labrusca L. and their chemical compositions (United States)

    Güder, Aytaç; Korkmaz, Halil; Gökce, Halil; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan


    In this study, isolation and characterization of trans-resveratrol (RES) as an antioxidant compound were carried out from VLE, VLG and VLS. Furthermore, antioxidant activities were evaluated by using six different methods. Finally, total phenolic, flavonoid, ascorbic acid, anthocyanin, lycopene, β-carotene and vitamin E contents were carried out. In addition, the FT-IR, 13C and 1H NMR chemical shifts and UV-vis. spectra of trans-resveratrol were experimentally recorded. Quantum chemical computations such as the molecular geometry, vibrational frequencies, UV-vis. spectroscopic parameters, HOMOs-LUMOs energies, molecular electrostatic potential (MEP), natural bond orbitals (NBO) and nonlinear optics (NLO) properties of title molecule have been calculated by using DFT/B3PW91 method with 6-311++G(d,p) basis set in ground state for the first time. The obtained results show that the calculated spectroscopic data are in a good agreement with experimental data.

  2. Quantum Dot Photovoltaics in the Extreme Quantum Confinement Regime: The Surface-Chemical Origins of Exceptional Air- and Light-Stability

    KAUST Repository

    Tang, Jiang


    We report colloidal quantum dot (CQDs) photovoltaics having a ∼930 nm bandgap. The devices exhibit AM1.5G power conversion efficiencies in excess of 2%. Remarkably, the devices are stable in air under many tens of hours of solar illumination without the need for encapsulation. We explore herein the origins of this ordersof-magnitude improvement in air stability compared to larger PbS dots. We find that small and large dots form dramatically different oxidation products, with small dots forming lead sulfite primarily and large dots, lead sulfate. The lead sulfite produced on small dots results in shallow electron traps that are compatible with excellent device performance; whereas the sulfates formed on large dots lead to deep traps, midgap recombination, and consequent catastrophic loss of performance. We propose and offer evidence in support of an explanation based on the high rate of oxidation of sulfur-rich surfaces preponderant in highly faceted large-diameter PbS colloidal quantum dots. © 2010 American Chemical Society.

  3. Scaling of spin-density-wave effects in the quantum critical (Cr{sub 86}Ru{sub 14}){sub 1-x}V{sub x} alloy system

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, L; Alberts, H L; Prinsloo, A R E; Strydom, A M, E-mail: [Department of Physics, University of Johannesburg, PO Box 524, Auckland Park, 2006 (South Africa)


    An analysis of experimental data on the electrical resistivity, Hall coefficient and electronic specific heat coefficient of a quantum critical (Cr{sub 86}Ru{sub 14}){sub 1-x}V{sub x} alloy system, is reported. The results give information on the role of spin-density-wave effects on the zero temperature relationships between these physical properties.

  4. Quantum chemical studies on electronic structure and photodynamics of ruthenium complexes

    International Nuclear Information System (INIS)

    Freitag, L.


    Ruthenium complexes have found their way into many applications in the last decades. Among those, ruthenium polypyridyl compounds have been employed as light harvesting devices and photosensitisers in artificial photosynthesis and molecular photocatalysis. Ruthenium nitrosyl complexes are rapidly emerging as NO delivery agents to biological tissues with promising applications in anticancer photodynamic therapy, thanks to their ability to photorelease nitric oxide (NO). This thesis encompasses computational studies on reactivity, electronic structure, excited states and photodynamics of several ruthenium nitrosyl and polypyridyl complexes. The first part of the thesis deals with ruthenium nitrosyls. The cis-trans isomerisation mechanism of RuHIndNO, a ruthenium nitrosyl derivate of the prominent anti-cancer drug candidate KP1019, is investigated with density functional theory calculations. Next, the electronic structure of the ground and the first excited triplet state of RuHIndNO is studied with multiconfigurational methods including the density-matrix renormalisation group (DMRG). The obtained multiconfigurational wavefunctions and DMRG-based orbital entanglement analysis provides theoretical insight into the non-innocence of the NO ligand in nitrosyl complexes by describing the electron correlation in the Ru--NO bond and assigning oxidation states to the metal and the NO ligand. Another study is performed on excited states of ruthenium nitrosyl complexes with quantum chemical calculations and surface-hopping dynamics to obtain insights into the photodissociation mechanism of NO. The second part of this thesis is devoted to the excited states and photophysics of ruthenium polypyridyl complexes. Accurate excitation energies of tris(2,2-bipyridine)ruthenium (II), the prototype ruthenium polypyridyl are obtained with multiconfigurational calculations assisted by an orbital entanglement analysis. Subsequently, the effect of the ligand substitution on the photophysics

  5. Quantum-chemical analysis of formation reactions of Со2+ complexes

    Directory of Open Access Journals (Sweden)

    Viktor F. Vargalyuk


    Full Text Available Based on the analysis of quantum chemical calculations results (GAMESS, density functional theory, B3LYP method as to coordination compounds of Co2+ions with H2O, NH3, OH–, F–, Cl–, Br–, I–, CN–, Ac–, Ak– generally given by [Co(H2O6–nLn]2+nx, it has been demonstrated that within the selected series of ligands, there is no correlation between the amount of energy of monosubstituted cobalt aqua complexes formation(∆Е and pK1,just like between the effective nuclear charge of the central atom (z*Со and pK1. According to the behavior of ∆Е and z*Со,we identified two groups of ligands. The first group (OH–, F–, Ac–, Ak–, CN–, NH3 demonstrates logical ∆Е decrease caused by the growth of z*Со. On the contrary, the second group (Cl–, Br–, I– demonstrates ∆Е increase caused by the growth of z*Со. This phenomenon is explained by the change in electronegativity and polarizability of donor atoms in groups and periods of the periodic table. It is established that linear correlations given by lgK = A + B·z*Со can be actualized only for complexes having ligands with similar donor atoms. Referring to the literature on stepwise complex formation of hydroxide, amine and chloride cobalt complexes in combination with z*Со calculations results, we determined A and B constants of lgK, z*Со-correlations for the atoms of oxygen (30.2, –17.7; nitrogen (125.4, –69.9 and chlorine (–6.3, 5.8. The existence of the detected correlation series enables us to lean on lgK,z*М–dependence parameters for the fixed donor atom and to determine Kn values for various complexes with complex-based ligands using calculations and z*М data. This applies to complexes having central atoms of the same nature as well as simple monodentate ligands. The mentioned approach was used to calculate the stability constants for acrylate cobalt complexes (lgK1 = 1.2 и lgК2 = 4.3, which are not covered in literature.

  6. Quantum chemical analysis of Со2+ aqua complexes electrochemical reduction

    Directory of Open Access Journals (Sweden)

    Viktor F. Vargalyuk


    Full Text Available Based on the analysis of quantum chemical calculations results (GAMESS, density functional theory, B3LYP method as to [Co(H2On]z(H2O6–n clusters for z = 0, 1, 2 and n=1÷6, it has been demonstrated that electrochemical reduction of [Co(H2O6]2+ aqua complexes runs stage-wise. At the first stage, an electron injected into the [Co(H2O6]2+ complex is entirely located in the orbital of the central atom, as z(Co herewith changes from +1.714 е to +0.777 е. The weakening of Со–ОН2 bonds leads to decomposition of resulting [Co(H2O6]+ particles into two energetically related forms – [Co(H2O4]+ and [Co(H2O3]+. Further reduction of these intermediates runs differently. Electron injection into the [Co(H2O3]+ intermediate terminatesthe transition of Со2+-ions to Со0 z(Co= –0.264 е. This process is accompanied by rapid decomposition of [Co(H2O3]0 product into monohydrate atom of cobalt Со(Н2О. On the contrary, electron injection into the [Co(H2O4]+ intermediate leads to emergence of a specific structure – [Co+(H2O–(Н2О3]¹0, whereby the electron is located in the atoms of cobalt only by 28%, and by 72% in cobalt-coordinated water molecules, clearly focusing on one of the. In this molecule, z(H2O changes from +0.148 е to –0.347 е. There is an assumption that a non-equilibrium [Co+(H2O–(Н2О3]0¹ form transits to [Co(ОH(Н2О3]0 hydroxo-form, which further disproportionates turning into Co(ОH2 hydroxide. In order to reduce the impact of this unfavorable reaction pathway on the overall reaction rate Со2+ + 2ē = Со0, we suggest raising the temperature to ensure complete dissociation of [Co(H2O4]+ to [Co(H2O3]+.

  7. Chemical potentials and thermodynamic characteristics of ideal Bose- and Fermi-gases in the region of quantum degeneracy (United States)

    Sotnikov, A. G.; Sereda, K. V.; Slyusarenko, Yu. V.


    Calculations of chemical potentials for ideal monatomic gases with Bose-Einstein and Fermi-Dirac statistics as functions of temperature, across the temperature region that is typical for the collective quantum degeneracy effect, are presented. Numerical calculations are performed without any additional approximations, and explicit dependences of the chemical potentials on temperature are constructed at a fixed density of gas particles. Approximate polynomial dependences of chemical potentials on temperature are obtained that allow for the results to be used in further studies without re-applying the involved numerical methods. The ease of using the obtained representations is demonstrated on examples of deformation of distribution for a population of energy states at low temperatures, and on the impact of quantum statistics (exchange interaction) on the equations of state for ideal gases and some of the thermodynamic properties thereof. The results of this study essentially unify two opposite limiting cases in an intermediate region that are used to describe the equilibrium states of ideal gases, which are well known from university courses on statistical physics, thus adding value from an educational point of view.

  8. Quantum criticality in photorefractive optics: Vortices in laser beams and antiferromagnets (United States)

    Čubrović, Mihailo; Petrović, Milan S.


    We study vortex patterns in a prototype nonlinear optical system: counterpropagating laser beams in a photorefractive crystal, with or without the background photonic lattice. The vortices are effectively planar and have two "flavors" because there are two opposite directions of beam propagation. In a certain parameter range, the vortices form stable equilibrium configurations which we study using the methods of statistical field theory and generalize the Berezinsky-Kosterlitz-Thouless transition of the XY model to the "two-flavor" case. In addition to the familiar conductor and insulator phases, we also have the perfect conductor (vortex proliferation in both beams or "flavors") and the frustrated insulator (energy costs of vortex proliferation and vortex annihilation balance each other). In the presence of disorder in the background lattice, a phase appears which shows long-range correlations and absence of long-range order, thus being analogous to glasses. An important benefit of this approach is that qualitative behavior of patterns can be known without intensive numerical work over large areas of the parameter space. The observed phases are analogous to those in magnetic systems, and make (classical) photorefractive optics a fruitful testing ground for (quantum) condensed matter systems. As an example, we map our system to a doped O(3 ) antiferromagnet with Z2 defects, which has the same structure of the phase diagram.

  9. Micromechanical measurement of beating patterns in the quantum oscillatory chemical potential of InGaAs quantum wells due to spin-orbit coupling

    Energy Technology Data Exchange (ETDEWEB)

    Herzog, Florian, E-mail:; Wilde, Marc A., E-mail: [Lehrstuhl für Physik funktionaler Schichtsysteme, Physik Department, Technische Universität München, James-Franck-Strasse 1, D-85748 Garching b. München (Germany); Heyn, Christian [Institut für Nanostruktur- und Festkörperphysik, Universität Hamburg, Jungiusstr. 11, D-20355 Hamburg (Germany); Hardtdegen, Hilde; Schäpers, Thomas [Peter Grünberg Institut (PGI-9) and JARA-FIT Jülich-Aachen Research Alliance, Forschungszentrum Jülich, D-52425 Jülich (Germany); Grundler, Dirk [Lehrstuhl für Physik funktionaler Schichtsysteme, Physik Department, Technische Universität München, James-Franck-Strasse 1, D-85748 Garching b. München (Germany); Laboratory of Nanoscale Magnetic Materials and Magnonics (LMGN), Institute of Materials, École Polytechnique Fédérale de Lausanne, CH-1015 Lausanne (Switzerland)


    The quantum oscillatory magnetization M(B) and chemical potential μ(B) of a two-dimensional (2D) electron system provide important and complementary information about its ground state energy at low temperature T. We developed a technique that provides both quantities in the same cool-down process via a decoupled static operation and resonant excitation of a micromechanical cantilever. On InGaAs/InP heterostructures, we observed beating patterns in both M(B) and μ(B) attributed to spin-orbit interaction. A significantly enhanced sensitivity in μ enabled us to extract Rashba and Dresselhaus parameters with high accuracy. The technique is powerful for detailed investigations on the electronic properties of 2D materials.

  10. Electronic in-plane symmetry breaking at field-tuned quantum criticality in CeRhIn5. (United States)

    Ronning, F; Helm, T; Shirer, K R; Bachmann, M D; Balicas, L; Chan, M K; Ramshaw, B J; McDonald, R D; Balakirev, F F; Jaime, M; Bauer, E D; Moll, P J W


    Electronic nematic materials are characterized by a lowered symmetry of the electronic system compared to the underlying lattice, in analogy to the directional alignment without translational order in nematic liquid crystals. Such nematic phases appear in the copper- and iron-based high-temperature superconductors, and their role in establishing superconductivity remains an open question. Nematicity may take an active part, cooperating or competing with superconductivity, or may appear accidentally in such systems. Here we present experimental evidence for a phase of fluctuating nematic character in a heavy-fermion superconductor, CeRhIn 5 (ref. 5). We observe a magnetic-field-induced state in the vicinity of a field-tuned antiferromagnetic quantum critical point at H c  ≈ 50 tesla. This phase appears above an out-of-plane critical field H* ≈ 28 tesla and is characterized by a substantial in-plane resistivity anisotropy in the presence of a small in-plane field component. The in-plane symmetry breaking has little apparent connection to the underlying lattice, as evidenced by the small magnitude of the magnetostriction anomaly at H*. Furthermore, no anomalies appear in the magnetic torque, suggesting the absence of metamagnetism in this field range. The appearance of nematic behaviour in a prototypical heavy-fermion superconductor highlights the interrelation of nematicity and unconventional superconductivity, suggesting nematicity to be common among correlated materials.

  11. Quantum chemical calculation and experimental measurement of the 13C chemical shift tensors of vanillin and 3,4-dimethoxybenzaldehyde (United States)

    Zheng, Guang; Hu, Jianzhi; Zhang, Xiaodong; Shen, Lianfang; Ye, Chaohui; Webb, Graham A.


    The principal values of the 13C nuclear magnetic resonance chemical shift tensors in vanillin and 3,4-dimethoxybenzaldehyde are reported. Theoretical results of the 13C chemical shift tensors were obtained by employing the gauge included atomic orbital (GIAO) approach. The geometrical parameters were optimized by using the MNDO method. The observed chemical shifts of these two compounds were determined in powders by using the recently introduced magic angle turning (MAT) experiment. The results presented in this paper clearly demonstrate the importance of using tensor information in the study of molecular structures.

  12. A-minor tertiary interactions in RNA kink-turns. Molecular dynamics and quantum chemical analysis. (United States)

    Réblová, Kamila; Šponer, Judit E; Špačková, Naďa; Beššeová, Ivana; Šponer, Jiří


    likely supported by the surrounding protein and RNA molecules. A-0 may also be stabilized by additional kink-turn nucleotides not belonging to the kink-turn consensus, as shown for the kink-turn from ribosomal Helix 15. Quantum-chemical calculations on all four A-minor triples suggest that there is a different balance of electrostatic and dispersion stabilization in the A-I/G═C and A-I/C═G triples, which may explain different behavior of these otherwise isosteric triples in the context of kink-turns. © 2011 American Chemical Society

  13. Role of the chemical bonding for the time-dependent electron transport through an interacting quantum dot

    KAUST Repository

    Goker, Ali


    A combination of ab initio and many-body calculations is utilized to determine the effects of the bonding in Au electrodes on the time dependent current through a quantum dot suddenly shifted into the Kondo regime by a gate voltage. For an asymmetrically coupled system the instantaneous conductance exhibits fluctuations. The frequencies of the fluctuations turn out to be proportional to the energetic separation between the dominating peaks in the density of states and the Fermi level. The chemical bonding in the electrodes, thus, drastically alters the transient current, which can be accessed by ultrafast pump-probe techniques. © 2011 Elsevier B.V. All rights reserved.

  14. Photocatalytic oxidation dynamics of acetone on TiO2: tight-binding quantum chemical molecular dynamics study

    International Nuclear Information System (INIS)

    Lv Chen; Wang Xiaojing; Agalya, Govindasamy; Koyama, Michihisa; Kubo, Momoji; Miyamoto, Akira


    The clarification of the excited states dynamics on TiO 2 surface is important subject for the design of the highly active photocatalysts. In the present study, we applied our novel tight-binding quantum chemical molecular dynamics method to the investigation on the photocatalytic oxidation dynamics of acetone by photogenerated OH radicals on the hydrated anatase TiO 2 surface. The elucidated photocatalytic reaction mechanism strongly supports the previous experimental proposal and finally the effectiveness of our new approach for the clarification of the photocatalytic reaction dynamics employing the large simulation model was confirmed

  15. Quantum chemical approach for condensed-phase thermochemistry (V): Development of rigid-body type harmonic solvation model (United States)

    Tarumi, Moto; Nakai, Hiromi


    This letter proposes an approximate treatment of the harmonic solvation model (HSM) assuming the solute to be a rigid body (RB-HSM). The HSM method can appropriately estimate the Gibbs free energy for condensed phases even where an ideal gas model used by standard quantum chemical programs fails. The RB-HSM method eliminates calculations for intra-molecular vibrations in order to reduce the computational costs. Numerical assessments indicated that the RB-HSM method can evaluate entropies and internal energies with the same accuracy as the HSM method but with lower calculation costs.

  16. Quantum chemical calculations of Cr2O3/SnO2 using density functional theory method (United States)

    Jawaher, K. Rackesh; Indirajith, R.; Krishnan, S.; Robert, R.; Das, S. Jerome


    Quantum chemical calculations have been employed to study the molecular effects produced by Cr2O3/SnO2 optimised structure. The theoretical parameters of the transparent conducting metal oxides were calculated using DFT / B3LYP / LANL2DZ method. The optimised bond parameters such as bond lengths, bond angles and dihedral angles were calculated using the same theory. The non-linear optical property of the title compound was calculated using first-order hyperpolarisability calculation. The calculated HOMO-LUMO analysis explains the charge transfer interaction between the molecule. In addition, MEP and Mulliken atomic charges were also calculated and analysed.

  17. Investigation of gold fluorides and noble gas complexes by matrix-isolation spectroscopy and quantum-chemical calculations. (United States)

    Wang, Xuefeng; Andrews, Lester; Willmann, Knut; Brosi, Felix; Riedel, Sebastian


    Noble with a difference: Matrix-isolation experiments and quantum-chemical calculations have led to the characterization of two new compounds, namely first open-shell binary gold fluoride, AuF(2), and a NeAuF complex. Moreover, ArAuF, AuF(3), Au(2)F(6), and monomeric AuF(5) have been produced and identified under cryogenic conditions in neon and argon matrices. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Trans Hoogsteen/sugar edge base pairing in RNA. Structures, energies, and stabilities from quantum chemical calculations

    Czech Academy of Sciences Publication Activity Database

    Mládek, Arnošt; Sharma, P.; Mitra, A.; Bhattacharyya, D.; Šponer, Jiří; Šponer, Judit E.


