WorldWideScience

Sample records for quantum chemical methods

  1. Chemical Reactivity as Described by Quantum Chemical Methods

    Directory of Open Access Journals (Sweden)

    F. De Proft

    2002-04-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-06-01

    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.

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

    Energy Technology Data Exchange (ETDEWEB)

    Kaviyarasu, K., E-mail: kaviyarasuloyolacollege@gmail.com [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: maniphysics@gmail.com [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: likmaaz@gmail.com [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)

    2015-11-15

    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.

  4. Evaluation of quantum-chemical methods of radiolysis stability for macromolecular structures

    International Nuclear Information System (INIS)

    Postolache, Cristian; Matei, Lidia

    2005-01-01

    The behavior of macromolecular structures in ionising fields was analyzed by quantum-chemical methods. In this study the primary radiolytic effect was analyzed using a two-step radiolytic mechanism: a) ionisation of molecule and spatial redistribution of atoms in order to reach a minimum value of energy, characteristic to the quantum state; b) neutralisation of the molecule by electron capture and its rapid dissociation into free radicals. Chemical bonds suspected to break are located in the distribution region of LUMO orbital and have minimal homolytic dissociation energies. Representative polymer structures (polyethylene, polypropylene, polystyrene, poly α and β polystyrene, polyisobutylene, polytetrafluoroethylene, poly methylsiloxanes) were analyzed. (authors)

  5. Combined Docking with Classical Force Field and Quantum Chemical Semiempirical Method PM7

    Directory of Open Access Journals (Sweden)

    A. V. Sulimov

    2017-01-01

    Full Text Available Results of the combined use of the classical force field and the recent quantum chemical PM7 method for docking are presented. Initially the gridless docking of a flexible low molecular weight ligand into the rigid target protein is performed with the energy function calculated in the MMFF94 force field with implicit water solvent in the PCM model. Among several hundred thousand local minima, which are found in the docking procedure, about eight thousand lowest energy minima are chosen and then energies of these minima are recalculated with the recent quantum chemical semiempirical PM7 method. This procedure is applied to 16 test complexes with different proteins and ligands. For almost all test complexes such energy recalculation results in the global energy minimum configuration corresponding to the ligand pose near the native ligand position in the crystalized protein-ligand complex. A significant improvement of the ligand positioning accuracy comparing with MMFF94 energy calculations is demonstrated.

  6. Combined Docking with Classical Force Field and Quantum Chemical Semiempirical Method PM7.

    Science.gov (United States)

    Sulimov, A V; Kutov, D C; Katkova, E V; Sulimov, V B

    2017-01-01

    Results of the combined use of the classical force field and the recent quantum chemical PM7 method for docking are presented. Initially the gridless docking of a flexible low molecular weight ligand into the rigid target protein is performed with the energy function calculated in the MMFF94 force field with implicit water solvent in the PCM model. Among several hundred thousand local minima, which are found in the docking procedure, about eight thousand lowest energy minima are chosen and then energies of these minima are recalculated with the recent quantum chemical semiempirical PM7 method. This procedure is applied to 16 test complexes with different proteins and ligands. For almost all test complexes such energy recalculation results in the global energy minimum configuration corresponding to the ligand pose near the native ligand position in the crystalized protein-ligand complex. A significant improvement of the ligand positioning accuracy comparing with MMFF94 energy calculations is demonstrated.

  7. Accurate quantum chemical calculations

    Science.gov (United States)

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

    1989-01-01

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

  8. ELECTROREDUCTION MECHANISM OF Ni(DMG)-2 COMPLEX STUDIED WITH QUANTUM CHEMICAL METHOD

    Institute of Scientific and Technical Information of China (English)

    倪亚明; 任镜清; 黎健; 王德民; 梁伟根; 朱芝仙; 高小霞

    1990-01-01

    The electronic structures of the species Ni(DMG)2, (Ni(DMG)2)- and (Ni(DMG)2)2- have been studied by INDO quantum chemical method. The results have clearly shown that in the first stage of the electroreduction of Ni(DMG)2, one electron interacts with the d orbitals on the nickel atom, while in the further stage the second electron interacts with the p orbitals on the nitrogen atoms. It conforms with our electrochemical experimental studies which showed that not only Ni(Ⅱ) is reduced but also DMG is catalytically reduced during the reduction of Ni(DMG)2.