    Roč. 113, č. 6 (2009), s. 1743-1755 ISSN 1520-6106 R&D Projects: GA AV ČR(CZ) IAA400550701; GA AV ČR(CZ) IAA400040802; GA AV ČR(CZ) 1QS500040581; GA MŠk(CZ) LC06030 Grant - others:GA MŠk(CZ) LC512 Program:LC Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702; CEZ:AV0Z40550506 Keywords : quantum chemical calculations * base pairing * RNA Subject RIV: BO - Biophysics Impact factor: 3.471, year: 2009

  19. Lake Orta chemical status 25 years after liming: problems solved and emerging critical issues

    Directory of Open Access Journals (Sweden)

    Michela Rogora


    Full Text Available Lake Orta, located in Piedmont, northwestern Italy, has been severely affected by industrial pollution since the 1930s. A successful liming intervention, performed in 1988-1990, returned pH levels in the lake to neutrality, and accelerated the reduction of aqueous trace metal concentrations. In this paper, we present an update knowledge of the chemical status of Lake Orta, focusing on the data collected from 1990 to 2014. In this period we sampled the lake at its deepest point (Qualba station, on a monthly (1990-2000 or seasonal (since 2001 basis. Samples were collected at nine depths through the water column, and analyzed for pH, conductivity, alkalinity, major ions, nutrients, and trace metals. Collectively, these data allowed us to evaluate the long-term response of the lake to the restoration treatment, with particular regard to its acid-base status; they also provided insights into emerging or potential critical issues, including eutrophication and re-suspension of trace metals that still linger in the lake. Furthermore, the evaluation of the present chemical condition of the lake is a precondition for any successive restoration measure, such as fish introduction. The recent data confirmed the lake’s water quality has recovered, i.e. returned to a pre-pollution chemical state. Lake water values of pH and concentrations of ammonium, sulphate and base cations have stabilized. Alkalinity and nitrate concentrations are also expected to reach stable level in the next few years. Levels of nitrate, reactive silica, and phosphorus compounds are now regulated by algal uptake, providing indirect evidence of a partial biological recovery. For instance, both the inter-annual average decline and the reappearance of a seasonal signal in silica confirmed the presence of a stable diatom community. The lake is presently oligotrophic, and concentrations of both N and P compounds are steady and low throughout the year. However, a monthly check of nutrient

  20. Quantum Critical Point and Entanglement in a Matrix Product Ground State


    Tribedi, Amit; Bose, Indrani


    In this paper, we study the entanglement properties of a spin-1 model the exact ground state of which is given by a Matrix Product state. The model exhibits a critical point transition at a parameter value a=0. The longitudinal and transverse correlation lengths are known to diverge as a tends to zero. We use three different entanglement measures S(i) (the one-site von Neumann entropy), S(i,j) (the two-body entanglement) and G(2,n) (the generalized global entanglement) to determine the entang...

  1. Universal Signatures of Quantum Critical Points from Finite-Size Torus Spectra: A Window into the Operator Content of Higher-Dimensional Conformal Field Theories. (United States)

    Schuler, Michael; Whitsitt, Seth; Henry, Louis-Paul; Sachdev, Subir; Läuchli, Andreas M


    The low-energy spectra of many body systems on a torus, of finite size L, are well understood in magnetically ordered and gapped topological phases. However, the spectra at quantum critical points separating such phases are largely unexplored for (2+1)D systems. Using a combination of analytical and numerical techniques, we accurately calculate and analyze the low-energy torus spectrum at an Ising critical point which provides a universal fingerprint of the underlying quantum field theory, with the energy levels given by universal numbers times 1/L. We highlight the implications of a neighboring topological phase on the spectrum by studying the Ising* transition (i.e. the transition between a Z_{2} topological phase and a trivial paramagnet), in the example of the toric code in a longitudinal field, and advocate a phenomenological picture that provides qualitative insight into the operator content of the critical field theory.

  2. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment (United States)

    Pham, Chuyen V.; Krueger, Michael; Eck, Michael; Weber, Stefan; Erdem, Emre


    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g = 2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  3. Demonstration of a rapidly-swept external cavity quantum cascade laser for rapid and sensitive quantification of chemical mixtures (United States)

    Brumfield, B. E.; Taubman, M. S.; Phillips, M. C.


    A rapidly-swept external-cavity quantum cascade laser with an open-path Herriott cell is used to quantify gas-phase chemical mixtures of D2O and HDO at an update rate of 40 Hz (25 ms measurement time). The chemical mixtures were generated by evaporating D2O liquid near the open-path Herriott cell, allowing the H/D exchange reaction with ambient H2O to produce HDO. Fluctuations in the ratio of D2O and HDO on timescales of measurement time are estimated for D2O and HDO respectively with a 127 m optical path. These detection limits are reduced to 23.0 and 24.0 ppbv with a 1 s averaging time for D2O and HDO respectively. Detection limits measurement time.

  4. Quantum gases. Critical dynamics of spontaneous symmetry breaking in a homogeneous Bose gas. (United States)

    Navon, Nir; Gaunt, Alexander L; Smith, Robert P; Hadzibabic, Zoran


    Kibble-Zurek theory models the dynamics of spontaneous symmetry breaking, which plays an important role in a wide variety of physical contexts, ranging from cosmology to superconductors. We explored these dynamics in a homogeneous system by thermally quenching an atomic gas with short-range interactions through the Bose-Einstein phase transition. Using homodyne matter-wave interferometry to measure first-order correlation functions, we verified the central quantitative prediction of the Kibble-Zurek theory, namely the homogeneous-system power-law scaling of the coherence length with the quench rate. Moreover, we directly confirmed its underlying hypothesis, the freezing of the correlation length near the transition. Our measurements agree with a beyond-mean-field theory and support the expectation that the dynamical critical exponent for this universality class is z = 3/2. Copyright © 2015, American Association for the Advancement of Science.

  5. Chemically Triggered Formation of Two-Dimensional Epitaxial Quantum Dot Superlattices

    NARCIS (Netherlands)

    Walravens, Willem; De Roo, Jonathan; Drijvers, Emile; Ten Brinck, Stephanie; Solano, Eduardo; Dendooven, Jolien; Detavernier, Christophe; Infante, Ivan; Hens, Zeger


    Two dimensional superlattices of epitaxially connected quantum dots enable size-quantization effects to be combined with high charge carrier mobilities, an essential prerequisite for highly performing QD devices based on charge transport. Here, we demonstrate that surface active additives known to

  6. A Quantum Chemical Exploration of the Horner-Wadsworth-Emmons Reaction

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Martin, Ivar


    The mechanism of the Horner-Wadsworth-Emmons (HWE) reaction has been investigated using high level quantum mechanical calculations on a realistic model system. The solvation contribution has been evaluated using the PCM/DIR method. In the free, anionic system, the rate determining step was found...

  7. Aqueous synthesis of CdTe/CdS/ZnS quantum dots and their optical and chemical properties. (United States)

    Li, Zhong; Dong, Chaoqing; Tang, Lichuan; Zhu, Xin; Chen, Hongjin; Ren, Jicun


    In this paper, we described a strategy for synthesis of thiol-coated CdTe/CdS/ZnS (core-shell-shell) quantum dots (QDs) via aqueous synthesis approach. The synthesis conditions were systematically optimized, which included the size of CdTe core, the refluxing time and the number of monolayers and the ligands, and then the chemical and optical properties of the as-prepared products were investigated. We found that the mercaptopropionic acid (MPA)-coated CdTe/CdS/ZnS QDs presented highly photoluminescent quantum yields (PL QYs), good photostability and chemical stability, good salt tolerance and pH tolerance and favorable biocompatibility. The characterization of high-resolution transmission electron microscopy (HRTEM), X-ray powder diffraction (XRD) and fluorescence correlation spectroscopy (FCS) showed that the CdTe/CdS/ZnS QDs had good monodispersity and crystal structure. The fluorescence life time spectra demonstrated that CdTe/CdS/ZnS QDs had a longer lifetime in contrast to fluorescent dyes and CdTe QDs. Furthermore, the MPA-stabilized CdTe/CdS/ZnS QDs were applied for the imaging of cells. Compared with current synthesis methods, our synthesis approach was reproducible and simple, and the reaction conditions were mild. More importantly, our method was cost-effective, and was very suitable for large-scale synthesis of CdTe/CdS/ZnS QDs for future applications. Copyright © 2010 John Wiley & Sons, Ltd.

  8. Time-Resolved Quantum Cascade Laser Absorption Spectroscopy of Pulsed Plasma Assisted Chemical Vapor Deposition Processes Containing BCl3 (United States)

    Lang, Norbert; Hempel, Frank; Strämke, Siegfried; Röpcke, Jürgen


    In situ measurements are reported giving insight into the plasma chemical conversion of the precursor BCl3 in industrial applications of boriding plasmas. For the online monitoring of its ground state concentration, quantum cascade laser absorption spectroscopy (QCLAS) in the mid-infrared spectral range was applied in a plasma assisted chemical vapor deposition (PACVD) reactor. A compact quantum cascade laser measurement and control system (Q-MACS) was developed to allow a flexible and completely dust-sealed optical coupling to the reactor chamber of an industrial plasma surface modification system. The process under the study was a pulsed DC plasma with periodically injected BCl3 at 200 Pa. A synchronization of the Q-MACS with the process control unit enabled an insight into individual process cycles with a sensitivity of 10-6 cm-1·Hz-1/2. Different fragmentation rates of the precursor were found during an individual process cycle. The detected BCl3 concentrations were in the order of 1014 molecules·cm-3. The reported results of in situ monitoring with QCLAS demonstrate the potential for effective optimization procedures in industrial PACVD processes.

  9. Complementing high-throughput X-ray powder diffraction data with quantum-chemical calculations: Application to piroxicam form III. (United States)

    Naelapää, Kaisa; van de Streek, Jacco; Rantanen, Jukka; Bond, Andrew D


    High-throughput crystallisation and characterisation platforms provide an efficient means to carry out solid-form screening during the pre-formulation phase. To determine the crystal structures of identified new solid phases, however, usually requires independent crystallisation trials to produce single crystals or bulk samples of sufficient quantity to carry out high-quality X-ray diffraction measurements. This process could be made more efficient by a robust procedure for crystal structure determination directly from high-throughput X-ray powder diffraction (XRPD) data. Quantum-chemical calculations based on dispersion-corrected density functional theory (DFT-D) have now become feasible for typical small organic molecules used as active pharmaceutical ingredients. We demonstrate how these calculations can be applied to complement high-throughput XRPD data by determining the crystal structure of piroxicam form III. These combined experimental/quantum-chemical methods can provide access to reliable structural information in the course of an intensive experimentally based solid-form screening activity or in other circumstances wherein single crystals might never be viable, for example, for polymorphs obtained only during high-energy processing such as spray drying or milling. Copyright © 2012 Wiley Periodicals, Inc.

  10. Prediction of Radical Scavenging Activities of Anthocyanins Applying Adaptive Neuro-Fuzzy Inference System (ANFIS) with Quantum Chemical Descriptors (United States)

    Jhin, Changho; Hwang, Keum Taek


    Radical scavenging activity of anthocyanins is well known, but only a few studies have been conducted by quantum chemical approach. The adaptive neuro-fuzzy inference system (ANFIS) is an effective technique for solving problems with uncertainty. The purpose of this study was to construct and evaluate quantitative structure-activity relationship (QSAR) models for predicting radical scavenging activities of anthocyanins with good prediction efficiency. ANFIS-applied QSAR models were developed by using quantum chemical descriptors of anthocyanins calculated by semi-empirical PM6 and PM7 methods. Electron affinity (A) and electronegativity (χ) of flavylium cation, and ionization potential (I) of quinoidal base were significantly correlated with radical scavenging activities of anthocyanins. These descriptors were used as independent variables for QSAR models. ANFIS models with two triangular-shaped input fuzzy functions for each independent variable were constructed and optimized by 100 learning epochs. The constructed models using descriptors calculated by both PM6 and PM7 had good prediction efficiency with Q-square of 0.82 and 0.86, respectively. PMID:25153627

  11. An investigation into the effective surface passivation of quantum dots by a photo-assisted chemical method (United States)

    Joo, So-Yeong; Park, Hyun-Su; Kim, Do-yeon; Kim, Bum-Sung; Lee, Chan Gi; Kim, Woo-Byoung


    In this study, we have developed an effective amino passivation process for quantum dots (QDs) at room temperature and have investigated a passivation mechanism using a photo-assisted chemical method. As a result of the reverse reaction of the H2O molecules, the etching kinetics of the photo-assisted chemical method increased upon increasing the 3-amino-1-propanol (APOL)/H2O ratio of the etching solution. Photon-excited electron-hole pairs lead to strong bonding between the organic and surface atoms of the QDs, and results in an increase of the quantum yield (QY%). This passivation method is also applicable to CdSe/ZnSe core/shell structures of QDs, due to the passivation of mid-gap defects states at the interface. The QY% of the as-synthesized CdSe QDs is dramatically enhanced by the amino passivation from 37% to 75% and the QY% of the CdSe/ZnSe core/shell QDs is also improved by ˜28%.

  12. Chemical potential for the interacting classical gas and the ideal quantum gas obeying a generalized exclusion principle

    International Nuclear Information System (INIS)

    Sevilla, F J; Olivares-Quiroz, L


    In this work, we address the concept of the chemical potential μ in classical and quantum gases towards the calculation of the equation of state μ = μ(n, T) where n is the particle density and T the absolute temperature using the methods of equilibrium statistical mechanics. Two cases seldom discussed in elementary textbooks are presented with detailed calculations. The first one refers to the explicit calculation of μ for the interacting classical gas exemplified by van der Waals gas. For this purpose, we used the method described by van Kampen (1961 Physica 27 783). The second one refers to the calculation of μ for ideal quantum gases that obey a generalized Pauli's exclusion principle that leads to statistics that go beyond the Bose-Einstein and Fermi-Dirac cases. The audience targeted in this work corresponds mainly to advanced undergraduates and graduate students in the physical-chemical sciences but it is not restricted to them. In regard of this, we have put a special emphasis on showing some additional details of calculations that usually do not appear explicitly in textbooks. (paper)

  13. Quantum-chemical study and FTIR jet spectroscopy of CHCl(3)-NH(3) association in the gas phase. (United States)

    Hippler, Michael; Hesse, Susanne; Suhm, Martin A


    High level ab initio quantum chemical calculations have been performed on the association of chloroform with ammonia in the gas phase (counterpoise corrected MP2 and coupled-cluster CCSD(T) calculations with 6-311++G(d,p) basis functions). Minimum energy equilibrium structures have been found for CHCl(3)-NH(3) dimer, CHCl(3)-(NH(3))(2) trimer and CHCl(3)-(NH(3))(3) tetramer. Association is characterised by a CHN hydrogen bond between a chloroform and an ammonia molecule, with further ammonia units attached by hydrogen bonds to ammonia and by an electrostatic NHCl interaction to chloroform. Cooperative effects provide additional stabilisation. The complexes exhibit characteristic shifts of vibrational bands and change of IR intensity; in particular there is a pronounced progressive shift of the CH-stretching vibration towards lower wavenumber with each unit of ammonia attached in the complex. The shift is accompanied by an up to 600 fold increase in IR intensity. The experimental FTIR jet spectra have provided firm evidence of CHCl(3)-NH(3) association, with the clearest effects seen in the region of the CH-stretching vibration. First tentative assignments have been made based on the dependence of relative intensities of cluster features on the concentration of monomers, and assignments have been corroborated by the quantum chemical calculations. The present combined ab initio and FTIR spectroscopy study reveals the structure and energetics of cluster formation and intermolecular bonding in CHCl(3)-NH(3) association.

  14. An investigation into the effective surface passivation of quantum dots by a photo-assisted chemical method

    Directory of Open Access Journals (Sweden)

    So-Yeong Joo


    Full Text Available In this study, we have developed an effective amino passivation process for quantum dots (QDs at room temperature and have investigated a passivation mechanism using a photo-assisted chemical method. As a result of the reverse reaction of the H2O molecules, the etching kinetics of the photo-assisted chemical method increased upon increasing the 3-amino-1-propanol (APOL/H2O ratio of the etching solution. Photon-excited electron-hole pairs lead to strong bonding between the organic and surface atoms of the QDs, and results in an increase of the quantum yield (QY%. This passivation method is also applicable to CdSe/ZnSe core/shell structures of QDs, due to the passivation of mid-gap defects states at the interface. The QY% of the as-synthesized CdSe QDs is dramatically enhanced by the amino passivation from 37% to 75% and the QY% of the CdSe/ZnSe core/shell QDs is also improved by ∼28%.

  15. Intra- und intermolecular hydrogen bonds. Spectroscopic, quantum chemical and molecular dynamics studies

    International Nuclear Information System (INIS)

    Simperler, A.


    Intra- and intermolecular H-bonds have been investigated with spectroscopic, quantum chemical, and molecular dynamics methods. The work is divided into the following three parts: 1. Intramolecular interactions in ortho-substituted phenols. Theoretical and experimental data that characterizes the intramolecular hydrogen bonds in 48 different o-substituted phenols are discussed. The study covers various kinds of O-H ... Y -type interactions (Y= N, O, S, F, Cl, Br, I, C=C, C=-C, and C-=N). The bond strength sequences for several series of systematically related compounds as obtained from IR spectroscopy data (i.e., v(OH) stretching frequencies) are discussed and reproduced with several theoretical methods (B3LYP/6-31G(d,p), B3LYP/6-311G(d,p), B3LYP/6-31++G(d,p), B3LYP/DZVP, MP2/6-31G(d,p), and MP2/6-31++G(d,p) levels of theory). The experimentally determined sequences are interpreted in terms of the intrinsic properties of the molecules: hydrogen bond distances, Mulliken partial charges, van der Waals radii, and electron densities of the Y-proton acceptors. 2. Competitive hydrogen bonds and conformational equilibria in 2,6-disubstituted phenols containing two different carbonyl substituents. The rotational isomers of ten unsymmetrical 2,6-disubstituted phenols as obtained by combinations of five different carbonyl substituents (COOH, COOCH 3 , CHO, COCH 3 , and CONH 2 ) have been theoretically investigated at the B3LYP/6-31G(d,p) level of theory. The relative stability of four to five conformers of each compound were determined by full geometry optimization for free molecules as well as for molecules in reaction fields with dielectric constants up to ε=37.5. A comparison with IR spectroscopic data of available compounds revealed excellent agreement with the theoretically predicted stability sequences and conformational equilibria. The stability of a conformer could be interpreted to be governed by the following two contributions: (i) an attractive hydrogen bond

  16. A critical Action Research approach to curriculum development in a laboratory-based chemical engineering course (United States)

    White, Scott R.

    This dissertation is a report of an attempt to critically evaluate a novel laboratory course from within the context of a chemical engineering curriculum. The research was done in a college classroom-laboratory setting, entrenched in the everydayness of classroom activities. All of the students, instructors, and educational researchers were knowing participants in this Action Research study. The students, a mixture of juniors, seniors, & graduate students, worked together on semester-long projects in groups that were mixed by age, gender and academic level. Qualitative techniques were used to gather different forms of representations of the students and instructors' experiences. Emergent patterns from the data gave strength to emergent knowledge claims that informed the instructors and the researcher about what the students were learning about performing experimental work and communicating results with their peers and instructor. The course challenged and in some cases changed the conceptions of instruction previously held by the students and the instructors. The course did not proceed without problems, yet the majority of these problems were overcome by the design of the course. Assertions and recommendations for improvement and application to other educational contexts are suggested.

  17. The critical role of didodecyldimethylammonium bromide on physico-chemical, technological and biological properties of NLC. (United States)

    Carbone, C; Campisi, A; Manno, D; Serra, A; Spatuzza, M; Musumeci, T; Bonfanti, R; Puglisi, G


    Exploiting the experimental factorial design and the potentiality of Turbiscan AG Station, we developed and characterized unmodified and DDAB-coated NLC prepared by a low energy organic solvent free phase inversion temperature technique. A 22 full factorial experimental design was developed in order to study the effects of two independent variables (DDAB and ferulic acid) and their interaction on mean particle size and zeta potential values. The factorial planning was validated by ANOVA analysis; the correspondence between the predicted values of size and zeta and those measured experimentally confirmed the validity of the design and the equation applied for its resolution. The DDAB-coated NLC were significantly affected in their physico-chemical properties by the presence of DDAB, as showed by the results of the experimental design. The coated NLC showed higher physical stability with no particles aggregation compared to the unmodified NLC, as demonstrated by Turbiscan(®) AGS measurements. X-ray diffraction, Raman spectroscopy and Cryo-TEM images allowed us to assert that DDAB plays a critical role in increasing the lipids structural order with a consequent enhancement of the NLC physical stability. Furthermore, the results of the in vitro biological studies allow the revisiting of the role of DDAB to the benefit of glioblastoma treatment, due to its efficacy in increasing the NLC uptake and reducing the viability of human glioblastoma cancer cells (U87MG). Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Antiferromagnetic and Orbital Ordering on a Diamond Lattice Near Quantum Criticality

    Directory of Open Access Journals (Sweden)

    K. W. Plumb


    Full Text Available We present neutron scattering measurements on powder samples of the spinel FeSc_{2}S_{4} that reveal a previously unobserved magnetic ordering transition occurring at 11.8(2 K. Magnetic ordering occurs subsequent to a subtle cubic-to-tetragonal structural transition that distorts Fe coordinating sulfur tetrahedra and lifts the orbital degeneracy. The orbital ordering is not truly long ranged, but occurs over finite-sized domains that limit magnetic correlation lengths. The application of 1 GPa hydrostatic pressure appears to destabilize this Néel state, reducing the transition temperature to 8.6(8 K and redistributing magnetic spectral weight to higher energies. The relative magnitudes of ordered ⟨m⟩^{2}=3.1(2 μ_{B}^{2} and fluctuating moments ⟨δm⟩=13(1 μ_{B}^{2} show that the magnetically ordered state of FeSc_{2}S_{4} is drastically renormalized and close to criticality.

  19. Chemical Reaction CO+OH(•) → CO2+H(•) Autocatalyzed by Carbon Dioxide: Quantum Chemical Study of the Potential Energy Surfaces. (United States)

    Masunov, Artëm E; Wait, Elizabeth; Vasu, Subith S


    The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO2 to OH radical and CO molecule, hydrogen transfer from oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO2 medium. It may open a new venue for controlling reaction rates for chemical manufacturing.

  20. dx^2-y^2 paring symmetry of heavy fermion CeIrIn5 remote from antiferromagnetic quantum critical point (United States)

    Kasahara, Yuichi; Iwasawa, T.; Shimizu, Y.; Shishido, H.; Shibauchi, T.; Vekhter, I.; Matsuda, Y.


    Quasi-two dimensional heavy Fermion CeIrIn5 involves two distinct superconducting domes in the phase diagram, which appear as a function of pressure or Rh substitution of Ir. In the analogy to CeCu2Si2, two distinct superconducting domes with different symmetry has been invoked. We report on the results of low-temperature thermal transport of CeIrIn5 in the second dome, which locates away from an antiferromagnetic quantum critical point. The thermal conductivity is measured under a magnetic field rotated with respect to the crystal axes, which give direct evidence for superconducting gap structure. Clear fourfold oscillation with minima at [110] and [1-10] directions is observed as rotating magnetic field within the basal ab-plane, while no oscillation is observed within the bc-plane. In sharp contrast to previous reports that suggested Eg symmetry with horizontal line node within the ab-plane [1], our results are most consistent with dx^2- y^2 symmetry with vertical line nodes along the c-axis. These results imply that two superconducting domes have the same gap symmetry which appears to be mediated by antiferromagnetic spin fluctuations. [1] H. Shakeripour et al., Phys. Rev. Lett. 99, 187004 (2007).

  1. The critical review of methodologies and approaches to assess the inherent skin sensitization potential (skin allergies) of chemicals. Part II

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre


    To identify specific cases, classes or specific use situations of chemicals for which 'safety thresholds' or 'safety limits' were set (in regulations, standards, in scientific research/clinical work, etc.) and critically review the scientific and methodological parameters used to set those limits....

  2. Synthesis of copper quantum dots by chemical reduction method and tailoring of its band gap

    Energy Technology Data Exchange (ETDEWEB)

    Prabhash, P. G.; Nair, Swapna S., E-mail: [Department of Physics, School of Mathematical and Physical Sciences, Central University of Kerala, Kasaragod, Kerala - 671 314 (India)


    Metallic copper nano particles are synthesized with citric acid and CTAB (cetyltrimethylammonium bromide) as surfactant and chlorides as precursors. The particle size and surface morphology are analyzed by High Resolution Transmission Electron Microscopy. The average size of the nano particle is found to be 3 - 10 nm. The optical absorption characteristics are done by UV-Visible spectrophotometer. From the Tauc plots, the energy band gaps are calculated and because of their smaller size the particles have much higher band gap than the bulk material. The energy band gap is changed from 3.67 eV to 4.27 eV in citric acid coated copper quantum dots and 4.17 eV to 4.52 eV in CTAB coated copper quantum dots.

  3. Synthesis of copper quantum dots by chemical reduction method and tailoring of its band gap (United States)

    Prabhash, P. G.; Nair, Swapna S.


    Metallic copper nano particles are synthesized with citric acid and CTAB (cetyltrimethylammonium bromide) as surfactant and chlorides as precursors. The particle size and surface morphology are analyzed by High Resolution Transmission Electron Microscopy. The average size of the nano particle is found to be 3 - 10 nm. The optical absorption characteristics are done by UV-Visible spectrophotometer. From the Tauc plots, the energy band gaps are calculated and because of their smaller size the particles have much higher band gap than the bulk material. The energy band gap is changed from 3.67 eV to 4.27 eV in citric acid coated copper quantum dots and 4.17 eV to 4.52 eV in CTAB coated copper quantum dots.

  4. Synthesis of copper quantum dots by chemical reduction method and tailoring of its band gap

    Directory of Open Access Journals (Sweden)

    P. G. Prabhash


    Full Text Available Metallic copper nano particles are synthesized with citric acid and CTAB (cetyltrimethylammonium bromide as surfactant and chlorides as precursors. The particle size and surface morphology are analyzed by High Resolution Transmission Electron Microscopy. The average size of the nano particle is found to be 3 - 10 nm. The optical absorption characteristics are done by UV-Visible spectrophotometer. From the Tauc plots, the energy band gaps are calculated and because of their smaller size the particles have much higher band gap than the bulk material. The energy band gap is changed from 3.67 eV to 4.27 eV in citric acid coated copper quantum dots and 4.17 eV to 4.52 eV in CTAB coated copper quantum dots.

  5. The bell that rings light a primer in quantum mechanics and chemical bonding

    CERN Document Server

    Wallace, Dorothy


    This book is an introduction to quantum mechanics and mathematics that leads to the solution of the Schrodinger equation. It can be read and understood by undergraduates without sacrificing the mathematical details necessary for a complete solution giving the shapes of molecular orbitals seen in every chemistry text. Readers are introduced to many mathematical topics new to the undergraduate curriculum, such as basic representation theory, Schur's lemma, and the Legendre polynomials.

  6. Synthesis and characterization of CdSe quantum dots dispersed in PVA matrix by chemical route

    Energy Technology Data Exchange (ETDEWEB)

    Khan, Zubair M. S. H.; Ganaie, Mohsin; Husain, M.; Zulfequar, M., E-mail: [Department of Physics, Jamia Millia Islamia, New Delhi-110025 (India); Khan, Shamshad A. [Department of Physics St. Andrews College, Gorakhpur-273001,U.P,-India (India)


    CdSe quantum dots using polyvinyl alcohol as a capping agent have been synthesized via a simple heat induced thermolysis technique. The structural analysis of CdSe/PVA thin film was studied by X-ray diffraction, which confirms crystalline nature of the prepared film. The surface morphology and particle size of the prepared sample was studied by Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM). The SEM studies of CdSe/PVA thin film shows the average size of particles in the form of clusters of several quantum dots in the range of 10-20 nm. The morphology of CdSe/PVA thin film was further examined by TEM. The TEM image shows the fringes of tiny dots with average sizes of 4-7 nm. The optical properties of CdSe/PVA thin film were studied by UV-VIS absorption spectroscopy. The CdSe/PVA quantum dots follow the role of direct transition and the optical band gap is found to be 4.03 eV. From dc conductivity measurement, the observed value of activation energy was found to be 0.71 eV.

  7. Developing Quantum Chemical and Polyparameter Models for Predicting Environmentally Significant Parameters for New Munition Compounds (United States)


    solute partition coefficient between two phases, K, for the changes in molecular interaction energies involved in transferring a chemical between the...Office of chemical safety and pollution prevention. Washington, D.C: US EPA. 2012. 46. American Society for Testing and Materials. E1963 − 09: Standard...

  8. Identification of critical chemical features for Aurora kinase-B inhibitors using Hip-Hop, virtual screening and molecular docking (United States)

    Sakkiah, Sugunadevi; Thangapandian, Sundarapandian; John, Shalini; Lee, Keun Woo


    This study was performed to find the selective chemical features for Aurora kinase-B inhibitors using the potent methods like Hip-Hop, virtual screening, homology modeling, molecular dynamics and docking. The best hypothesis, Hypo1 was validated toward a wide range of test set containing the selective inhibitors of Aurora kinase-B. Homology modeling and molecular dynamics studies were carried out to perform the molecular docking studies. The best hypothesis Hypo1 was used as a 3D query to screen the chemical databases. The screened molecules from the databases were sorted based on ADME and drug like properties. The selective hit compounds were docked and the hydrogen bond interactions with the critical amino acids present in Aurora kinase-B were compared with the chemical features present in the Hypo1. Finally, we suggest that the chemical features present in the Hypo1 are vital for a molecule to inhibit the Aurora kinase-B activity.

  9. Quantum-chemical, NMR, FT IR, and ESI MS studies of complexes of colchicine with Zn(II). (United States)

    Jankowski, Wojciech; Kurek, Joanna; Barczyński, Piotr; Hoffmann, Marcin


    Colchicine is a tropolone alkaloid from Colchicinum autumnale. It shows antifibrotic, antimitotic, and anti-inflammatory activities, and is used to treat gout and Mediterranean fever. In this work, complexes of colchicine with zinc(II) nitrate were synthesized and investigated using DFT, 1 H and 13 C NMR, FT IR, and ESI MS. The counterpoise-corrected and uncorrected interaction energies of these complexes were calculated. We also calculated their 1 H, 13 C NMR, and IR spectra and compared them with the corresponding experimentally obtained data. According to the ESI MS mass spectra, colchicine forms stable complexes with zinc(II) nitrate that have various stoichiometries: 2:1, 1:1:1, and 2:1:1 with respect to colchichine, Zn(II), and nitrate ion. All of the complexes were investigated using the quantum theory of atoms in molecules (QTAIM). The calculated and the measured spectra showed differences before and after the complexation process. Calculated electron densities and bond critical points indicated the presence of bonds between the ligands and the central cation in the investigated complexes that satisfied the quantum theory of atoms in molecules. Graphical Abstract DFT, NMR, FT IR, ESI MS, QTAIM and puckering studies of complexes of colchicine with Zn(II).

  10. The effect of cadmium vacancies on the optical properties of chemically prepared CdS quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Madan, Shikha; Kumar, Jitender; Singh, Inderpreet; Madhwal, Devinder; Bhatnagar, P K; Mathur, P C, E-mail: [Material Science Laboratory, Department of Electronic Science, University of Delhi South Campus, Benito Juarez Road, New Delhi-110021 (India)


    CdS quantum dots (QDs) in a polyvinyl alcohol (PVA) matrix have been grown by a chemical method and are characterized by transmission electron microscopy (TEM), UV-vis absorption, photoluminescence (PL) and energy dispersive x-ray diffraction (EDX). TEM studies of CdS films show that a nearly spherical cluster of CdS QDs with an average radius of 10-15 nm is formed. From absorption measurements, it is observed that with increasing the PVA concentration from 5 to 8 wt.%, the absorption edge shifts from 3.1 to 3.6 eV, which is attributed to an increase in quantum confinement with decreasing the QD size. PL studies in an energy range of 1.8-3.3 eV show two distinct peaks. The higher-energy peak corresponds to band edge emission, whereas the lower-energy peak corresponds to defect emission. EDX results revealed that the atomic concentration of cadmium is much lower than that of sulfur, indicating that cadmium vacancies are predominant. It was concluded that cadmium vacancies are mainly responsible for defect emission in the PL spectrum.

  11. A new low temperature solid modification in 1-isothiocyanato-4-(trans‑4-propylcyclohexyl)benzene (3CHBT) probed by Raman spectroscopy and quantum chemical calculations (United States)

    Vikram, K.; Singh, Ranjan K.; Gupta, Satyendra Nath


    Raman spectra of 1-isothiocyanato-4-(trans 4-propylcyclohexyl)benzene (3CHBT) were studied in the region, 1450-2300 cm- 1 at twenty two different temperatures in the range, 83-293 K in cooling and heating cycles. All bands in this region were critically evaluated in term of linewidth, peak position and relative intensity. Raman bands at 2085 cm- 1 and 2120 cm- 1 shows clear evidence of a solid modification through anomaly in temperature dependence peak positions and linewidths variation in the temperature range 173-203 K. A detailed analysis of the variation of the linewidth and peak position of the two component bands leads to the conclusion that the molecular/dimer arrangement in crystalline packing changed between 173 K and 203 K. This solid modification was also analyzed at the molecular level. The 2085 cm- 1 and 2120 cm- 1 bands were corresponded as parallel and anti-parallel dimers of 3CHBT, which are identified as dimer I (D1) and dimer II (D2), respectively. The structures of both the dimers have been optimized by quantum chemical calculations employing density functional theoretic (DFT) methods.

  12. NMR chemical shift and J coupling parameterization and quantum mechanical reference spectrum simulation for selected nerve agent degradation products in aqueous conditions. (United States)

    Koskela, Harri; Anđelković, Boban


    The spectral parameters of selected nerve agent degradation products relevant to the Chemical Weapons Convention, namely, ethyl methylphosphonate, isopropyl methylphosphonate, pinacolyl methylphosphonate and methylphosphonic acid, were studied in wide range of pH conditions and selected temperatures. The pH and temperature dependence of chemical shifts and J couplings was parameterized using Henderson-Hasselbalch-based functions. The obtained parameters allowed calculation of precise chemical shifts and J coupling constants in arbitrary pH conditions and typical measurement temperatures, thus facilitating quantum mechanical simulation of reference spectra in the chosen magnetic field strength for chemical verification. Copyright © 2017 John Wiley & Sons, Ltd. Copyright © 2017 John Wiley & Sons, Ltd.

  13. Prebiotic routes to nucleosides: A quantum chemical insight into the energetics of the multistep reaction pathways

    Czech Academy of Sciences Publication Activity Database

    Šponer, Judit E.; Šponer, Jiří; Fuentes-Cabrera, M.


    Roč. 17, č. 3 (2011), s. 847-854 ISSN 0947-6539 R&D Projects: GA MŠk(CZ) LC06030; GA AV ČR(CZ) IAA400040802; GA ČR(CZ) GAP208/10/2302; GA ČR(CZ) GA203/09/1476; GA ČR(CZ) GD203/09/H046 Grant - others:GA MŠk(CZ) LC512 Program:LC Institutional research plan: CEZ:AV0Z50040507; CEZ:AV0Z50040702 Keywords : quantum chemistry * prebiotic chemistry * RNA Subject RIV: BO - Biophysics Impact factor: 5.925, year: 2011

  14. Resonance Raman and quantum chemical studies of short polyene radical cations

    DEFF Research Database (Denmark)

    Keszthelyi, T.; Wilbrandt, R.; Bally, T.


    The results of our investigations of the geometric and vibrational structures of some short conjugated polyene radical cations are reported. The radical cations of 1,3-butadiene and three of its deuterated isotopomers, trans- and cis-1,3-pentadiene, 2-methyl-1,3-butadiene, and E- and Z-1...... and to assist assignment of the resonance Raman spectra. A new and improved scaled quantum mechanical force field for the butadiene radical cation was also determined. The presence of more than one rotamer was observed in all the polyene radical cations we investigated. (C) 1997 Elsevier Science B.V....

  15. Wavelength tuning of InAs quantum dots grown on InP (100) by chemical-beam epitaxy

    International Nuclear Information System (INIS)

    Gong, Q.; Noetzel, R.; Veldhoven, P.J. van; Eijkemans, T.J.; Wolter, J.H.


    We report on an effective way to continuously tune the emission wavelength of InAs quantum dots (QDs) grown on InP (100) by chemical-beam epitaxy. The InAs QD layer is embedded in a GaInAsP layer lattice matched to InP. With an ultrathin GaAs layer inserted between the InAs QD layer and the GaInAsP buffer, the peak wavelength from the InAs QDs can be continuously tuned from above 1.6 μm down to 1.5 μm at room temperature. The major role of the thin GaAs layer is to greatly suppress the As/P exchange during the deposition of InAs and subsequent growth interruption under arsenic flux, as well as to consume the segregated surface In layer floating on the GaInAsP buffer layer

  16. Atmospheric-pressure epitaxial growth technique of a multiple quantum well by mist chemical vapor deposition based on Leidenfrost droplets (United States)

    Kawaharamura, Toshiyuki; Dang, Giang T.; Nitta, Noriko


    A multiple quantum well α-Fe2O3/α-Ga2O3 with parallel and coherent formation of uniform and highly single-crystalline layers on a sapphire substrate has been fabricated by open-air atmospheric-pressure solution-processed mist chemical vapor deposition (Mist CVD). This report demonstrates that complicated structures with atomic-level control can be fabricated even in non-vacuum conditions by the Mist CVD. This can be achieved via the precise control of the precursor flow and ambient temperature combined with the formation of mist droplets of the special Leidenfrost state, which increased the atomic migration length by 108 times more than that of traditional vacuum techniques. This work could be a milestone in the transformation from vacuum to non-vacuum thin film deposition techniques towards a green and sustainable industry.

  17. Quantum chemical investigation of the thermal pyrolysis reactions of the carboxylic group in a brown coal model. (United States)

    Liu, Shengyu; Zhang, Zhiqiang; Wang, Huifang


    Different reaction pathways of the carboxylic group in a brown coal model were investigated by applying density function quantum chemical theory, examining the possible cross-linking and decomposition reactions between the hydrogen bonded carboxylic group-carboxylic group and the carboxylic group-hydroxyl group during the thermal pyrolysis process. The results show that bimolecular dehydration and decarboxylation of hydrogen bonded carboxylic groups have distinctly lower activation barriers and therefore, proceed preferentially at low temperature. The esterification reaction between the hydrogen bonded carboxylic group and hydroxyl group, together with unimolecular decarboxylation of isolated single carboxylic groups were also possible at moderate temperature. Aryl-aryl coupling is thought to occur via radical pyrolysis and recombination at relatively high temperature.

  18. Interwell coupling effect in Si/SiGe quantum wells grown by ultra high vacuum chemical vapor deposition

    Directory of Open Access Journals (Sweden)

    Loh Ter-Hoe


    Full Text Available AbstractSi/Si0.66Ge0.34coupled quantum well (CQW structures with different barrier thickness of 40, 4 and 2 nm were grown on Si substrates using an ultra high vacuum chemical vapor deposition (UHV-CVD system. The samples were characterized using high resolution x-ray diffraction (HRXRD, cross-sectional transmission electron microscopy (XTEM and photoluminescence (PL spectroscopy. Blue shift in PL peak energy due to interwell coupling was observed in the CQWs following increase in the Si barrier thickness. The Si/SiGe heterostructure growth process and theoretical band structure model was validated by comparing the energy of the no-phonon peak calculated by the 6 + 2-bandk·pmethod with experimental PL data. Close agreement between theoretical calculations and experimental data was obtained.

  19. A modular architecture for multi-channel external cavity quantum cascade laser-based chemical sensors: a systems approach

    Energy Technology Data Exchange (ETDEWEB)

    Taubman, Matthew S.; Myers, Tanya L.; Bernacki, Bruce E.; Stahl, Robert D.; Cannon, Bret D.; Schiffern, John T.; Phillips, Mark C.


    A multi-channel laser-based chemical sensor platform is presented, in which a modular architecture allows the exchange of complete sensor channels without disruption to overall operation. Each sensor channel contains custom optical and electronics packages, which can be selected to access laser wavelengths, interaction path lengths and modulation techniques optimal for a given application or mission. Although intended primarily to accommodate mid-infrared (MIR) external cavity quantum cascade lasers (ECQCLs)and astigmatic Herriott cells, channels using visible or near infrared (NIR) lasers or other gas cell architectures can also be used, making this a truly versatile platform. Analog and digital resources have been carefully chosen to facilitate small footprint, rapid spectral scanning, ow-noise signal recovery, failsafe autonomous operation, and in-situ chemometric data analysis, storage and transmission. Results from the demonstration of a two-channel version of this platform are also presented.

  20. Combined EXAFS Spectroscopic and Quantum Chemical Study on the Complex Formation of Am(III) with Formate. (United States)

    Fröhlich, Daniel R; Kremleva, Alena; Rossberg, André; Skerencak-Frech, Andrej; Koke, Carsten; Krüger, Sven; Rösch, Notker; Panak, Petra J


    The complexation of Am(III) with formate in aqueous solution is studied as a function of the pH value using a combination of extended X-ray absorption fine structure (EXAFS) spectroscopy, iterative transformation factor analysis (ITFA), and quantum chemical calculations. The Am L III -edge EXAFS spectra are analyzed to determine the molecular structure (coordination numbers; Am-O and Am-C distances) of the formed Am(III)-formate species and to track the shift of the Am(III) speciation with increasing pH. The experimental data are compared to predictions from density functional calculations. The results indicate that formate binds to Am(III) in a monodentate fashion, in agreement with crystal structures of lanthanide formates. Furthermore, the investigations are complemented by thermodynamic speciation calculations to verify further the results obtained.