  9. Hybrid quantum and classical methods for computing kinetic isotope effects of chemical reactions in solutions and in enzymes.

    Science.gov (United States)

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

    2008-01-01

    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.

  10. Structure activity studies of an analgesic drug tapentadol hydrochloride by spectroscopic and quantum chemical methods

    Science.gov (United States)

    Arjunan, V.; Santhanam, R.; Marchewka, M. K.; Mohan, S.; Yang, Haifeng

    2015-11-01

    Tapentadol is a novel opioid pain reliever drug with a dual mechanism of action, having potency between morphine and tramadol. Quantum chemical calculations have been carried out for tapentadol hydrochloride (TAP.Cl) to determine the properties. The geometry is optimised and the structural properties of the compound were determined from the optimised geometry by B3LYP method using 6-311++G(d,p), 6-31G(d,p) and cc-pVDZ basis sets. FT-IR and FT-Raman spectra are recorded in the solid phase in the region of 4000-400 and 4000-100 cm-1, respectively. Frontier molecular orbital energies, LUMO-HOMO energy gap, ionisation potential, electron affinity, electronegativity, hardness and chemical potential are also calculated. The stability of the molecule arising from hyperconjugative interactions and charge delocalisation has been analysed using NBO analysis. The 1H and 13C nuclear magnetic resonance chemical shifts of the molecule are analysed.

  11. How to compute isomerization energies of organic molecules with quantum chemical methods.

    Science.gov (United States)

    Grimme, Stefan; Steinmetz, Marc; Korth, Martin

    2007-03-16

    The reaction energies for 34 typical organic isomerizations including oxygen and nitrogen heteroatoms are investigated with modern quantum chemical methods that have the perspective of also being applicable to large systems. The experimental reaction enthalpies are corrected for vibrational and thermal effects, and the thus derived "experimental" reaction energies are compared to corresponding theoretical data. A series of standard AO basis sets in combination with second-order perturbation theory (MP2, SCS-MP2), conventional density functionals (e.g., PBE, TPSS, B3-LYP, MPW1K, BMK), and new perturbative functionals (B2-PLYP, mPW2-PLYP) are tested. In three cases, obvious errors of the experimental values could be detected, and accurate coupled-cluster [CCSD(T)] reference values have been used instead. It is found that only triple-zeta quality AO basis sets provide results close enough to the basis set limit and that sets like the popular 6-31G(d) should be avoided in accurate work. Augmentation of small basis sets with diffuse functions has a notable effect in B3-LYP calculations that is attributed to intramolecular basis set superposition error and covers basic deficiencies of the functional. The new methods based on perturbation theory (SCS-MP2, X2-PLYP) are found to be clearly superior to many other approaches; that is, they provide mean absolute deviations of less than 1.2 kcal mol-1 and only a few (computational thermochemistry methods.

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

    International Nuclear Information System (INIS)

    Vetere, V.

    2002-09-01

    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)

  13. Cation solvation with quantum chemical effects modeled by a size-consistent multi-partitioning quantum mechanics/molecular mechanics method.

    Science.gov (United States)

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

    2017-07-21

    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.

  14. Quantum chemical studies of estrogenic compounds

    Science.gov (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 ...

  15. New generation of docking programs: Supercomputer validation of force fields and quantum-chemical methods for docking.