  1. A quantum chemical analysis of Zn and Sb doping and co-doping in SnO2

    Directory of Open Access Journals (Sweden)

    Luis Villamagua


    Full Text Available This work presents a quantum chemical study of Zn and Sb doping and co-doping in SnO2 carried out by a DFT+U method. The analysis has been developed by introducing three different modifications in the otherwise pure SnO2 system. In the first place, an oxygen vacancy was introduced within the crystal. Following, such a system was doped (separately by Zn or Sb impurities. Finally, the best energetic positions for both Zn and Sb atoms were simultaneously introduced within the lattice. Results of the simulations show that the confined charge that appeared due to the introduction of the oxygen vacancy interacts with the dopants atoms, being this interaction mostly responsible of the observed effects, i.e., EG shrinkage, F-centers formations, and magnetic momentum rise.

  2. Quantum chemical modeling of the reaction path of chorismate mutase based on the experimental substrate/product complex. (United States)

    Burschowsky, Daniel; Krengel, Ute; Uggerud, Einar; Balcells, David


    Chorismate mutase is a well-known model enzyme, catalyzing the Claisen rearrangement of chorismate to prephenate. Recent high-resolution crystal structures along the reaction coordinate of this enzyme enabled computational analyses at unprecedented detail. Using quantum chemical simulations, we investigated how the catalytic reaction mechanism is affected by electrostatic and hydrogen-bond interactions. Our calculations showed that the transition state (TS) was mainly stabilized electrostatically, with Arg90 playing the leading role. The effect was augmented by selective hydrogen-bond formation to the TS in the wild-type enzyme, facilitated by a small-scale local induced fit. We further identified a previously underappreciated water molecule, which separates the negative charges during the reaction. The analysis includes the wild-type enzyme and a non-natural enzyme variant, where the catalytic arginine was replaced with an isosteric citrulline residue.

  3. Quantum computation by measurement and quantum memory

    International Nuclear Information System (INIS)

    Nielsen, Michael A.


    What resources are universal for quantum computation? In the standard model of a quantum computer, a computation consists of a sequence of unitary gates acting coherently on the qubits making up the computer. This requirement for coherent unitary dynamical operations is widely believed to be the critical element of quantum computation. Here we show that a very different model involving only projective measurements and quantum memory is also universal for quantum computation. In particular, no coherent unitary dynamics are involved in the computation

  4. Steepest-entropy-ascent nonequilibrium quantum thermodynamic framework to model chemical reaction rates at an atomistic level. (United States)

    Beretta, G P; Al-Abbasi, Omar; von Spakovsky, M R


    The steepest entropy ascent (SEA) dynamical principle provides a general framework for modeling the dynamics of nonequilibrium (NE) phenomena at any level of description, including the atomistic one. It has recently been shown to provide a precise implementation and meaning to the maximum entropy production principle and to encompass many well-established theories of nonequilibrium thermodynamics into a single unifying geometrical framework. Its original formulation in the framework of quantum thermodynamics (QT) assumes the simplest and most natural Fisher-Rao metric to geometrize from a dynamical standpoint the manifold of density operators, which represent the thermodynamic NE states of the system. This simplest SEAQT formulation is used here to develop a general mathematical framework for modeling the NE time evolution of the quantum state of a chemically reactive mixture at an atomistic level. The method is illustrated for a simple two-reaction kinetic scheme of the overall reaction F+H_{2}⇔HF+F in an isolated tank of fixed volume. However, the general formalism is developed for a reactive system subject to multiple reaction mechanisms. To explicitly implement the SEAQT nonlinear law of evolution for the density operator, both the energy and the particle number eigenvalue problems are set up and solved analytically under the dilute gas approximation. The system-level energy and particle number eigenvalues and eigenstates are used in the SEAQT equation of motion to determine the time evolution of the density operator, thus effectively describing the overall kinetics of the reacting system as it relaxes toward stable chemical equilibrium. The predicted time evolution in the near-equilibrium limit is compared to the reaction rates given by a standard detailed kinetic model so as to extract the single time constant needed by the present SEA model.

  5. Coherent chemical kinetics as quantum walks. II. Radical-pair reactions in Arabidopsis thaliana (United States)

    Chia, A.; Górecka, A.; Kurzyński, P.; Paterek, T.; Kaszlikowski, D.


    We apply the quantum-walk approach proposed in the preceding paper [A. Chia et al., preceding paper, Phys. Rev. E 93, 032407 (2016), 10.1103/PhysRevE.93.032407] to a radical-pair reaction where realistic estimates for the intermediate transition rates are available. The well-known average hitting time from quantum walks can be adopted as a measure of how quickly the reaction occurs and we calculate this for varying degrees of dephasing in the radical pair. The time for the radical pair to react to a product is found to be independent of the amount of dephasing introduced, even in the limit of no dephasing where the transient population dynamics exhibits strong coherent oscillations. This can be seen to arise from the existence of a rate-limiting step in the reaction and we argue that in such examples, a purely classical model based on rate equations can be used for estimating the time scale of the reaction but not necessarily its population dynamics.

  6. Calculations of the charge distribution in dodecyltrimethylammonium: a quantum chemical investigation. (United States)

    Minisini, Benoît; Chavand, Sylvain; Barthelery, Rudolph; Tsobnang, François


    In this work we report the atomic partial charges evaluated on dodecyltrimethylammonium ion. The values obtained from 17 quantum methods [CHELP, CHELPG, MK, NPA at (HF, LDA, PBE, B3LYP)//6-31G++(d,p) level and APT at B3LYP//6-31G++(d,p)] on the molecule optimised at B3LYP/6-31G++(d,p) level were compared to two semiempirical methods (Gasteiger and Qeq) and the commercial force field PCFF. All methods based on quantum calculation gave a positive charge delocalised on at least the first four alkyl groups of the tail. However, those deriving partial charges from the electrostatic potential gave an unrealistic set of alternative positive and negative alkyl group charges along the tail. In comparison, the NPA and APT methods lead to a steady decrease in the partial charges from the third alkyl group, and agreed closely with the representation of the electrostatic potential mapped onto the 0.002 au isodensity surface. The choice of the exchange correlation treatment does not drastically influence the atomic partial charges.

  7. Chemical solutions in a quantum solvent: anionic electrolytes in 4He nanodroplets. (United States)

    Coccia, Emanuele; Marinetti, Fabio; Bodo, Enrico; Gianturco, Francesco A


    Variational and diffusion Monte Carlo (VMC and DMC) calculations are presented for anionic electrolytes solvated in (4)He. The electrolytes have the general structure X(-)(He)(N), with X=F, Cl, Br and I, and N varying up to 40 (41 for I(-)). The overall interaction potential is obtained from accurate ab initio data for the two-body components and then using the sum-of-potentials approximation. Our computational scheme is a robust procedure, giving us accurate trial wavefunctions that can be used to perform high-quality DMC calculations. The results indicate very marked delocalization and permanence of the liquid-like quantum features of the solvent adatoms surrounding the anionic impurities. This finding stands in contrast to the more structured, solid-like behavior of the quantum solutions with alkali metal cations embedded in He nanodroplets. While other negatively charged species such as H(-) have shown an overall repulsive interaction with He, the present calculations clearly indicate that the halogen anions remain solvated within liquid-like solvent "bubbles" of species-dependent size.

  8. Exploring the Structure of a DNA Hairpin with the Help of NMR Spin-Spin Coupling Constants: An Experimental and Quantum Chemical Investigation

    Czech Academy of Sciences Publication Activity Database

    Sychrovský, Vladimír; Vacek, Jaroslav; Hobza, Pavel; Žídek, L.; Sklenář, V.; Cremer, D.


    Roč. 106, - (2002), s. 10242-10250 ISSN 1089-5639 R&D Projects: GA MŠk LN00A032 Institutional research plan: CEZ:AV0Z4040901 Keywords : DNA * help of NMR spin-spin coupling constants * quantum chemical investigation Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.765, year: 2002

  9. QSPR models based on molecular mechanics and quantum chemical calculations. 1. Construction of Boltzmann averaged descriptors for alkanes, alcohols, diols, ethers and cyclic compounds

    DEFF Research Database (Denmark)

    Dyekjær, Jane Dannow; Rasmussen, Kjeld; Jonsdottir, Svava Osk


    -averaged by selection of the most relevant conformers out of a set of possible molecular conformers generated by a systematic scheme presented in this paper. Six of these descriptors are calculated with molecular mechanics and three with quantum chemical methods. Especially interesting descriptors are the relative van...

  10. Field data reveal low critical chemical concentrations for river benthic invertebrates. (United States)

    Berger, Elisabeth; Haase, Peter; Oetken, Matthias; Sundermann, Andrea


    River ecosystems are of immense ecological and social importance. Despite the introduction of wastewater treatment plants and advanced chemical authorization procedures in Europe, chemical pollution is still a major threat to freshwater ecosystems. Here, large-scale monitoring data was exploited to identify taxon-specific chemical concentrations beyond which benthic invertebrate taxa are unlikely to occur using Threshold Indicator Taxa Analysis (TITAN). 365 invertebrate taxa and 25 organic chemicals including pesticides, pharmaceuticals, plasticisers, flame retardants, complexing agents, a surfactant and poly- and monocyclic aromatic hydrocarbons from a total of 399 sites were analysed. The number of taxa that responded to each of these chemicals varied between 0% and 21%. These sensitive taxa belonged predominantly to the groups Plecoptera, Coleoptera, Trichoptera, Ephemeroptera, Turbellaria, Megaloptera, Crustacea, and Diptera. Strong effects were observed in response to wastewater-associated compounds, confirming that wastewater is an important cause of biological degradation. The majority of change points identified for each compound were well below predicted no-effect concentrations derived from laboratory toxicity studies. Thus, the results show that chemicals are likely to induce effects in the environment at concentrations much lower than expected based on laboratory experiments. Overall, it is confirmed that chemical pollution is still an important factor shaping the distribution of invertebrate taxa, suggesting the need for continued efforts to reduce chemical loads in rivers. Copyright © 2015 Elsevier B.V. All rights reserved.

  11. Quantum chemistry

    CERN Document Server

    Lowe, John P


    Praised for its appealing writing style and clear pedagogy, Lowe's Quantum Chemistry is now available in its Second Edition as a text for senior undergraduate- and graduate-level chemistry students. The book assumes little mathematical or physical sophistication and emphasizes an understanding of the techniques and results of quantum chemistry, thus enabling students to comprehend much of the current chemical literature in which quantum chemical methods or concepts are used as tools. The book begins with a six-chapter introduction of standard one-dimensional systems, the hydrogen atom,

  12. Efficient Implementation of Many-body Quantum Chemical Methods on the Intel Xeon Phi Coprocessor

    Energy Technology Data Exchange (ETDEWEB)

    Apra, Edoardo; Klemm, Michael; Kowalski, Karol


    This paper presents the implementation and performance of the highly accurate CCSD(T) quantum chemistry method on the Intel Xeon Phi coprocessor within the context of the NWChem computational chemistry package. The widespread use of highly correlated methods in electronic structure calculations is contingent upon the interplay between advances in theory and the possibility of utilizing the ever-growing computer power of emerging heterogeneous architectures. We discuss the design decisions of our implementation as well as the optimizations applied to the compute kernels and data transfers between host and coprocessor. We show the feasibility of adopting the Intel Many Integrated Core Architecture and the Intel Xeon Phi coprocessor for developing efficient computational chemistry modeling tools. Remarkable scalability is demonstrated by benchmarks. Our solution scales up to a total of 62560 cores with the concurrent utilization of Intel Xeon processors and Intel Xeon Phi coprocessors.

  13. Activation of Soil and Chemical Reagents Exposed to the Neutrons Released by the JCO Criticality Accident in Tokai-mura


    YOSHIMASA, MURATA; TOSHIHARU, MUROYAMA; YOSHIKO, KAWABATA; MASAYOSHI, YAMAMOTO; KAZUHISA, KOMURA; Low Level Radioactivity Laboratory, Kanazawa University; Low Level Radioactivity Laboratory, Kanazawa University; Low Level Radioactivity Laboratory, Kanazawa University; Low Level Radioactivity Laboratory, Kanazawa University; Low Level Radioactivity Laboratory, Kanazawa University


    Specific activities (Bq/g-element) of residual neutron-induced radionuclides by the JCO criticality accident were measured for soil, concrete block and chemical reagent samples collected in the JCO campus. Induced radionuclides such as ^Na, ^Sc, ^Mn, ^Fe, ^Co, ^Zn, ^Br, ^Sb, ^Cs and ^La were detected in the samples, depending on the ground distance from the accident point and the sampling date. Apparent thermal, epi-thermal and fast neutron fluences, which reached the sample at each point, we...

  14. The critical review of methodologies and approaches to assess the inherent skin sensitization potential (skin allergies) of chemicals. Part III

    DEFF Research Database (Denmark)

    Thyssen, Jacob P; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre


    For those chemicals identified in point 2 above, to collect and critically analyse clinical and statistical evidence on the incidence and morbidity (clinical picture) of skin contact allergy (contact dermatitis) cases in the EU before (at least 3 years) and after the limits were set, so as to allow...... an assessment of the possible effect of the limits in the reduction/prevention of the incidence and morbidity of contact dermatitis....

  15. The critical review of methodologies and approaches to assess the inherent skin sensitization potential (skin allergies) of chemicals. Part III. (United States)

    Thyssen, Jacob P; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre; Menné, Torkil; Boman, Anders; Schnuch, Axel


    For those chemicals identified in point 2 above, to collect and critically analyse clinical and statistical evidence on the incidence and morbidity (clinical picture) of skin contact allergy (contact dermatitis) cases in the EU before (at least 3 years) and after the limits were set, so as to allow an assessment of the possible effect of the limits in the reduction/prevention of the incidence and morbidity of contact dermatitis. © 2012 John Wiley & Sons A/S.


    Tipikin, Dmitriy S; Swarts, Steven G; Sidabras, Jason W; Trompier, François; Swartz, Harold M


    Exposure of finger- and toe-nails to ionizing radiation generates an Electron Paramagnetic Resonance (EPR) signal whose intensity is dose dependent and stable at room temperature for several days. The dependency of the radiation-induced signal (RIS) on the received dose may be used as the basis for retrospective dosimetry of an individual's fortuitous exposure to ionizing radiation. Two radiation-induced signals, a quasi-stable (RIS2) and stable signal (RIS5), have been identified in nails irradiated up to a dose of 50 Gy. Using X-band EPR, both RIS signals exhibit a singlet line shape with a line width around 1.0 mT and an apparent g-value of 2.0044. In this work, we seek information on the exact chemical nature of the radiation-induced free radicals underlying the signal. This knowledge may provide insights into the reason for the discrepancy in the stabilities of the two RIS signals and help develop strategies for stabilizing the radicals in nails or devising methods for restoring the radicals after decay. In this work an analysis of high field (94 GHz and 240 GHz) EPR spectra of the RIS using quantum chemical calculations, the oxidation-reduction properties and the pH dependence of the signal intensities are used to show that spectroscopic and chemical properties of the RIS are consistent with a semiquinone-type radical underlying the RIS. It has been suggested that semiquinone radicals formed on trace amounts of melanin in nails are the basis for the RIS signals. However, based on the quantum chemical calculations and chemical properties of the RIS, it is likely that the radicals underlying this signal are generated from the radiolysis of L-3,4-dihydroxyphenylalanine (DOPA) amino acids in the keratin proteins. These DOPA amino acids are likely formed from the exogenous oxidation of tyrosine in keratin by the oxygen from the air prior to irradiation. We show that these DOPA amino acids can work as radical traps, capturing the highly reactive and unstable sulfur

  17. Carbonado: Physical and chemical properties, a critical evaluation of proposed origins, and a revised genetic model (United States)

    Haggerty, Stephen E.


    Carbonado-diamond is the most controversial of all diamond types and is found only in Brazil, and the Central African Republic (Bangui). Neither an affinity to Earth's mantle, nor an origin in the crust can be unequivocally established. Carbonado-diamond is at least 3.8 Ga old, an age about 0.5 Ga older than the oldest diamonds yet reported in kimberlites and lamproites on Earth. Derived from Neo- to Mid-Proterozoic meta-conglomerates, the primary magmatic host rock has not been identified. Discovered in 1841, the material is polycrystalline, robust and coke-like, and is best described as a strongly bonded micro-diamond ceramic. It is characteristically porous, which precludes an origin at high pressures and high temperatures in Earth's deep interior, yet it is also typically patinated, with a glass-like surface that resembles melting. With exotic inclusions of highly reduced metals, carbides, and nitrides the origin of carbonado-diamond is made even more challenging. But the challenge is important because a new diamondiferous host rock may be involved, and the development of a new physical process for generating diamond is possibly assured. The combination of micro-crystals and random crystal orientation leads to extreme mechanical toughness, and a predicable super-hardness. The physical and chemical properties of carbonado are described with a view to the development of a mimetic strategy to synthesize carbonado and to duplicate its extreme toughness and super-hardness. Textural variations are described with an emphasis on melt-like surface features, not previously discussed in the literature, but having a very clear bearing on the history and genesis of carbonado. Selected physical properties are presented and the proposed origins, diverse in character and imaginatively novel, are critically reviewed. From our present knowledge of the dynamic Earth, all indications are that carbonado is unlikely to be of terrestrial origin. A revised model for the origin of

  18. Broadband mid-infrared and THz chemical detection with quantum cascade laser multi-heterodyne spectrometers (Conference Presentation) (United States)

    Westberg, Jonas; Sterczewski, Lukasz A.; Patrick, Link; Wysocki, Gerard


    Majority of chemical species of interest in security and safety applications (e.g. explosives) have complex molecular structures that produce unresolved rotational-vibrational spectroscopic signatures in the mid-infrared. This requires spectroscopic techniques that can provide broadband coverage in the mid-IR region to target broadband absorbers and high resolution to address small molecules that exhibit well-resolved spectral lines. On the other hand, many broadband mid-IR absorbers exhibit well-resolved rotational components in the THz spectral region. Thus, development of spectroscopic sensing technologies that can address both spectral regions is of great importance. Here we demonstrate recent progress towards broadband high-resolution spectroscopic sensing applications with Fabry-Perot quantum cascade lasers (QCLs) and frequency combs using multi-heterodyne spectroscopy (MHS) techniques. In this paper, we will present spectroscopic sensing of large and small molecules in the mid-IR region using QCLs operating at 8.5µm. An example high-resolution, broadband MHS of ammonia (small molecule) and isobutane (broadband absorber) at atmospheric pressure in the 1165-1190 cm^-1 range will be discussed. We have developed a balanced MHS system for mitigation of the laser intensity fluctuations. Absorption spectroscopy as well as dispersion spectroscopy with minimum fractional absorption down to 10^-4/Hz1/2 and fast spectral acquisition capabilities down to 10 µs/spectrum range will be demonstrated. In order to mitigate the shortcomings of the limited chemical selectivity in the mid-IR, THz QCL based spectrometer is currently under development to provide spectral de-congestion and thus significantly improve chemical identification. Preliminary characterization of the performance of THZ QCL combs for the THz QCL-MHS will be presented.

  19. Quantum chemical study of the thermal decomposition of o-quinone methide (6-methylene-2,4-cyclohexadien-1-one). (United States)

    Silva, Gabriel da; Bozzelli, Joseph W


    o-Quinone methide (o-QM), or 6-methylene-2,4-cyclohexadiene-1-one, has been identified as an important intermediate in lignin and alkyl benzene combustion, and the thermal decomposition of o-QM is therefore relevant to the combustion of transportation fuels (which contain toluene) and of biomass and low-rank coals (which contain lignin). We present a comprehensive reaction mechanism for the unimolecular conversion of o-QM to the reaction intermediates tropone and fulvene, calculated using theoretical quantum chemical techniques. Enthalpies of formation for all reactants, products, and intermediates are calculated using the CBS-QB3 theoretical method. Transition states are determined with the CBS-QB3 method, which we use to obtain rate constants as a function of temperature from transition-state theory, with Wigner tunneling corrections applied to hydrogen-shift reactions. Barrier heights are also calculated with the BB1K density functional theory (DFT) method for thermochemical kinetics. Reaction pathways are identified leading to tropone (which rapidly decomposes to benzene + CO) and to fulvene + CO, via initial hydrogen transfer to 2-hydroxyphenylcarbene and via ring opening to 1,3,5,6-heptatetraen-1-one, respectively. Quantum Rice-Ramsperger-Kassel (QRRK) theory analysis of the reaction kinetics indicates that the dominant reaction pathway is formation of tropone via 2-hydroxyphenylcarbene; the formation of fulvene + CO via initial ring opening constitutes a secondary pathway, which becomes more important with increasing temperature. Our calculations, using BB1K barrier heights, yield the rate equation k(T) [s(-1)] = 2.64 x 10(14) exp(-35.9/T [K]) for o-QM decomposition, which is in relatively good agreement with the experimental rate equation. Calculations provide an apparent activation energy of 71.3 kcal mol(-1), versus 67.2 kcal mol(-1) from experiment.

  20. Carboxymethyl chitosan based nanocomposites containing chemically bonded quantum dots and magnetic nanoparticles (United States)

    Ding, Yongling; Yin, Hong; Chen, Rui; Bai, Ru; Chen, Chunying; Hao, Xiaojuan; Shen, Shirley; Sun, Kangning; Liu, Futian


    A biocompatible nanocomposite consisting of fluorescent quantum dots (QDs) and magnetic nanoparticles (MNPs) has been constructed via carboxymethyl chitosan (CMCS), resulting in magnetic-fluorescent nanoparticles (MFNPs). In these MFNPs, QDs and MNPs are successfully conjugated via covalent bonds onto the surface of CMCS. The composite retains favorable magnetic and fluorescent properties and shows a good colloidal stability in physiological environments. Folate (FA) as a specific targeting ligand was further incorporated into the nanocomposites to form a delivery vehicle with a targeting function. The therapeutic activity was achieved by loading chemotherapeutic drug doxorubicin (DOX) through electrostatic and hydrophobic interactions. The cumulative DOX release profile shows pH-sensitive. Both flow cytometry analysis and confocal laser scanning microscopic observation suggested that these nanocomposites were uptaken by cancer cells via FA receptor-mediated endocytosis pathway. In summary, the CMCS based nanocomposites developed in this work have a great potential for effective cancer-targeting and drug delivery, as well as in situ cellular imaging.

  1. Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table. (United States)

    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


    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.

  2. Application of scattering quantum theory for simple chemical reaction calculations. Electron scattering by biatomic molecules

    International Nuclear Information System (INIS)

    Pozdneev, S.A.; Shcheglov, V.A.


    Theory of multiple scattering in the three-body system, which mathematical base is L.D. Fadeev's equations, is applied for calculating the simplest chemical reactions proceeding in electron collision with two-atom molecules. Calculations of cross sections of elastic scattering, excitation, dissociation and dissociative electron attachment to two-atom molecules being in different excited rotational-vibrational states have been performed on the basis of the developed theory

  3. Geometrical criteria versus quantum chemical criteria for assessment of intramolecular hydrogen bond (IMHB) interaction: A computational comparison into the effect of chlorine substitution on IMHB of salicylic acid in its lowest energy ground state conformer

    International Nuclear Information System (INIS)

    Paul, Bijan Kumar; Guchhait, Nikhil


    Highlights: ► Intramolecular hydrogen bonding (IMHB) in salicylic acid and its chloro derivatives. ► A complex effect of +R and −I effect of chlorine substituents on IMHB energy. ► Interplay between IMHB energy and aromaticity. ► Directional nature of IMHB from quantum chemical assessment. ► Quantum chemical treatment vs. geometrical criteria to assess weak interaction. - Abstract: Density functional theory based computational study has been performed to characterize intramolecular hydrogen bonding (IMHB) interaction in a series of salicylic acid derivatives varying in chlorine substitution on the benzene ring. The molecular systems studied are salicylic acid, 5-chlorosalicylic acid, 3,5-dichlorosalicylic acid and 3,5,6-tricholorosalicylic acid. Major emphasis is rendered on the analysis of IMHB interaction by calculation of electron density ρ(r) and Laplacian ∇ 2 ρ(r) at the bond critical point using atoms-in-molecule theory. Topological features, energy densities based on ρ(r) through perturbing the intramolecular H-bond distances suggest that at equilibrium geometry the IMHB interaction develops certain characteristics typical of covalent interaction. The interplay between aromaticity and resonance-assisted hydrogen bonding (RAHB) is discussed using both geometrical and magnetic criteria as the descriptors of aromaticity. The optimized geometry features, molecular electrostatic potential map analysis are also found to produce a consensus view in relation with the formation of RAHB in these systems

  4. B{sub 36} borophene as an electronic sensor for formaldehyde: Quantum chemical analysis

    Energy Technology Data Exchange (ETDEWEB)

    Shahbazi Kootenaei, Amirhossein, E-mail: [Department of Chemical Engineering, Mahshahr Branch, Islamic Azad University, Mahshahr (Iran, Islamic Republic of); Ansari, Goodarz [Department of Chemistry, Mahshahr Branch, Islamic Azad University, Mahshahr (Iran, Islamic Republic of)


    Pristine carbon nanotubes and graphene show great sensitivity toward several lethal gases but cannot identify some extremely toxic chemicals such as formaldehyde (HCOH). Recent successful synthesis of all-boron graphene-like sheets attracted strong interest in exploring their possible applications. Herein, we inspected the potential application of B{sub 36} borophene sheet as a sensor for HCOH detection, using density functional theory computations. Different theoretical levels including B97D and Minnesota 06 functionals with different basis sets were employed. It was predicted that the electrical conductivity of B{sub 36} borophene significantly increases at the presence of HCOH molecules, thereby generating an electrical signal. The electrical signal is increased by increasing the number of adsorbed HCOH molecules, indicating that this sensor is sensitive to the concentration (or pressure) of HCOH gas. These results suggest that the pristine borophene may be used in the HCOH chemical sensors. - Highlights: • B{sub 36} borophene sheet can be used as a chemical sensor for HCOH detection. • The B{sub 36} is sensitive to the concentration of HCOH. • When the B{sub 36} adsorbs HCOH molecules, it is converted to a p-type semiconductor.

  5. Signatures of Quantum Phase Transitions via Quantum Information Theoretic Measures (United States)

    Bose, I.; Tribedi, A.

    Quantum phase transitions (QPTs) in many body systems occur at T = 0 brought about by tuning a non-thermal parameter, e.g. pressure, chemical composition or external magnetic field [1, 2]. In a QPT, the ground state wave function undergoes qualitative changes at the transition point. The transition is driven by quantum fluctuations whereas ordinary phase transitions occurring at nonzero temperatures are driven by thermal fluctuations. Like a thermal phase transition, a QPT can be first order, second order or higher order. The thermal critical point, associated with a second-order phase transition, is characterized by the presence of thermal fluctuations on all length scales resulting in a divergent correlation length. The free energy and the thermodynamic functions develop singularities as temperature Trightarrow T_{textrm{c}} , the critical temperature. At the quantum critical point (QCP), quantum fluctuations occur on all length scales leading to a divergent correlation length. The ground state and related physical quantities become non-analytic as the tuning parameter g tends to the critical value g c . The influence of QPTs extends into the finite T part of the phase diagram so that experimental detection of QPTs is possible.

  6. Charge carrier mobility in sulphonated and non-sulphonated Ni phthalocyanines: experiment and quantum chemical calculations

    Czech Academy of Sciences Publication Activity Database

    Šebera, Jakub; Nešpůrek, Stanislav; Kratochvílová, Irena; Záliš, Stanislav; Chaidogiannos, G.; Glezos, N.


    Roč. 72, č. 3 (2009), s. 385-395 ISSN 1434-6028 R&D Projects: GA MŠk OC 139; GA MŠk OC 137; GA AV ČR KAN401770651; GA AV ČR KAN200100801; GA ČR GA203/08/1594; GA MŠk OC 138 Institutional research plan: CEZ:AV0Z40400503; CEZ:AV0Z40500505; CEZ:AV0Z10100520 Keywords : Ni Phthalocyanine s * chemical calculations * polymers Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.466, year: 2009

  7. Quantum chemical computations, vibrational spectroscopic analysis and antimicrobial studies of 2,3-Pyrazinedicarboxylic acid (United States)

    Beaula, T. Joselin; Packiavathi, A.; Manimaran, D.; Joe, I. Hubert; Rastogi, V. K.; Jothy, V. Bena


    Density Functional Theory (DFT) calculations at B3PW91 level with 6-311G (d) basis sets were carried out for 2,3-Pyrazinedicarboxylic acid (PDCA) to analyze in detail the equilibrium geometries and vibrational spectra. Calculations reveal that the optimized geometry closely resembles the experimental XRD data. Vibrational spectra were analyzed on the basis of potential energy distribution (PED) of each vibrational mode, which provides quantitative as well as qualitative interpretation of IR and Raman spectra. Information about size, shape, charge density distribution and site of chemical reactivity of the molecule were obtained by mapping electron density isosurface with the electrostatic potential surface (ESP). Based on optimized ground state geometries, NBO analysis was performed to study donor-acceptor (bond-antibond) interactions. TD-DFT analysis was also performed to calculate energies, oscillator strength of electronic singlet-singlet transitions and the absorption wavelengths. The 13C and 1H nuclear magnetic resonance (NMR) chemical shifts of the molecule in the ground state were calculated by gauge independent atomic orbital (GIAO) method and compared with the experimental values. PDCA was screened for its antimicrobial activity and found to exhibit antifungal and antibacterial effects. Molecular docking was also performed for the different receptors.

  8. Anti-oxidant behavior of functionalized chalcone-a combined quantum chemical and crystallographic structural investigation (United States)

    Mathew, Bijo; Adeniyi, Adebayo A.; Joy, Monu; Mathew, Githa Elizabeth; Singh-Pillay, Ashona; Sudarsanakumar, C.; Soliman, Mahmoud E. S.; Suresh, Jerad


    Compound (2E)-3-(methoxyphenyl)-1-(4-methylphenyl) prop-2-en-1-one (Ch) was synthesized by the Claisen-Schmidt condensation reaction between para-methylacetophenone and para-methoxybenzaldehyde under basic condition. The structure of the molecule was elucidated using X-ray diffraction. Compound (Ch) demonstrated higher antioxidant activities in the DPPH test and H2O2 assay (IC50 = 12.23 ± 0.53 and 15.62 ± 0.98) than with the standard ascorbic acid (IC50 = 17.32 ± 0.44 and 19.07 ± 0.35). An evaluation of the atomic and molecular properties of ascorbic acid and Ch were computed based on their antioxidant activities. The molecular properties give insight into possible reasons for the enhanced antioxidant properties of Ch compared to ascorbic acid. The atomic properties provide further insight into chemical changes of the atoms of the compounds. Such changes include electronic shifting of the compounds electrophilic and/or nucleophilic states which highlight chemical moieties which characterize the antioxidant activity but do not directly relate to a variation in their antioxidant activities. The results obtained reflect oxygen atoms having significant nucleophilic interactions of each of the compounds. This was characterized by higher Fukui indices, isotropic and anisotropic hyperfine and orbital coupling stability energy.

  9. Principles of quantum chemistry

    CERN Document Server

    George, David V


    Principles of Quantum Chemistry focuses on the application of quantum mechanics in physical models and experiments of chemical systems.This book describes chemical bonding and its two specific problems - bonding in complexes and in conjugated organic molecules. The very basic theory of spectroscopy is also considered. Other topics include the early development of quantum theory; particle-in-a-box; general formulation of the theory of quantum mechanics; and treatment of angular momentum in quantum mechanics. The examples of solutions of Schroedinger equations; approximation methods in quantum c

  10. Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics. (United States)

    Masunov, Artëm E; Wait, Elizabeth E; Atlanov, Arseniy A; Vasu, Subith S


    In oxy-fuel combustion, the pure oxygen (O 2 ), diluted with CO 2 is used as oxidant instead air. Hence, the combustion products (CO 2 and H 2 O) are free from pollution by nitrogen oxides. Moreover, high pressures result in the near-liquid density of CO 2 at supercritical state (sCO 2 ). Unfortunately, the effects of sCO 2 on the combustion kinetics are far from being understood. To assist in this understanding, in this work we are using quantum chemistry methods. Here we investigate potential energy surfaces of important combustion reactions in the presence of the carbon dioxide molecule. All transition states and reactant and product complexes are reported for three reactions: H 2 CO + HO 2 → HCO + H 2 O 2 (R1), 2HO 2 → H 2 O 2 + O 2 (R2), and CO + OH → CO 2 + H (R3). In reaction R3, covalent binding of CO 2 to the OH radical and then the CO molecule opens a new pathway, including hydrogen transfer from oxygen to carbon atoms followed by CH bond dissociation. Compared to the bimolecular OH + CO mechanism, this pathway reduces the activation barrier by 5 kcal/mol and is expected to accelerate the reaction. In the case of hydroperoxyl self-reaction 2HO 2 → H 2 O 2 + O 2 the intermediates, containing covalent bonds to CO 2 are found not to be competitive. However, the spectator CO 2 molecule can stabilize the cyclic transition state and lower the barrier by 3 kcal/mol. Formation of covalent intermediates is also discovered in the H 2 CO + HO 2 → HCO + H 2 O 2 reaction, but these species lead to substantially higher activation barriers, which makes them unlikely to play a role in hydrogen transfer kinetics. The van der Waals complexation with carbon dioxide also stabilizes the transition state and reduces the reaction barrier. These results indicate that the CO 2 environment is likely to have a catalytic effect on combustion reactions, which needs to be included in kinetic combustion mechanisms in supercritical CO 2 .

  11. Vibrational studies of Thyroxine hormone: Comparative study with quantum chemical calculations (United States)

    Borah, Mukunda Madhab; Devi, Th. Gomti


    The FTIR and Raman techniques have been used to record spectra of Thyroxine. The stable geometrical parameters and vibrational wave numbers were calculated based on potential energy distribution (PED) using vibrational energy distribution analysis (VEDA) program. The vibrational energies are assigned to monomer, chain dimer and cyclic dimers of this molecule using the basis set B3LYP/LANL2DZ. The computational scaled frequencies are in good agreements with the experimental results. The study is extended to calculate the HOMO-LUMO energy gap, Molecular Electrostatic Potential (MEP) surface, hardness (η), chemical potential (μ), Global electrophilicity index (ω) and different thermo dynamical properties of Thyroxine in different states. The calculated HOMO-LUMO energies show the charge transfer occurs within the molecule. The calculated Natural bond orbital (NBO) analysis confirms the presence of intra-molecular charge transfer as well as the hydrogen bonding interaction.

  12. Spectroscopic (vibrational, NMR and UV-vis.) and quantum chemical investigations on 4-hexyloxy-3-methoxybenzaldehyde. (United States)

    Abbas, Ashgar; Gökce, Halil; Bahçeli, Semiha


    In this study, the 4-hexyloxy-3-methoxybenzaldehyde compound as one of the derivatives of vanillin which is a well known flavoring agent, C14H20O3, has been investigated by experimentally and extensively utilizing density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. In this context, the optimized geometry, vibrational frequencies, (1)H and (13)C NMR chemical shifts, UV-vis. (in gas phase and in methanol solvent) spectra, HOMO-LUMO analysis, molecular electrostatic potential (MEP), thermodynamic parameters and atomic charges of 4-hexyloxy-3-methoxybenzaldehyde have been calculated. In addition, theoretically predicted IR, Raman and UV-vis. (in gas phase and in methanol solvent) spectra of the mentioned molecule have been constructed. The results calculated were compared with the experimental data. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Spectroscopic (vibrational, NMR and UV-vis.) and quantum chemical investigations on 4-hexyloxy-3-methoxybenzaldehyde (United States)

    Abbas, Ashgar; Gökce, Halil; Bahçeli, Semiha


    In this study, the 4-hexyloxy-3-methoxybenzaldehyde compound as one of the derivatives of vanillin which is a well known flavoring agent, C14H20O3, has been investigated by experimentally and extensively utilizing density functional theory (DFT) at the B3LYP/6-311++G(d,p) level. In this context, the optimized geometry, vibrational frequencies, 1H and 13C NMR chemical shifts, UV-vis. (in gas phase and in methanol solvent) spectra, HOMO-LUMO analysis, molecular electrostatic potential (MEP), thermodynamic parameters and atomic charges of 4-hexyloxy-3-methoxybenzaldehyde have been calculated. In addition, theoretically predicted IR, Raman and UV-vis. (in gas phase and in methanol solvent) spectra of the mentioned molecule have been constructed. The results calculated were compared with the experimental data.

  14. Real-Time Monitoring of Critical Care Analytes in the Bloodstream with Chemical Sensors: Progress and Challenges. (United States)

    Frost, Megan C; Meyerhoff, Mark E


    We review approaches and challenges in developing chemical sensor-based methods to accurately and continuously monitor levels of key analytes in blood related directly to the status of critically ill hospitalized patients. Electrochemical and optical sensor-based technologies have been pursued to measure important critical care species in blood [i.e., oxygen, carbon dioxide, pH, electrolytes (K(+), Na(+), Cl(-), etc.), glucose, and lactate] in real-time or near real-time. The two main configurations examined to date for achieving this goal have been intravascular catheter sensors and patient attached ex vivo sensors with intermittent blood sampling via an attached indwelling catheter. We discuss the status of these configurations and the main issues affecting the accuracy of the measurements, including cell adhesion and thrombus formation on the surface of the sensors, sensor drift, sensor selectivity, etc. Recent approaches to mitigate these nagging performance issues that have prevented these technologies from clinical use are also discussed.

  15. Toward prethreshold gate-based quantum simulation of chemical dynamics: using potential energy surfaces to simulate few-channel molecular collisions (United States)

    Sornborger, Andrew T.; Stancil, Phillip; Geller, Michael R.


    One of the most promising applications of an error-corrected universal quantum computer is the efficient simulation of complex quantum systems such as large molecular systems. In this application, one is interested in both the electronic structure such as the ground state energy and dynamical properties such as the scattering cross section and chemical reaction rates. However, most theoretical work and experimental demonstrations have focused on the quantum computation of energies and energy surfaces. In this work, we attempt to make the prethreshold (not error-corrected) quantum simulation of dynamical properties practical as well. We show that the use of precomputed potential energy surfaces and couplings enables the gate-based simulation of few-channel but otherwise realistic molecular collisions. Our approach is based on the widely used Born-Oppenheimer approximation for the structure problem coupled with a semiclassical method for the dynamics. In the latter the electrons are treated quantum mechanically but the nuclei are classical, which restricts the collisions to high energy or temperature (typically above ≈ 10 eV). By using operator splitting techniques optimized for the resulting time-dependent Hamiltonian simulation problem, we give several physically realistic collision examples, with 3-8 channels and circuit depths < 1000.

  16. The origins of the research on the foundations of quantum mechanics (and other critical activities) in Italy during the 1970s (United States)

    Baracca, Angelo; Bergia, Silvio; Del Santo, Flavio


    We present a reconstruction of the studies on the Foundations of Quantum Mechanics carried out in Italy at the turn of the 1960s. Actually, they preceded the revival of the interest of the American physicists towards the foundations of quantum mechanics around mid-1970s, recently reconstructed by David Kaiser in a book of 2011. An element common to both cases is the role played by the young generation, even though the respective motivations were quite different. In the US they reacted to research cuts after the war in Vietnam, and were inspired by the New Age mood. In Italy the dissatisfaction of the young generations was rooted in the student protests of 1968 and the subsequent labour and social fights, which challenged the role of scientists. The young generations of physicists searched for new scientific approaches and challenged their own scientific knowledge and role. The criticism to the foundations of quantum mechanics and the perspectives of submitting them to experimental tests were perceived as an innovative research field and this attitude was directly linked to the search for an innovative and radical approach in the history of science. All these initiatives gave rise to booming activity throughout the 1970s, contributing to influence the scientific attitude and the teaching approach.