    Science.gov (United States)

    Sulimov, Alexey V; Kutov, Danil C; Katkova, Ekaterina V; Ilin, Ivan S; Sulimov, Vladimir B

    2017-11-01

    Discovery of new inhibitors of the protein associated with a given disease is the initial and most important stage of the whole process of the rational development of new pharmaceutical substances. New inhibitors block the active site of the target protein and the disease is cured. Computer-aided molecular modeling can considerably increase effectiveness of new inhibitors development. Reliable predictions of the target protein inhibition by a small molecule, ligand, is defined by the accuracy of docking programs. Such programs position a ligand in the target protein and estimate the protein-ligand binding energy. Positioning accuracy of modern docking programs is satisfactory. However, the accuracy of binding energy calculations is too low to predict good inhibitors. For effective application of docking programs to new inhibitors development the accuracy of binding energy calculations should be higher than 1kcal/mol. Reasons of limited accuracy of modern docking programs are discussed. One of the most important aspects limiting this accuracy is imperfection of protein-ligand energy calculations. Results of supercomputer validation of several force fields and quantum-chemical methods for docking are presented. The validation was performed by quasi-docking as follows. First, the low energy minima spectra of 16 protein-ligand complexes were found by exhaustive minima search in the MMFF94 force field. Second, energies of the lowest 8192 minima are recalculated with CHARMM force field and PM6-D3H4X and PM7 quantum-chemical methods for each complex. The analysis of minima energies reveals the docking positioning accuracies of the PM7 and PM6-D3H4X quantum-chemical methods and the CHARMM force field are close to one another and they are better than the positioning accuracy of the MMFF94 force field. Copyright © 2017 Elsevier Inc. All rights reserved.

  16. 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

    2014-12-01

    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.

  17. Quantum indistinguishability in chemical reactions.

    Science.gov (United States)

    Fisher, Matthew P A; Radzihovsky, Leo

    2018-05-15

    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.

  18. 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

    2018-01-01

    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%.

  19. Incorporation of Mn2+ into CdSe quantum dots by chemical bath co-deposition method for photovoltaic enhancement of quantum dot-sensitized solar cells.

    Science.gov (United States)

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

    2018-03-01

    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.

  20. Combinatorial computational chemistry approach of tight-binding quantum chemical molecular dynamics method to the design of the automotive catalysts

    International Nuclear Information System (INIS)

    Ito, Yuki; Jung, Changho; Luo, Yi; Koyama, Michihisa; Endou, Akira; Kubo, Momoji; Imamura, Akira; Miyamoto, Akira

    2006-01-01

    Recently, we have developed a new tight-binding quantum chemical molecular dynamics program 'Colors' for combinatorial computational chemistry approach. This methodology is based on our original tight-binding approximation and realized over 5000 times acceleration compared to the conventional first-principles molecular dynamics method. In the present study, we applied our new program to the simulations on various realistic large-scale models of the automotive three-way catalysts, ultrafine Pt particle/CeO 2 (111) support. Significant electron transfer from the Pt particle to the CeO 2 (111) surface was observed and it was found to strongly depend on the size of the Pt particle. Furthermore, our simulation results suggest that the reduction of the Ce atom due to the electron transfer from the Pt particle to the CeO 2 surface is a main reason for the strong interaction of the Pt particle and CeO 2 (111) support

  1. Synthesis of copper quantum dots by chemical reduction method and tailoring of its band gap

    Directory of Open Access Journals (Sweden)

    P. G. Prabhash

    2016-05-01

    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.

  2. Prediction of pKa Values for Druglike Molecules Using Semiempirical Quantum Chemical Methods.

    Science.gov (United States)

    Jensen, Jan H; Swain, Christopher J; Olsen, Lars

    2017-01-26

    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.

  3. Calculation of 0-0 excitation energies of organic molecules by CIS(D) quantum chemical methods

    International Nuclear Information System (INIS)

    Grimme, Stefan; Izgorodina, Ekaterina I.

    2004-01-01

    The accuracy and reliability of the CIS(D) quantum chemical method and a spin-component scaled variant (SCS-CIS(D)) are tested for calculating 0-0 excitation energies of organic molecules. The ground and excited state geometries and the vibrational zero-point corrections are taken from (TD)DFT-B3LYP calculations. In total 32 valence excited states of different character are studied: π → π* states of polycyclic aromatic compounds/polyenes and n → π* states of carbonyl, thiocarbonyl and aza(azo)-aromatic compounds. This set is augmented by two systems of special interest, i.e., indole and the TICT state of dimethylaminbenzonitrile (DMABN). Both methods predict excitation energies that are on average higher than experiment by about 0.2 eV. The errors are found to be quite systematic (with a standard deviation of about 0.15 eV) and especially SCS-CIS(D) provides a more balanced treatment of π → π* vs. n → π* states. For the test suite of states, both methods clearly outperform the (TD)DFT-B3LYP approach. Opposed to previous conclusions about the performance of CIS(D), these methods can be recommended as reliable and efficient tools for computational studies of excited state problems in organic chemistry. In order to obtain conclusive results, however, the use of optimized excited state geometries and comparison with observables (0-0 excitation energies) are necessary

  4. Quantum mechanical tunneling in chemical physics

    CERN Document Server

    Nakamura, Hiroki

    2016-01-01

    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...

  5. Semiempirical Quantum-Chemical Orthogonalization-Corrected Methods: Benchmarks for Ground-State Properties.

    Science.gov (United States)

    Dral, Pavlo O; Wu, Xin; Spörkel, Lasse; Koslowski, Axel; Thiel, Walter

    2016-03-08

    The semiempirical orthogonalization-corrected OMx methods (OM1, OM2, and OM3) go beyond the standard MNDO model by including additional interactions in the electronic structure calculation. When augmented with empirical dispersion corrections, the resulting OMx-Dn approaches offer a fast and robust treatment of noncovalent interactions. Here we evaluate the performance of the OMx and OMx-Dn methods for a variety of ground-state properties using a large and diverse collection of benchmark sets from the literature, with a total of 13035 original and derived reference data. Extensive comparisons are made with the results from established semiempirical methods (MNDO, AM1, PM3, PM6, and PM7) that also use the NDDO (neglect of diatomic differential overlap) integral approximation. Statistical evaluations show that the OMx and OMx-Dn methods outperform the other methods for most of the benchmark sets.

  6. Optimization of the geometry of the diphenylamine molecule by semiempirical quantum chemical methods

    International Nuclear Information System (INIS)

    Pankratov, A.N.; Mushtakova, S.P.; Gribov, L.A.

    1986-01-01

    Available data on experimental study of the geometry of the diphenylamine molecule (I) in solution and in the crystal are fragmentary and not always reliable. Previously, they did a conformational analysis of molecule I using the atom-atom potential method. In order to refine the geometric parameters found for molecule I, optimization of its geometry is provided in the paper using the CNDO/2, INDO, MINDO/3 methods with the use of programs for the BESM-6 computer which are part of the VIKING program set. The angles of rotation for the phenyl rings relative to the CNC plane, the bond angles C 2 N 7 C 8 and C 2 N 7 H 19 , and also the dihedral angle H 19 N 7 C 8 C 9 were subjected to optimization. For any set of values for the indicated parameters, the bond angle C 8 N 7 H 19 is determined unambiguously. The results of the calculations are evidence that the MINDO/3 method is not suitable for optimization of the geometry for molecules of the indicated series; in particular, it leads to much too high a value for the CNC angles (135.9 0 ). The CNDO/2 method reproduces well the real value of the CNC angle (124.1 0 ) and confirms the known pyrimidal character of the nitrogen atom, the sum of the bond angles of which proved to be equal to 353.6 0 . The calculation in the INDO approximation successfully gives the basic characteristics of the molecular geometry of (I); according to this approximation, the CNC angle is equal to 123.2 0 , the CNH angles are equal to 118.0 and 118.8 0 , the sum of the angles for the nitrogen atom is 360.0 0

  7. Maximum Quantum Entropy Method

    OpenAIRE

    Sim, Jae-Hoon; Han, Myung Joon

    2018-01-01

    Maximum entropy method for analytic continuation is extended by introducing quantum relative entropy. This new method is formulated in terms of matrix-valued functions and therefore invariant under arbitrary unitary transformation of input matrix. As a result, the continuation of off-diagonal elements becomes straightforward. Without introducing any further ambiguity, the Bayesian probabilistic interpretation is maintained just as in the conventional maximum entropy method. The applications o...