  17. Simulation and design of the emission wavelength of multiple quantum well structures fabricated by selective area metalorganic chemical vapor deposition

    International Nuclear Information System (INIS)

    Shioda, Tomonari; Doi, Takeshi; Al Amin, Abdullah; Song Xueliang; Sugiyama, Masakazu; Shimogaki, Yukihiro; Nakano, Yoshiaki


    Selective area metalorganic chemical vapor deposition (SA-MOCVD) is effective for the monolithic integration of semiconductor optical devices. Using appropriate patterns of SiO 2 masks on a substrate, we can fabricate multiple quantum wells (MQWs) of In 1-x Ga x As y P 1-y alloys with various emission wavelengths. Therefore, we can fabricate both passive elements and active components for different wavelengths on a substrate by a single growth. To make the best use of this SA-MOCVD process, we need a simulation tool that predicts the performance of the grown layer for a given mask pattern. We constructed a simulation that predicts the emission wavelength of MQW structures grown by SA-MOCVD. The simulation took into account the gas-phase diffusion of the precursors of In and Ga and their incorporation to the growth area. The rate parameters of these processes were extracted from the growth-rate profile in the SA-MOCVD of InP and GaAs. Based on these data, we simulated the photoluminescence (PL) peak wavelength of (1) In 1-x Ga x As y P 1-y bulk films and (2) MQWs consisting of these quaternary alloys. The simulated results agreed with experimental results, indicating the feasibility of computer-assisted design (CAD) of the mask patterns for SA-MOCVD

  18. Syntheses, structural elucidation, thermal properties, theoretical quantum chemical studies (DFT and biological studies of barbituric–hydrazone complexes

    Directory of Open Access Journals (Sweden)

    Amina A. Soayed


    Full Text Available Condensation of barbituric acid with hydrazine hydrate yielded barbiturichydrazone (L which was characterized using IR, 1H NMR and mass spectra. The Co(II, Ni(II and Cu(II complexes derived from this ligand have been synthesized and structurally characterized by elemental analyses, spectroscopic methods (IR, UV–Vis and ESR and thermal analyses (TGA, DTG and DTA and the structures were further elucidated using quantum chemical density functional theory. Complexes of L were found to have the ML.nH2O stoichiometry with either tetrahedral or octahedral geometry. The ESR data showed the Cu(II complex to be in a tetragonal geometry. Theoretical investigation of the electronic structure of metal complexes at the TD-DFT/B3LYP level of theory has been carried out and discussed. The fundamental vibrational wavenumbers were calculated and a good agreement between observed and scaled calculated wavenumbers was achieved. Thermal studies were performed to deduce the stabilities of the ligand and complexes. Thermodynamic parameters, such as the order of reactions (n, activation energy ΔE∗, enthalpy of reaction ΔH∗ and entropy ΔS∗ were calculated from DTA curves using Horowitz–Metzger method. The ligand L and its complexes have been screened for their antifungal and antibacterial activities and were found to possess better biological activities compared to those of unsubstituted barbituric acid complexes.

  19. Fluorescent carbon quantum dots synthesized by chemical vapor deposition: An alternative candidate for electron acceptor in polymer solar cells (United States)

    Cui, Bo; Yan, Lingpeng; Gu, Huimin; Yang, Yongzhen; Liu, Xuguang; Ma, Chang-Qi; Chen, Yongkang; Jia, Husheng


    Excitation-wavelength-dependent blue-greenish fluorescent carbon quantum dots (CQDs) with graphite structure were synthesized by chemical vapor deposition (CVD) method. In comparison with those synthesized by hydrothermal method (named H-CQDs), C-CQDs have less hydrophilic terminal groups, showing good solubility in common organic solvents. Furthermore, these synthesized C-CQDs show a low LUMO energy level (LUMO = -3.84 eV), which is close to that of phenyl-C61-butyric acid methyl ester (PC61BM, LUMO = -4.01 eV), the most widely used electron acceptor in polymer solar cells. Photoluminescence quenching of the poly(3-hexylthiophene-2,5-diyl):C-CQDs blended film (P3HT:C-CQDs) indicated that a photo-induced charge transfer between P3HT and C-CQDs occurs in such a composite film. Bulk heterojunction solar cells using C-CQDs as electron acceptors or doping materials were fabricated and tested. High fill factors were achieved for these C-CQDs based polymer solar cells, demonstrating that CQDs synthesized by CVD could be alternative to the fullerene derivatives for applying in polymer solar cells.

  20. Quantum Chemical Calculations on the Interaction between Flavonol and Functional Monomers (Methacrylic Acid and 4-Vinylpyridine in Molecularly Imprinted Polymers

    Directory of Open Access Journals (Sweden)

    Luis Enrique Gómez-Pineda


    Full Text Available Quantum chemical calculations were performed to characterize the interaction of the flavonol molecule (FL with methacrylic acid (MAA and 4-vinylpyridine (4VPy in the formation of imprinted polymers. The polarizable continuum model (PCM was used to gain insight on the type of interaction between the reactant molecules under vacuum conditions and in the presence of different solvents. The effect of solvent on the pre-polymerization complex formation was evaluated through the stability energy, in which chloroform behaves as the best solvent for the synthesis of the imprinted polymers since it facilitates the reaction by lowering its degree of stabilization. The reactivity was analyzed in terms of the electrostatic surface potential (ESP and Mulliken charge. By means of these results, it has been possible to determine two potential recognition sites for the interaction of the MAA monomer and one for the 4VPy in relation to the strength of interaction with FL. In this concern, the interaction of the system FL-MAA is stronger than FL-4VPy.

  1. Quantum chemical investigation of the primary thermal pyrolysis reactions of the sodium carboxylate group in a brown coal model. (United States)

    Li, Jian; Zhang, Baisheng; Zhang, Zhiqiang; Yan, Kefeng; Kang, Lixun


    The primary pyrolysis mechanisms of the sodium carboxylate group in sodium benzoate-used as a model compound of brown coal-were studied by performing quantum chemical computations using B3LYP and the CBS method. Various possible reaction pathways involving reactions such as unimolecular and bimolecular decarboxylation and decarbonylation, crosslinking, and radical attack in the brown coal matrix were explored. Without the participation of reactive radicals, unimolecular decarboxylation to release CO2 was calculated to be the most energetically favorable primary reaction pathway at the B3LYP/6-311+G (d, p) level of theory, and was also found to be more energetically favorable than decarboxylation of an carboxylic acid group. When CBS-QBS results were included, crosslinking between the sodium carboxylate group and the carboxylic acid and the decarboxylation of the sodium carboxylate group (catalyzed by the phenolic hydroxyl group) were found to be possible; this pathway competes with unimolecular decarboxylation of the sodium carboxylate group. Provided that H and CH3 radicals are present in the brown coal matrix and can access the sodium carboxylate group, accelerated pyrolysis of the sodium carboxylate group becomes feasible, leading to the release of an Na atom or an NaCO2 radical at the B3LYP/6-311+G (d, p) or CBS-QB3 level of theory, respectively.

  2. Non-Covalent Interactions and Internal Dynamics in Pyridine-Ammonia a Combined Quantum-Chemical and Microwave Spectroscopy Study (United States)

    Spada, Lorenzo; Tasinato, Nicola; Vazart, Fanny; Barone, Vincenzo; Caminati, Walther; Puzzarini, Cristina


    The 1:1 complex of ammonia with pyridine has been characterized by using state-of-the-art quantum-chemical computations combined with pulsed-jet Fourier-Transform microwave spectroscopy. The computed potential energy landscape pointed out the formation of a stable σ-type complex, which has been confirmed experimentally: the analysis of the rotational spectrum showed the presence of only one 1:1 pyridine - ammonia adduct. Each rotational transition is split into several components due to the internal rotation of NH_3 around its C_3 axis and to the hyperfine structure of both ^{14}N quadrupolar nuclei, thus providing the unequivocal proof that the two molecules form a σ-type complex involving both a N-H\\cdotsN and a C-H\\cdotsN hydrogen bond. The dissociation energy (BSSE and ZPE corrected) has been estimated to be 11.5 kJ\\cdotmol^{-1}. This work represents the first application of an accurate, yet efficient computational scheme, designed for the investigation of small biomolecules, to a molecular cluster.

  3. Electrochemical and quantum chemical studies of some indole derivatives as corrosion inhibitors for C38 steel in molar hydrochloric acid

    Energy Technology Data Exchange (ETDEWEB)

    Lebrini, M. [Laboratoire Materiaux et Molecules en Milieu Amazonien, CNRS 8172-UMR ECOFOG, Campus Trou Biran, Cayenne 97337, French Guiana (France); Robert, F. [Laboratoire Materiaux et Molecules en Milieu Amazonien, UAG-UMR ECOFOG, Campus Trou Biran, Cayenne 97337, French Guiana (France); Vezin, H. [Laboratoire de Chimie Organique et Macromoleculaire, UMR-CNRS 8009, USTL BatC4 F-59655 Villeneuve d' Ascq Cedex (France); Roos, C., E-mail: christophe.roos@guyane.univ-ag.f [Laboratoire Materiaux et Molecules en Milieu Amazonien, UAG-UMR ECOFOG, Campus Trou Biran, Cayenne 97337, French Guiana (France)


    A comparative study of 9H-pyrido[3,4-b]indole (norharmane) and 1-methyl-9H-pyrido[3,4-b]indole (harmane) as inhibitors for C38 steel corrosion in 1 M HCl solution at 25 {sup o}C was carried out. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques were applied to study the metal corrosion behavior in the absence and presence of different concentrations of these inhibitors. The OCP as a function of time were also established. Cathodic and anodic polarization curves show that norharmane and harmane are a mixed-type inhibitors. Adsorption of indole derivatives on the C38 steel surface, in 1 M HCl solution, follows the Langmuir adsorption isotherm model. The {Delta}G{sub ads}{sup o} values were calculated and discussed. The potential of zero charge (PZC) of the C38 steel in inhibited solution was studied by the EIS method, and a mechanism for the adsorption process was proposed. Raman spectroscopy confirmed that indole molecules strongly adsorbed onto the steel surface. The electronic properties of indole derivates, obtained using the AM1 semi-empirical quantum chemical approach, were correlated with their experimental efficiencies using the linear resistance model (LR).

  4. Chemical redox modulated fluorescence of nitrogen-doped graphene quantum dots for probing the activity of alkaline phosphatase. (United States)

    Liu, JingJing; Tang, Duosi; Chen, Zhitao; Yan, Xiaomei; Zhong, Zhou; Kang, Longtian; Yao, Jiannian


    Alkaline phosphatase (ALP) as an essential enzyme plays an important role in clinical diagnoses and biomedical researches. Hence, the development of convenient and sensitivity assay for monitoring ALP is extremely important. In this work, on the basis of chemical redox strategy to modulate the fluorescence of nitrogen-doped graphene quantum dots (NGQDs), a novel label-free fluorescent sensing system for the detection of alkaline phosphatase (ALP) activity has been developed. The fluorescence of NGQDs is firstly quenched by ultrathin cobalt oxyhydroxide (CoOOH) nanosheets, and then restored by ascorbic acid (AA), which can reduce CoOOH to Co 2+ , thus the ALP can be monitored based on the enzymatic hydrolysis of L-ascorbic acid-2-phosphate (AAP) by ALP to generate AA. Quantitative evaluation of ALP activity in a range from 0.1 to 5U/L with the detection limit of 0.07U/L can be realized in this sensing system. Endowed with high sensitivity and selectivity, the proposed assay is capable of detecting ALP in biological system with satisfactory results. Meanwhile, this sensing system can be easily extended to the detection of various AA-involved analytes. Copyright © 2017 Elsevier B.V. All rights reserved.

  5. Quantum chemical investigation on the mechanism and kinetics of OH radical-initiated atmospheric oxidation of PCB-47. (United States)

    Sun, Yanhui; Zhang, Qingzhu; Wang, Hui; Wang, Wenxing


    The OH radical-initiated atmospheric oxidation degradation of 2,2',4,4'-tetrachlorobiphenyl (PCB-47) was investigated by using quantum chemical calculations. All possible pathways involved in the oxidation process were discussed. Potential barriers and reaction heats have been obtained to assess the energetically favorable reaction pathways and the relatively stable products. The study shows that the OH radicals are more likely to attack the C3 and C5 atom of the aromatic ring in the PCB-47 molecule to form PCB-OH adducts. Subsequent reactions are the addition of O2 or NO2 molecule to the PCB-OH adducts at the ortho position of the OH group. Water molecule plays an important role during the whole degradation process. The individual and overall rate constants were calculated by using the Rice-Ramsperger-Kassel-Marcus (RRKM) theory over the temperature range of 180-370K. At 298K, the atmospheric lifetime of PCB-47 determined by OH radicals is about 9.1d. The computational results are crucial to risk assessment and pollution prevention of PCBs. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Quantum and classical studies of collisional excitation in H + CO and two other projects in theoretical chemical dynamics

    International Nuclear Information System (INIS)

    Geiger, L.C.


    This dissertation is a collection of four projects in theoretical chemical dynamics. In the first two projects collisional excitation in H + CO was studied using the quasiclassical trajectory method and the quantum infinite order sudden approximation (QIOS). Integral cross sections calculated using these methods were found to agree well with experimental and classical IOS results. The trajectory study was also used to examine the effects of potential energy surface features on the dynamics. Two surfaces were examined: a fitted surface based on ab initio points and a global ab initio surface. Next, the quasiclassical trajectory method was used to obtain cross sections and rate constants for O + H 2 → OH + H and analogous deuterium isotope reactions. The results using the Johnson and Winter surface agreed well with those of transition state theory (TST) and experiment, except for O + HD → OH + D. TST rate constants were calculated using an ab initio surface. These results were in poor agreement with calculations using the Johnson and Winter surface. A theory of action-angle variables for coupled oscillator systems was developed in the fourth project

  7. Quantum Chemical Calculations Using Accelerators: Migrating Matrix Operations to the NVIDIA Kepler GPU and the Intel Xeon Phi. (United States)

    Leang, Sarom S; Rendell, Alistair P; Gordon, Mark S


    Increasingly, modern computer systems comprise a multicore general-purpose processor augmented with a number of special purpose devices or accelerators connected via an external interface such as a PCI bus. The NVIDIA Kepler Graphical Processing Unit (GPU) and the Intel Phi are two examples of such accelerators. Accelerators offer peak performances that can be well above those of the host processor. How to exploit this heterogeneous environment for legacy application codes is not, however, straightforward. This paper considers how matrix operations in typical quantum chemical calculations can be migrated to the GPU and Phi systems. Double precision general matrix multiply operations are endemic in electronic structure calculations, especially methods that include electron correlation, such as density functional theory, second order perturbation theory, and coupled cluster theory. The use of approaches that automatically determine whether to use the host or an accelerator, based on problem size, is explored, with computations that are occurring on the accelerator and/or the host. For data-transfers over PCI-e, the GPU provides the best overall performance for data sizes up to 4096 MB with consistent upload and download rates between 5-5.6 GB/s and 5.4-6.3 GB/s, respectively. The GPU outperforms the Phi for both square and nonsquare matrix multiplications.

  8. Profiling of cyclic hexadepsipeptides roseotoxins synthesized in vitro and in vivo: a combined tandem mass spectrometry and quantum chemical study. (United States)

    Jegorov, Alexandr; Paizs, Béla; Zabka, Martin; Kuzma, Marek; Havlícek, Vladimír; Giannakopulos, Anastassios E; Derrick, Peter J


    High-performance liquid chromatography and tandem mass spectrometry (HPLC/MS/MS) was used for the detection of cyclic hexadepsipeptides roseotoxins produced by Trichothecium roseum. Roseotoxins were found in both submerged standard cultivation on CzapekDox medium and in vivo cultivation extract obtained from an apple. Roseotoxin chromatographic profiles from these two experiments were compared. Product-ion collision-induced dissociation (CID) spectra obtained on an ion trap (electrospray ionisation, ESI) were used for the identification of natural roseotoxins A, B, C and of minor destruxins A and B. The dissociation behavior of roseotoxins is discussed in terms of a fragmentation scheme proposed for describing the dissociation pathways of cyclic peptides. This scheme involves opening of the cyclopeptide ring via formation of oxazolone derivatives and fragmentation of the resulting linear species, which have a free N-terminus and an oxazolone ring at the C-terminus. Some aspects of this fragmentation scheme are underlined by modeling the dissociation channels of roseotoxin A using quantum chemical calculations. The structures of roseotoxin A and destruxin B were verified by nuclear magnetic resonance (NMR) spectroscopy. Structures of three new minor natural roseotoxins [Val(4)]RosA, [MeLxx(4)]RosA and [MeLxx(4)]RosB were deduced by ion cyclotron resonance Fourier transform mass spectrometry (ICR-FT-MS) and ion trap tandem mass spectrometry by examining the pre-separated roseotoxin fraction.

  9. Raman enhancement on ultra-clean graphene quantum dots produced by quasi-equilibrium plasma-enhanced chemical vapor deposition. (United States)

    Liu, Donghua; Chen, Xiaosong; Hu, Yibin; Sun, Tai; Song, Zhibo; Zheng, Yujie; Cao, Yongbin; Cai, Zhi; Cao, Min; Peng, Lan; Huang, Yuli; Du, Lei; Yang, Wuli; Chen, Gang; Wei, Dapeng; Wee, Andrew Thye Shen; Wei, Dacheng


    Graphene is regarded as a potential surface-enhanced Raman spectroscopy (SERS) substrate. However, the application of graphene quantum dots (GQDs) has had limited success due to material quality. Here, we develop a quasi-equilibrium plasma-enhanced chemical vapor deposition method to produce high-quality ultra-clean GQDs with sizes down to 2 nm directly on SiO 2 /Si, which are used as SERS substrates. The enhancement factor, which depends on the GQD size, is higher than conventional graphene sheets with sensitivity down to 1 × 10 -9  mol L -1 rhodamine. This is attributed to the high-quality GQDs with atomically clean surfaces and large number of edges, as well as the enhanced charge transfer between molecules and GQDs with appropriate diameters due to the existence of Van Hove singularities in the electronic density of states. This work demonstrates a sensitive SERS substrate, and is valuable for applications of GQDs in graphene-based photonics and optoelectronics.

  10. Chemical Structure, Ensemble and Single-Particle Spectroscopy of Thick-Shell InP-ZnSe Quantum Dots. (United States)

    Reid, Kemar R; McBride, James R; Freymeyer, Nathaniel J; Thal, Lucas B; Rosenthal, Sandra J


    Thick-shell (>5 nm) InP-ZnSe colloidal quantum dots (QDs) grown by a continuous-injection shell growth process are reported. The growth of a thick crystalline shell is attributed to the high temperature of the growth process and the relatively low lattice mismatch between the InP core and ZnSe shell. In addition to a narrow ensemble photoluminescence (PL) line-width (∼40 nm), ensemble and single-particle emission dynamics measurements indicate that blinking and Auger recombination are reduced in these heterostructures. More specifically, high single-dot ON-times (>95%) were obtained for the core-shell QDs, and measured ensemble biexciton lifetimes, τ 2x ∼ 540 ps, represent a 7-fold increase compared to InP-ZnS QDs. Further, high-resolution energy dispersive X-ray (EDX) chemical maps directly show for the first time significant incorporation of indium into the shell of the InP-ZnSe QDs. Examination of the atomic structure of the thick-shell QDs by high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) reveals structural defects in subpopulations of particles that may mitigate PL efficiencies (∼40% in ensemble), providing insight toward further synthetic refinement. These InP-ZnSe heterostructures represent progress toward fully cadmium-free QDs with superior photophysical properties important in biological labeling and other emission-based technologies.

  11. Mid-IR quantum cascade lasers as an enabling technology for a new generation of chemical analyzers for liquids (United States)

    Lendl, B.; Reidl-Leuthner, C.; Ritter, W.


    This presentation introduces a chemical analyzer (The ERACHECK) which is based on quantum cascade laser technology for measuring oil-in-water. Using these mid-IR lasers, it was possible to develop a portable, robust and highly precise analyzer for the measurement of oil-in-water, a parameter which is vital in the petrochemical industry for process control and environmental analysis. The overall method employs a liquid-liquid extraction step of the aqueous sample using a cyclic, aliphatic hydrocarbon such as cyclohexane. Quantification is based on measurement of the C-H deformation vibrations of the extracted hydrocarbons in the cyclic extraction solvent. The developed method is linear from 0.5 - 2000 ppm of oil in water, with precisions well below 15% in terms of r.s.d for repeated measurements. The portability of the ERACHECK and its robustness has been key for its successful use on oil rigs as well as petrochemical production sites on land. The values provided by the ERACHECK correlate well with those obtained by the former CFC (Freon 113) based method for oil in water, which is no longer in use in industrialized countries due to the ozone depleting effect of the CFCs employed.