  8. Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

    Science.gov (United States)

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

    2014-03-11

    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.

  9. 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

    2009-01-01

    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.

  10. Approximate quantum chemical methods for modelling carbohydrate conformation and aromatic interactions: β-cyclodextrin and its adsorption on a single-layer graphene sheet.

    Science.gov (United States)

    Jaiyong, Panichakorn; Bryce, Richard A

    2017-06-14

    Noncovalent functionalization of graphene by carbohydrates such as β-cyclodextrin (βCD) has the potential to improve graphene dispersibility and its use in biomedical applications. Here we explore the ability of approximate quantum chemical methods to accurately model βCD conformation and its interaction with graphene. We find that DFTB3, SCC-DFTB and PM3CARB-1 methods provide the best agreement with density functional theory (DFT) in calculation of relative energetics of gas-phase βCD conformers; however, the remaining NDDO-based approaches we considered underestimate the stability of the trans,gauche vicinal diol conformation. This diol orientation, corresponding to a clockwise hydrogen bonding arrangement in the glucosyl residue of βCD, is present in the lowest energy βCD conformer. Consequently, for adsorption on graphene of clockwise or counterclockwise hydrogen bonded forms of βCD, calculated with respect to this unbound conformer, the DFTB3 method provides closer agreement with DFT values than PM7 and PM6-DH2 approaches. These findings suggest approximate quantum chemical methods as potentially useful tools to guide the design of carbohydrate-graphene interactions, but also highlights the specific challenge to NDDO-based methods in capturing the relative energetics of carbohydrate hydrogen bond networks.

  11. Quantum dynamics of fast chemical reactions

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-01

    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.

  12. molecular dynamics simulations and quantum chemical calculations

    African Journals Online (AJOL)

    ABSTRACT. The molecular dynamic (MD) simulation and quantum chemical calculations for the adsorption of [2-(2-Henicos-10- .... electronic properties of molecule clusters, surfaces and ... The local reactivity was analyzed by determining the.

  13. Thermal transformation of bioactive caffeic acid on fumed silica seen by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry and quantum chemical methods.

    Science.gov (United States)

    Kulik, Tetiana V; Lipkovska, Natalia O; Barvinchenko, Valentyna M; Palyanytsya, Borys B; Kazakova, Olga A; Dudik, Olesia O; Menyhárd, Alfréd; László, Krisztina

    2016-05-15

    Thermochemical studies of hydroxycinnamic acid derivatives and their surface complexes are important for the pharmaceutical industry, medicine and for the development of technologies of heterogeneous biomass pyrolysis. In this study, structural and thermal transformations of caffeic acid complexes on silica surfaces were studied by UV-Vis spectroscopy, thermogravimetric analysis, temperature programmed desorption mass spectrometry (TPD MS) and quantum chemical methods. Two types of caffeic acid surface complexes are found to form through phenolic or carboxyl groups. The kinetic parameters of the chemical reactions of caffeic acid on silica surface are calculated. The mechanisms of thermal transformations of the caffeic chemisorbed surface complexes are proposed. Thermal decomposition of caffeic acid complex chemisorbed through grafted ester group proceeds via three parallel reactions, producing ketene, vinyl and acetylene derivatives of 1,2-dihydroxybenzene. Immobilization of phenolic acids on the silica surface improves greatly their thermal stability. Copyright © 2016 Elsevier Inc. All rights reserved.

  14. Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions

    OpenAIRE

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

    2014-01-01

    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 transfe...

  15. Stochastic methods in quantum mechanics

    CERN Document Server

    Gudder, Stanley P

    2005-01-01

    Practical developments in such fields as optical coherence, communication engineering, and laser technology have developed from the applications of stochastic methods. This introductory survey offers a broad view of some of the most useful stochastic methods and techniques in quantum physics, functional analysis, probability theory, communications, and electrical engineering. Starting with a history of quantum mechanics, it examines both the quantum logic approach and the operational approach, with explorations of random fields and quantum field theory.The text assumes a basic knowledge of fun

  16. Distribution of electron density and internal rotation in phospha-alkenes according to data from quantum-chemical calculations by the MNDO method

    International Nuclear Information System (INIS)

    Boldeskul, I.E.; Pen'kovskii, V.V.; Povolotskii, M.I.