  12. Chemical approach to neutral-ionic valence instability, quantum phase transition, and relaxor ferroelectricity in organic charge-transfer complexes

    International Nuclear Information System (INIS)

    Horiuchi, Sachio; Kumai, Reiji; Okimoto, Yoichi; Tokura, Yoshinori


    Neutral-ionic (NI) phase transition is a reversible switching of organic charge-transfer complexes between distinct valence states by external stimuli. This phase transformation in the low-dimensional system is demonstrated to provide a variety of novel dielectric, structural, and electronic properties. Importantly, ionization of the electron donor-acceptor pairs is usually accompanied by a ferroelectric or antiferroelectric order of the molecular lattice, leading to huge dielectric response near the transition point. Although these characteristics are potentially useful for future electronic and optical applications, the thermally accessible NI transition (TINIT) is still an extremely rare case. The TINIT compounds including some new materials are overviewed in order to provide convenient guides to their design and experimental identifications. The phase transition and dielectric properties can be closely controlled in various ways depending on chemical and physical modifications of the crystals. Among them, a quantum phase transition and relaxor ferroelectricity, both of which are currently attracting subjects from both scientific and practical perspectives, are highlighted as the first achievements in organic charge-transfer complexes

  13. National needs for critically evaluated physical and chemical data. (the 'codan' report). Final report

    International Nuclear Information System (INIS)

    Stockmayer, W.H.


    The report assesses the level of critical evaluation of numerical data needed to meet national needs for reliable scientific data, and the funding needed therefor. The report (1) surveys the organizations that currently carry out critical data evaluation and determines the present level of funding for such activities; (2) studies the role of organized data collections and the required depth of evaluation of the data in previous RandD programs and assesses the benefits of such activities relative to their cost; (3) identifies current and future data needs in major national RandD programs, particularly those concerned with energy, environmental quality, and materials utilization. The report, concluding that the present level of data evaluation activities is about 1/3 to 1/2 that needed, makes several recommendations for administrative methods of action to help correct this situation

  14. Spoilt for choice: A critical review on the chemical and biological assessment of current wastewater treatment technologies. (United States)

    Prasse, Carsten; Stalter, Daniel; Schulte-Oehlmann, Ulrike; Oehlmann, Jörg; Ternes, Thomas A


    The knowledge we have gained in recent years on the presence and effects of compounds discharged by wastewater treatment plants (WWTPs) brings us to a point where we must question the appropriateness of current water quality evaluation methodologies. An increasing number of anthropogenic chemicals is detected in treated wastewater and there is increasing evidence of adverse environmental effects related to WWTP discharges. It has thus become clear that new strategies are needed to assess overall quality of conventional and advanced treated wastewaters. There is an urgent need for multidisciplinary approaches combining expertise from engineering, analytical and environmental chemistry, (eco)toxicology, and microbiology. This review summarizes the current approaches used to assess treated wastewater quality from the chemical and ecotoxicological perspective. Discussed chemical approaches include target, non-target and suspect analysis, sum parameters, identification and monitoring of transformation products, computational modeling as well as effect directed analysis and toxicity identification evaluation. The discussed ecotoxicological methodologies encompass in vitro testing (cytotoxicity, genotoxicity, mutagenicity, endocrine disruption, adaptive stress response activation, toxicogenomics) and in vivo tests (single and multi species, biomonitoring). We critically discuss the benefits and limitations of the different methodologies reviewed. Additionally, we provide an overview of the current state of research regarding the chemical and ecotoxicological evaluation of conventional as well as the most widely used advanced wastewater treatment technologies, i.e., ozonation, advanced oxidation processes, chlorination, activated carbon, and membrane filtration. In particular, possible directions for future research activities in this area are provided. Copyright © 2015 Elsevier Ltd. All rights reserved.

  15. Internal Domains of Natural Porous Media Revealed: Critical Locations for Transport, Storage, and Chemical Reaction

    Energy Technology Data Exchange (ETDEWEB)

    Zachara, John M.; Brantley, Susan L.; Chorover, Jon D.; Ewing, Robert P.; Kerisit, Sebastien N.; Liu, Chongxuan; Perfect, E.; Rother, Gernot; Stack, Andrew G.


    Internal pore domains exist within rocks, lithic fragments, subsurface sediments and soil aggregates. These domains, which we term internal domains in porous media (IDPM), contain a significant fraction of their porosity as nanopores, dominate the reactive surface area of diverse porous media types, and are important locations for chemical reactivity and hydrocarbon storage. Traditionally difficult to interrogate, advances in instrumentation and imaging methods are providing new insights on the physical structures and chemical attributes of IDPM. In this review we: discuss analytical methods to characterize IDPM, evaluate what has been learned about their size distributions, connectivity, and extended structures; determine whether they exhibit unique chemical reactivity; and assess potential for their inclusion in reactive transport models. Three key findings are noteworthy. 1) A combination of methods now allows complete characterization of the porosity spectrum of natural materials and its connectivity; while imaging microscopies are providing three dimensional representations of the interconnected pore network. 2) Chemical reactivity in pores <10 nm is expected to be different from micro and macropores, yet research performed to date is inconclusive on the nature, direction, and magnitude of effect. 3) Existing continuum reactive transport models treat IDPM as a sub-grid feature with average, empirical, scale-dependent parameters; and are not formulated to include detailed information on pore networks. Overall we find that IDPM are key features controlling hydrocarbon release from shales in hydrofracking systems, organic matter stabilization and recalcitrance in soil, weathering and soil formation, and long term inorganic and organic contaminant behavior in the vadose zone and groundwater. We conclude with an assessment of impactful research opportunities to advance understanding of IDPM, and to incorporate their important effects in reactive transport models

  16. Chemical nature and structure of organic coating of quantum dots is crucial for their application in imaging diagnostics (United States)

    Bakalova, Rumiana; Zhelev, Zhivko; Kokuryo, Daisuke; Spasov, Lubomir; Aoki, Ichio; Saga, Tsuneo


    Background: One of the most attractive properties of quantum dots is their potential to extend the opportunities for fluorescent and multimodal imaging in vivo. The aim of the present study was to clarify whether the composition and structure of organic coating of nanoparticles are crucial for their application in vivo. Methods: We compared quantum dots coated with non-crosslinked amino-functionalized polyamidoamine (PAMAM) dendrimers, quantum dots encapsulated in crosslinked carboxyl-functionalized PAMAM dendrimers, and silica-shelled amino-functionalized quantum dots. A multimodal fluorescent and paramagnetic quantum dot probe was also developed and analyzed. The probes were applied intravenously in anesthetized animals for visualization of brain vasculature using two-photon excited fluorescent microscopy and visualization of tumors using fluorescent IVIS® imaging (Caliper Life Sciences, Hopkinton, MA) and magnetic resonance imaging. Results: Quantum dots coated with non-crosslinked dendrimers were cytotoxic. They induced side effects in vivo, including vasodilatation with a decrease in mean arterial blood pressure and heart rate. The quantum dots penetrated the vessels, which caused the quality of fluorescent imaging to deteriorate. Quantum dots encapsulated in crosslinked dendrimers had low cytotoxicity and were biocompatible. In concentrations quantum dots/kg bodyweight, these nanoparticles did not affect blood pressure and heart rate, and did not induce vasodilatation or vasoconstriction. PEGylation (PEG [polyethylene glycol]) was an indispensable step in development of a quantum dot probe for in vivo imaging, based on silica-shelled quantum dots. The non-PEGylated silica-shelled quantum dots possessed low colloidal stability in high-salt physiological fluids, accompanied by rapid aggregation in vivo. The conjugation of silica-shelled quantum dots with PEG1100 increased their stability and half-life in the circulation without significant enhancement of their

  17. Adsorption, Thermodynamic and Quantum Chemical Studies of 1-hexyl-3-methylimidazolium Based Ionic Liquids as Corrosion Inhibitors for Mild Steel in HCl (United States)

    Mashuga, Motsie E.; Olasunkanmi, Lukman O.; Adekunle, Abolanle S.; Yesudass, Sasikumar; Kabanda, Mwadham M.; Ebenso, Eno E.


    The inhibition of mild steel corrosion in 1 M HCl solution by some ionic liquids (ILs) namely, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate [HMIM][TfO], 1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM][BF4], 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM][PF6], and 1-hexyl-3-methylimidazolium iodide [HMIM][I] was investigated using electrochemical measurements, spectroscopic analyses and quantum chemical calculations. All the ILs showed appreciably high inhibition efficiency. At 303 K, the results of electrochemical measurements indicated that the studied ILs are mixed-type inhibitors. The adsorption studies showed that all the four ILs adsorb spontaneously on steel surface with [HMIM][TfO], [HMIM][BF4] and [HMIM][I] obeying Langmuir adsorption isotherm, while [HMIM][PF6] conformed better with Temkin adsorption isotherm. Spectroscopic analyses suggested the formation of Fe/ILs complexes. Some quantum chemical parameters were calculated to corroborate experimental results.

  18. The inhibition effect of Azure A on mild steel in 1 M HCl. A complete study: Adsorption, temperature, duration and quantum chemical aspects

    International Nuclear Information System (INIS)

    Özkır, Demet; Kayakırılmaz, Kadriye; Bayol, Emel; Gürten, A. Ali; Kandemirli, Fatma


    Highlights: ► Azure A molecule is found to be a good inhibitor for mild steel in HCl solution. ► SEM results clearly indicate that a protective film formation occurred on the mild steel surface. ► The long term corrosion tests are cleared that the Azure A has effectively protected the mild steel in HCl solution. ► The quantum chemical measurements were cleared the reactive sites and charges of atoms in the molecule. - Abstract: In this study, inhibition effect of Azure A on mild steel in 1.0 M HCl were evaluated by using electrochemical impedance spectroscopy (EIS), linear polarization resistance (LPR), and potentiodynamic polarization and scanning electron microscope (SEM) methods. These studies were carried out at different concentrations, temperatures and durations. The inhibitor molecules were chemisorbed on electrode surface according to the Langmuir adsorption isotherm. The quantum chemical calculations were employed to give further insight into the inhibition mechanism of Azure A.

  19. Lower mantle hydrogen partitioning between periclase and perovskite: A quantum chemical modelling (United States)

    Merli, Marcello; Bonadiman, Costanza; Diella, Valeria; Pavese, Alessandro


    Partitioning of hydrogen (often referred to as H2O) between periclase (pe) and perovskite (pvk) at lower mantle conditions (24-80 GPa) was investigated using quantum mechanics, equilibrium reaction thermodynamics and by monitoring two H-incorporation models. One of these (MSWV) was based on replacements provided by Mg2+ ↔ 2H+ and Si4+ ↔ 4H+; while the other (MSWA) relied upon substitutions in 2Mg2+ ↔ Al3+ + H+ and Si4+ ↔ Al3+ + H+. H2O partitioning in these phases was considered in the light of homogeneous (Bulk Silicate Earth; pvk: 75%-pe:16% model contents) and heterogeneous (Layered Mantle; pvk:78%-pe:14% modal contents) mantle geochemical models, which were configured for lower and upper bulk water contents (BWC) at 800 and 1500 ppm, respectively. The equilibrium constant, BWCK(P,T), for the reactions controlling the H-exchange between pe and pvk exhibited an almost negligible dependence on P, whereas it was remarkably sensitive to T, BWC and the hydrogen incorporation scheme. Both MSWV and MSWA lead to BWCK(P,T) ⩽ 1, which suggests a ubiquitous shift in the exchange reaction towards an H2O-hosting perovskite. This took place more markedly in the latter incorporation mechanism, indicating that H2O-partitioning is affected by the uptake mechanism. In general, the larger the BWC, the smaller the BWCK(P,T). Over the BWC reference range, MSWV led to BWCK(P,T)-grand average () calculated along lower mantle P-T-paths of ≈0.875. With regard to the MSWA mechanism, was more sensitive to BWC (and LM over BSE), but its values remained within the rather narrow 0.61-0.78 range. The periclase-perovskite H2O concentration-based partition coefficient, KdH2Ope/pvk, was inferred using , assuming both hydrous and anhydrous-dominated systems. MSWV revealed a KdH2Ope/pvk -BWC linear interpolation slope which was close to 0 and KdH2Ope/pvk values of 0.36 and 0.56 (for anhydrous and hydrous system, respectively). MSWA, in turn, yielded a KdH2Ope/pvk trend with a slightly

  20. Experimental and quantum chemical studies of a novel synthetic prenylated chalcone

    Directory of Open Access Journals (Sweden)

    Espinoza-Hicks José C


    Full Text Available Abstract Background Chalcones are ubiquitous natural compounds with a wide variety of reported biological activities, including antitumoral, antiviral and antimicrobial effects. Furthermore, chalcones are being studied for its potential use in organic electroluminescent devices; therefore the description of their spectroscopic properties is important to elucidate the structure of these molecules. One of the main techniques available for structure elucidation is the use of Nuclear Magnetic Resonance Spectroscopy (NMR. Accordingly, the prediction of the NMR spectra in this kind of molecules is necessary to gather information about the influence of substituents on their spectra. Results A novel substituted chalcone has been synthetized. In order to identify the functional groups present in the new synthesized compound and confirm its chemical structure, experimental and theoretical 1H-NMR and 13C-NMR spectra were analyzed. The theoretical molecular structure and NMR spectra were calculated at both the Hartree-Fock and Density Functional (meta: TPSS; hybrid: B3LYP and PBE1PBE; hybrid meta GGA: M05-2X and M06-2X levels of theory in combination with a 6-311++G(d,p basis set. The structural parameters showed that the best method for geometry optimization was DFT:M06-2X/6-311++G(d,p, whereas the calculated bond angles and bond distances match experimental values of similar chalcone derivatives. The NMR calculations were carried out using the Gauge-Independent Atomic Orbital (GIAO formalism in a DFT:M06-2X/6-311++G(d,p optimized geometry. Conclusion Considering all HF and DFT methods with GIAO calculations, TPSS and PBE1PBE were the most accurate methods used for calculation of 1H-NMR and 13C-NMR chemical shifts, which was almost similar to the B3LYP functional, followed in order by HF, M05-2X and M06-2X methods. All calculations were done using the Gaussian 09 software package. Theoretical calculations can be used to predict and confirm the structure of

  1. Enhanced pairing of quantum critical metals near d=3+1

    Energy Technology Data Exchange (ETDEWEB)

    Fitzpatrick, A. Liam; Kachru, Shamit; Kaplan, Jared; Raghu, S.; Torroba, Gonzalo; Wang, Huajia


    We study the dynamics of a quantum critical boson coupled to a Fermi surface in intermediate energy regimes where the Landau damping of the boson can be parametrically controlled, either via large Fermi velocity or by large- N techniques. We develop a systematic approach to the BCS instability of such systems, including careful treatment of the enhanced log 2 and log 3 singularities which appear already at 1-loop. These singularities arise due to the exchange of a critical boson in the Cooper channel and are absent in Fermi liquid theory. We also treat possible instabilities to charge density wave (CDW) formation, and compare the scales Λ BCS and Λ CDW of the onset of the instabilities in different parametric regimes. We address the question of whether the dressing of the fermions into a non-Fermi liquid via interactions with the order parameter field can happen at energies > Λ BCS , Λ CDW .

  2. Synthesis of a new 1,2,3,4,5-pentasubstituted cyclohexanol and determining its stereochemistry by NMR spectroscopy and quantum-chemical calculations. (United States)

    Mamedov, Ibrahim; Abbasoglu, Rza; Bayramov, Musa; Maharramov, Abel


    The presence of substituents in cyclohexane can influence to the ratio of conformers; for some cases, the boat form is preferable. The new six-membered cyclohexanol derivative 2 has been obtained by the synthesis of (E)-1-(bromophenyl)-3-phenylpropen-2-one (1). The NMR and quantum-chemical conformational analysis for the 2 have carried out, and its possible mechanism of formation was given. Copyright © 2015 John Wiley & Sons, Ltd. Copyright © 2015 John Wiley & Sons, Ltd.

  3. Quantum Chemical and Experimental Studies on the Mechanism of Alkylation of β-Dicarbonyl Compounds. The Synthesis of Five and Six Membered Heterocyclic Spiro Derivatives

    Directory of Open Access Journals (Sweden)

    Ali Hüseyinli


    Full Text Available The alkylation of β-dicarbonyl compounds in a K2CO3/DMSO system wasfound to afford O- and C-alkylated derivatives, depending on the type of the β-dicarbonylcompound involved. The alkyl derivatives obtained were used in the synthesis of some newspiro barbituric acid derivatives. Quantum chemical calculations were carried out toelucidate the reaction mechanisms for some typical synthesis.

  4. Essential Oils’ Chemical Characterization and Investigation of Some Biological Activities: A Critical Review (United States)

    Dhifi, Wissal; Bellili, Sana; Jazi, Sabrine; Bahloul, Nada; Mnif, Wissem


    This review covers literature data summarizing, on one hand, the chemistry of essential oils and, on the other hand, their most important activities. Essential oils, which are complex mixtures of volatile compounds particularly abundant in aromatic plants, are mainly composed of terpenes biogenerated by the mevalonate pathway. These volatile molecules include monoterpenes (hydrocarbon and oxygenated monoterpens), and also sesquiterpenes (hydrocarbon and oxygenated sesquiterpens). Furthermore, they contain phenolic compounds, which are derived via the shikimate pathway. Thanks to their chemical composition, essential oils possess numerous biological activities (antioxidant, anti-inflammatory, antimicrobial, etc…) of great interest in food and cosmetic industries, as well as in the human health field. PMID:28930135

  5. Structure and Bonding in Uranyl(VI) Peroxide and Crown Ether Complexes; Comparison of Quantum Chemical and Experimental Data. (United States)

    Vallet, Valérie; Grenthe, Ingmar


    The structure, chemical bonding, and thermodynamics of alkali ions in M[12-crown-4] + , M[15-crown-5] + , and M[18-crown-6] + , M[UO 2 (O 2 )(OH 2 ) 2 ] + 4,5 , and M[UO 2 (O 2 )(OH)(OH 2 )] n 1-n (n = 4, 5) complexes have been explored by using quantum chemical (QC) calculations at the ab initio level. The chemical bonding has been studied in the gas phase in order to eliminate solvent effects. QTAIM analysis demonstrates features that are very similar in all complexes and typical for electrostatic M-O bonds, but with the M-O bonds in the uranyl peroxide systems about 20 kJ mol -1 stronger than in the corresponding crown ether complexes. The regular decrease in bond strength with increasing M-O bond distance is consistent with predominantly electrostatic contributions. Energy decomposition of the reaction energies in the gas phase and solvent demonstrates that the predominant component of the total attractive (ΔE elec + ΔE orb ) energy contribution is the electrostatic component. There are no steric constraints for coordination of large cations to small rings, because the M + ions are located outside the ring plane, [O n ], formed by the oxygen donors in the ligands; coordination of ions smaller than the ligand cavity results in longer than normal M-O distances or in a change in the number of bonds, both resulting in weaker complexes. The Gibbs energies, enthalpies, and entropies of reaction calculated using the conductor-like screening model, COSMO, to account for solvent effects deviate significantly from experimental values in water, while those in acetonitrile are in much better agreement. Factors that might affect the selectivity are discussed, but our conclusion is that present QC methods are not accurate enough to describe the rather small differences in selectivity, which only amount to 5-10 kJ mol -1 . We can, however, conclude on the basis of QC and experimental data that M[crown ether] + complexes in the strongly coordinating water solvent are of

  6. Spin excitations and quantum criticality in the quasi-one-dimensional Ising-like ferromagnet CoCl2·2D2O in a transverse field

    DEFF Research Database (Denmark)

    Larsen, J.; Schäffer, T. K.; Hansen, U. B.


    We present experimental evidence for a quantum phase transition in the easy-axis S = 3/2 anisotropic quasione-dimensional ferromagnet CoCl2 · 2D2O in a transverse field. Elastic neutron scattering shows that the magnetic order parameter vanishes at a transverse critical field μ0Hc = 16.05(4) T...... that the quantum phase transition in CoCl2 · 2D2O differs significantly from the textbook version of a S = 1/2 Ising chain in a transverse field. We attribute the difference to weak but finite three-dimensionality of the magnetic interactions......., while inelastic neutron scattering shows that the gap in the magnetic excitation spectrum vanishes at the same field value, and reopens for H>Hc. The field dependence of the order parameter and the gap are well described by critical exponents β = 0.45 ± 0.09 and zν close to 1/2, implying...

  7. Spin dynamics in the high-field phase of quantum-critical S =1/2 TlCuCl sub 3

    CERN Document Server

    Rueegg, C; Furrer, A; Krämer, K; Güdel, H U; Vorderwisch, P; Mutka, H


    An external magnetic field suppresses the spin-energy gap in singlet ground state S=1/2 TlCuCl sub 3. The system becomes quantum-critical at H sub c approx 5.7 T, where the energy of the lowest Zeeman-split triplet excitation crosses the nonmagnetic ground state. Antiferromagnetic ordering is reported above H sub c , which underlines the three-dimensional nature of the observed quantum phase transition. The intrinsic parameters of S=1/2 TlCuCl sub 3 allow us to access the critical region microscopically by neutron scattering. A substantial study of the spin dynamics in the high-field phase of TlCuCl sub 3 at T=1.5 K up to H=12 T was performed for the first time. The results possibly indicate two dynamical regimes, which can be understood within characteristically renormalized triplet modes and a low-lying dynamics of potentially collective origin. (orig.)

  8. Prediction of pKa Values for Druglike Molecules Using Semiempirical Quantum Chemical Methods. (United States)

    Jensen, Jan H; Swain, Christopher J; Olsen, Lars


    Rapid yet accurate pK a prediction for druglike molecules is a key challenge in computational chemistry. This study uses PM6-DH+/COSMO, PM6/COSMO, PM7/COSMO, PM3/COSMO, AM1/COSMO, PM3/SMD, AM1/SMD, and DFTB3/SMD to predict the pK a values of 53 amine groups in 48 druglike compounds. The approach uses an isodesmic reaction where the pK a value is computed relative to a chemically related reference compound for which the pK a value has been measured experimentally or estimated using a standard empirical approach. The AM1- and PM3-based methods perform best with RMSE values of 1.4-1.6 pH units that have uncertainties of ±0.2-0.3 pH units, which make them statistically equivalent. However, for all but PM3/SMD and AM1/SMD the RMSEs are dominated by a single outlier, cefadroxil, caused by proton transfer in the zwitterionic protonation state. If this outlier is removed, the RMSE values for PM3/COSMO and AM1/COSMO drop to 1.0 ± 0.2 and 1.1 ± 0.3, whereas PM3/SMD and AM1/SMD remain at 1.5 ± 0.3 and 1.6 ± 0.3/0.4 pH units, making the COSMO-based predictions statistically better than the SMD-based predictions. For pK a calculations where a zwitterionic state is not involved or proton transfer in a zwitterionic state is not observed, PM3/COSMO or AM1/COSMO is the best pK a prediction method; otherwise PM3/SMD or AM1/SMD should be used. Thus, fast and relatively accurate pK a prediction for 100-1000s of druglike amines is feasible with the current setup and relatively modest computational resources.

  9. Quantum Chemical Investigation on Photochemical Reactions of Nonanoic Acids at Air-Water Interface. (United States)

    Xiao, Pin; Wang, Qian; Fang, Wei-Hai; Cui, Ganglong


    Photoinduced chemical reactions of organic compounds at the marine boundary layer have recently attracted significant experimental attention because this kind of photoreactions has been proposed to have substantial impact on local new particle formation and their photoproducts could be a source of secondary organic aerosols. In this work, we have employed first-principles density functional theory method combined with cluster models to systematically explore photochemical reaction pathways of nonanoic acids (NAs) to form volatile saturated and unsaturated C 9 and C 8 aldehydes at air-water interfaces. On the basis of the results, we have found that the formation of C 9 aldehydes is not initiated by intermolecular Norrish type II reaction between two NAs but by intramolecular T 1 C-O bond fission of NA generating acyl and hydroxyl radicals. Subsequently, saturated C 9 aldehydes are formed through hydrogenation reaction of acyl radical by another intact NA. Following two dehydrogenation reactions, unsaturated C 9 aldehydes are generated. In parallel, the pathway to C 8 aldehydes is initiated by T 1 C-C bond fission of NA, which generates octyl and carboxyl radicals; then, an octanol is formed through recombination reaction of octyl with hydroxyl radical. In the following, two dehydrogenation reactions result into an enol intermediate from which saturated C 8 aldehydes are produced via NA-assisted intermolecular hydrogen transfer. Finally, two dehydrogenation reactions generate unsaturated C 8 aldehydes. In these reactions, water and NA molecules are found to play important roles. They significantly reduce relevant reaction barriers. Our work has also explored oxygenation reactions of NA with molecular oxygen and radical-radical dimerization reactions.

  10. How soil organic matter composition controls hexachlorobenzene-soil-interactions: adsorption isotherms and quantum chemical modeling. (United States)

    Ahmed, Ashour A; Kühn, Oliver; Aziz, Saadullah G; Hilal, Rifaat H; Leinweber, Peter


    Hazardous persistent organic pollutants (POPs) interact in soil with the soil organic matter (SOM) but this interaction is insufficiently understood at the molecular level. We investigated the adsorption of hexachlorobenzene (HCB) on soil samples with systematically modified SOM. These samples included the original soil, the soil modified by adding a hot water extract (HWE) fraction (soil+3 HWE and soil+6 HWE), and the pyrolyzed soil. The SOM contents increased in the order pyrolyzed soilsoilsoil+3 HWEsoil+6 HWE. For the latter three samples this order was also valid for the HCB adsorption. The pyrolyzed soil adsorbed more HCB than the other samples at low initial concentrations, but at higher concentrations the HCB adsorption became weaker than in the samples with HWE addition. This adsorption combined with the differences in the chemical composition between the soil samples suggested that alkylated aromatic, phenol, and lignin monomer compounds contributed most to the HCB adsorption. To obtain a molecular level understanding, a test set has been developed on the basis of elemental analysis which comprises 32 representative soil constituents. The calculated binding energy for HCB with each representative system shows that HCB binds to SOM stronger than to soil minerals. For SOM, HCB binds to alkylated aromatic, phenols, lignin monomers, and hydrophobic aliphatic compounds stronger than to polar aliphatic compounds confirming the above adsorption isotherms. Moreover, quantitative structure-activity relationship (QSAR) of the binding energy with independent physical properties of the test set systems for the first time indicated that the polarizability, the partial charge on the carbon atoms, and the molar volume are the most important properties controlling HCB-SOM interactions. Copyright © 2013 Elsevier B.V. All rights reserved.

  11. Kinetics of Natural Attenuation: Review of the Critical Chemical Conditions and Measurements at Bore Scale

    Directory of Open Access Journals (Sweden)

    O. Atteia


    Full Text Available This paper describes the chemical conditions that should favour the biodegradation of organic pollutants. Thermodynamic considerations help to define the reaction that can occur under defined chemical conditions. The BTEX (benzene, toluene, ethylbenzene, and xylene degradation is focused on benzene, as it is the most toxic oil component and also because it has the slowest degradation rate under most field conditions. Several studies on benzene degradation allow the understanding of the basic degradation mechanisms and their importance in field conditions. The use of models is needed to interpret field data when transport, retardation, and degradation occur. A detailed comparison of two existing models shows that the limits imposed by oxygen transport must be simulated precisely to reach correct plumes shapes and dimensions, and that first-order kinetic approaches may be misleading. This analysis led us to develop a technique to measure directly biodegradation in the field. The technique to recirculate water at the borehole scale and the CO2 analysis are depicted. First results of biodegradation show that this technique is able to easily detect the degradation of 1 mg/l of hydrocarbons and that, in oxic media, a fast degradation rate of mixed fuel is observed.

  12. Photon and neutron interrogation techniques for chemical explosives detection in air cargo: A critical review

    International Nuclear Information System (INIS)

    Runkle, Robert C.; White, Timothy A.; Miller, Erin A.; Caggiano, Joseph A.; Collins, Brian A.


    Scanning cargo transported via aircraft ('air cargo') for explosive threats is a problem that presently lacks a comprehensive technical solution. While chemical explosives detection in the baggage-scanning domain has a rich history that sheds light on potential solutions, air cargo differs in several important ways, and thus one cannot look to the present array of technologies. Some contemporary solutions, such as trace analysis, are not readily applied to cargo because of sampling challenges while the larger geometry of air cargo makes others less effective. This review article examines an array of interrogation techniques using photons and neutrons as incident particles. We first present a summary of the signatures and observables chemical explosives provide and review how they have been exploited in baggage scanning. Following this review is a description of the challenges posed by the air-cargo application space. After considering sources of photons and neutrons, we describe methods focused on transmission imaging, sub-surface examination, and elemental characterization. It is our goal to expand the understanding of each method's technical promise while largely deferring questions that revolve around footprint, safety, and conduct of operations. Our overarching intent is that a comprehensive understanding of potential techniques will foster the development of a comprehensive solution.

  13. Chemical Shifts of the Carbohydrate Binding Domain of Galectin-3 from Magic Angle Spinning NMR and Hybrid Quantum Mechanics/Molecular Mechanics Calculations. (United States)

    Kraus, Jodi; Gupta, Rupal; Yehl, Jenna; Lu, Manman; Case, David A; Gronenborn, Angela M; Akke, Mikael; Polenova, Tatyana


    Magic angle spinning NMR spectroscopy is uniquely suited to probe the structure and dynamics of insoluble proteins and protein assemblies at atomic resolution, with NMR chemical shifts containing rich information about biomolecular structure. Access to this information, however, is problematic, since accurate quantum mechanical calculation of chemical shifts in proteins remains challenging, particularly for 15 N H . Here we report on isotropic chemical shift predictions for the carbohydrate recognition domain of microcrystalline galectin-3, obtained from using hybrid quantum mechanics/molecular mechanics (QM/MM) calculations, implemented using an automated fragmentation approach, and using very high resolution (0.86 Å lactose-bound and 1.25 Å apo form) X-ray crystal structures. The resolution of the X-ray crystal structure used as an input into the AF-NMR program did not affect the accuracy of the chemical shift calculations to any significant extent. Excellent agreement between experimental and computed shifts is obtained for 13 C α , while larger scatter is observed for 15 N H chemical shifts, which are influenced to a greater extent by electrostatic interactions, hydrogen bonding, and solvation.

  14. Vibrational, NMR and quantum chemical investigations of acetoacetanilde, 2-chloroacetoacetanilide and 2-methylacetoacetanilide (United States)

    Arjunan, V.; Kalaivani, M.; Senthilkumari, S.; Mohan, S.


    The vibrational assignment and analysis of the fundamental modes of the compounds acetoacetanilide (AAA), 2-chloroacetoacetanilide (2CAAA) and 2-methylacetoacetanilide (2MAAA) have been performed. Density functional theory studies have been carried out with B3LYP method utilising 6-311++G** and cc-pVTZ basis sets to determine structural, thermodynamic and vibrational characteristics of the compounds and also to understand the influence of chloro and methyl groups on the characteristic frequencies of amide (sbnd CONHsbnd) group. Intramolecular hydrogen bond exists in acetoacetanilide and o-substituted acetoacetanilide molecules and the N⋯O distance is found to be around 2.7 Å. The 1H and 13C nuclear magnetic resonance chemical shifts of the molecules were determined and the same have been calculated using the gauge independent atomic orbital (GIAO) method. The energies of the frontier molecular orbitals have been determined. In AAA, 2CAAA and 2MAAA molecules, the nN → πCO∗ interaction between the nitrogen lone pair and the amide Cdbnd O antibonding orbital gives strong stabilization of 64.75, 62.84 and 64.18 kJ mol-1, respectively. The blue shift in amide-II band of 2MAAA is observed by 45-50 cm-1 than that of AAA. The steric effect of ortho methyl group significantly operating on the Nsbnd H bond properties. The amide-III, the Csbnd N stretching mode of methyl and chloro substituted acetoacetanilide compounds are not affected by the substitution while the amide-V band, the Nsbnd H out of plane bending mode of 2-chloroacetoacetanilide compound is shifted to a higher frequency than that of AAA. The substituent chlorine plays significantly and the blue shift in o-substituted compounds than the parent in the amide-V vibration is observed. The amide-VI, Cdbnd O out of plane bending modes of 2MAAA and 2CAAA are significantly raised than that of AAA. A blue shift of amide-VI, Cdbnd O out of plane bending modes of 2MAAA and 2CAAA than AAA is observed.

  15. Fabrication of Chemically Doped, High Upper Critical Field Magnesium Diboride Superconducting Wires

    International Nuclear Information System (INIS)

    Marzik, James V.


    Controlled chemical doping of magnesium diboride (MgB2) has been shown to substantially improve its superconducting properties to the levels required for high field magnets, but the doping is difficult to accomplish through the usual route of solid state reaction and diffusion. Further, superconducting cables of MgB2 are difficult to fabricate because of the friable nature of the material. In this Phase I STTR project, doped and undoped boron fibers were made by chemical vapor deposition (CVD). Several >100m long batches of doped and undoped fiber were made by CVD codeposition of boron plus dopants. Bundles of these fibers infiltrated with liquid magnesium and subsequently converted to MgB2 to form Mg-MgB2 metal matrix composites. In a parallel path, doped boron nano-sized powder was produced by a plasma synthesis technique, reacted with magnesium to produce doped MgB2 superconducting ceramic bodies. The doped powder was also fabricated into superconducting wires several meters long. The doped boron fibers and powders made in this program were fabricated into fiber-metal composites and powder-metal composites by a liquid metal infiltration technique. The kinetics of the reaction between boron fiber and magnesium metal was investigated in fiber-metal composites. It was found that the presence of dopants had significantly slowed the reaction between magnesium and boron. The superconducting properties were measured for MgB2 fibers and MgB2 powders made by liquid metal infiltration. Properties of MgB2 products (Jc, Hc2) from Phase I are among the highest reported to date for MgB2 bulk superconductors. Chemically doped MgB2 superconducting magnets can perform at least as well as NbTi and NbSn3 in high magnetic fields and still offer an improvement over the latter two in terms of operating temperature. These characteristics make doped MgB2 an effective material for high magnetic field applications, such as magnetic confined fusion, and medical MRI devices. Developing

  16. Fabrication of Chemically Doped, High Upper Critical Field Magnesium Diboride Superconducting Wires

    Energy Technology Data Exchange (ETDEWEB)

    Marzik, James, V.


    Controlled chemical doping of magnesium diboride (MgB2) has been shown to substantially improve its superconducting properties to the levels required for high field magnets, but the doping is difficult to accomplish through the usual route of solid state reaction and diffusion. Further, superconducting cables of MgB2 are difficult to fabricate because of the friable nature of the material. In this Phase I STTR project, doped and undoped boron fibers were made by chemical vapor deposition (CVD). Several >100m long batches of doped and undoped fiber were made by CVD codeposition of boron plus dopants. Bundles of these fibers infiltrated with liquid magnesium and subsequently converted to MgB2 to form Mg-MgB2 metal matrix composites. In a parallel path, doped boron nano-sized powder was produced by a plasma synthesis technique, reacted with magnesium to produce doped MgB2 superconducting ceramic bodies. The doped powder was also fabricated into superconducting wires several meters long. The doped boron fibers and powders made in this program were fabricated into fiber-metal composites and powder-metal composites by a liquid metal infiltration technique. The kinetics of the reaction between boron fiber and magnesium metal was investigated in fiber-metal composites. It was found that the presence of dopants had significantly slowed the reaction between magnesium and boron. The superconducting properties were measured for MgB2 fibers and MgB2 powders made by liquid metal infiltration. Properties of MgB2 products (Jc, Hc2) from Phase I are among the highest reported to date for MgB2 bulk superconductors. Chemically doped MgB2 superconducting magnets can perform at least as well as NbTi and NbSn3 in high magnetic fields and still offer an improvement over the latter two in terms of operating temperature. These characteristics make doped MgB2 an effective material for high magnetic field applications, such as magnetic confined fusion, and medical MRI devices. Developing

  17. Quantum discord and quantum phase transition in spin chains


    Dillenschneider, Raoul


    Quantum phase transitions of the transverse Ising and antiferromagnetic XXZ spin S=1/2 chains are studied using quantum discord. Quantum discord allows the measure of quantum correlations present in many-body quantum systems. It is shown that the amount of quantum correlations increases close to the critical points. The observations are in agreement with the information provided by the concurrence which measures the entanglement of the many-body system.

  18. A quantum chemical study of the N2H+ + e- → N2 + H reaction I: The linear dissociation path

    International Nuclear Information System (INIS)

    Talbi, D.


    A theoretical investigation of the dissociative recombination (DR) of linear N 2 H + (X 1 Σ g + ) to give N 2 + H has been undertaken because it is of interest for astrochemistry and also because it has been recently studied experimentally. Using state of the art quantum chemical methods, it is shown that the lowest 2 Σ repulsive state of N 2 H leading to the N 2 and H fragments in their ground electronic states does not cross the curve of the ion nor the one of the lowest N 2 H Rydberg state. This lowest 2 Σ repulsive state is very low in energy. Its curve passes below the 1 Σ N 2 H + state and below the lowest bound 2 Σ N 2 H states. However, it is also shown that there exist higher repulsive 2 Σ and 2 Δ states of N 2 H (the second and third repulsive states) crossing the ion curve. These states will lead to the formation of N 2 in its 3 Σ u + and 3 Δ u states. This study, the first of its type, shows that the DR of linear N 2 H + should involve the direct mechanism and that it should lead to N 2 in its first excited states. However this process may not be efficient for N 2 H + in its ground vibrational state (v = 0), a state in which it exists in the cold environment of the interstellar medium. For the DR to be efficient for N 2 H + in its ground v = 0 vibrational state, bent geometries of the ion might have to be considered

  19. Oolong tea: A critical review of processing methods, chemical composition, health effects, and risk. (United States)

    Ng, Kwan-Wai; Cao, Zi-Jun; Chen, Hu-Biao; Zhao, Zhong-Zhen; Zhu, Lin; Yi, Tao


    Oolong tea (OT) is a traditional Chinese tea (Camellia sinensis) and is especially popular in south China. This review is to comprehensively summarize the miscellaneous research that has been done towards to the processing, phytochemistry, health benefit, and risk of OT. These literatures were carried out not only from different electronic databases but also from text books written in English, Japanese, and Chinese, including those traditional records tracing back to the Tang Dynasty (A.D. 618-907). The full process OT producing is depicted below in this review. The phytochemistry of OT has been comprehensively investigated. More than 100 chemical compositions have been isolated and identified. In health benefit, OT performs outstandingly in reducing obesity and controlling diabetes explained by modern pharmacological studies. (-)-Epigallocatechin-3-gallate (6) in OT prevention of cancerous cells developing. OT can also improve and reduce on heart and vascular disease, protect teeth and bone, function as anti-oxidative and antibacterial agents. This review also mentioned the risk, summarized briefly on various forms of toxicity and harmful associated with OT. In short, this review can provided a natural product library of OT, gave inspirations for further new garden systems, designed idea on quality, bioactivity-oriented screening. In addition, it is suggested more scientists and education is necessary to guarantee the stability and safety of drinking OT.

  20. Synthesis of Aqueous CdTe/CdS/ZnS Core/shell/shell Quantum Dots by a Chemical Aerosol Flow Method

    Directory of Open Access Journals (Sweden)

    Chen Dong


    Full Text Available Abstract This work described a continuous method to synthesize CdTe/CdS/ZnS core/shell/shell quantum dots. In an integrated system by flawlessly combining the chemical aerosol flow system working at high temperature (200–300°C to generate CdTe/CdS intermediate products and an additional heat-up setup at relatively low temperature to overcoat the ZnS shells, the CdTe/CdS/ZnS multishell structures were realized. The as-synthesized CdTe/CdS/ZnS core/shell/shell quantum dots are characterized by photoluminescence spectra, X-ray diffraction (XRD, energy-dispersive X-ray spectra (EDS, transmission electron microscopy (TEM, and high-resolution transmission electron microscopy (HRTEM. Fluorescence and XRD results confirm that the obtained quantum dots have a core/shell/shell structure. It shows the highest quantum yield above 45% when compared to the rhodamine 6G. The core/shell/shell QDs were more stable via the oxidation experiment by H2O2.