    1988-01-01

    A quantum-chemical investigation of the characteristics of the phosphorus-carbon bond and the internal rotation around it in phospha-alkenes has been carried out in the MNDO approximation. The results of the calculation have been compared with experimental dynamic 1 H NMR data

  17. Quantum chemical investigation of mechanisms of silane oxidation

    DEFF Research Database (Denmark)

    Mader, Mary M.; Norrby, Per-Ola

    2001-01-01

    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...

  18. Chemical applications of molecular quantum theory

    International Nuclear Information System (INIS)

    Ungemach, S.R.

    1977-09-01

    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 2 , ClF 4 and Cl 3 radicals, and the ions ClF 2 + , ClF 2 - , ClF 4 + and ClF 4 - . The ClF 2 and Cl 3 radicals are predicted to be bent with bond angles of 145.2 0 and 158.6 0 , respectively, while the ions ClF 2 + and ClF 2 - are predicted to be bent with a bond angle of 97.4 0 and linear, respectively. The geometry predictions for the ClF 4 radical and the ClF 4 + ion are found to be notably basis set dependent. The ClF 4 - ion is predicted to be square-planar. Multi-configuration self-consistent field (MCSCF) calculations have yielded the dipole moment function for the 1 sigma + state of HI, which qualitatively confirms the experimental finding that the dipole derivative at R/sub e/ is negative. The 2 sigma + F + H 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

  19. Quantum mechanical facets of chemical bonds

    International Nuclear Information System (INIS)

    Daudel, R.

    1976-01-01

    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.)

  20. Quantum chemical approach to estimating the thermodynamics of metabolic reactions.

    Science.gov (United States)

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

    2014-11-12

    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.

  1. 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)

    1993-12-01

    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.

  2. Chemical sensors based on quantum cascade lasers

    Science.gov (United States)

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

    2002-09-01

    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.

  3. Accurate pKa Calculation of the Conjugate Acids of Alkanolamines, Alkaloids and Nucleotide Bases by Quantum Chemical Methods

    NARCIS (Netherlands)

    Gangarapu, S.; Marcelis, A.T.M.; Zuilhof, H.

    2013-01-01

    The pKa of the conjugate acids of alkanolamines, neurotransmitters, alkaloid drugs and nucleotide bases are calculated with density functional methods (B3LYP, M08-HX and M11-L) and ab initio methods (SCS-MP2, G3). Implicit solvent effects are included with a conductor-like polarizable continuum

  4. The use of semiempirical quantum chemical methods in studying the properties of large series of biologically active molecules

    International Nuclear Information System (INIS)

    Koeseoglu, Y.

    2004-01-01

    In this work, the productivity (temporal characteristics) of the so-called Electron Topological Method (ETM) proposed for the structure-activity relationships (SAR) investigation is studied. The method is standing aside the methods proposed for quantitative SAR (QSAR) studies because of the essential difference in the languages chosen for the compound structures description. ETM uses Electron Topological Matrices of Contiguity (ETMC) that include the most comprehensive data on the electronic structure of compounds and their topology. The flexibility of real molecules is taken into account in terms of two parameters, Δ 1 and Δ 2 , that characterise the accuracy allowed for atomic properties (diagonal matrix elements) and for bonds (non-diagonal ones). The dependence of the feature realisation on different values of Δ 1 and Δ 2 is studied and its graphical representation is given

  5. Accurate pKa calculation of the conjugate acids of alkanolamines, alkaloids and nucleotide bases by quantum chemical methods.

    Science.gov (United States)

    Gangarapu, Satesh; Marcelis, Antonius T M; Zuilhof, Han

    2013-04-02

    The pKa of the conjugate acids of alkanolamines, neurotransmitters, alkaloid drugs and nucleotide bases are calculated with density functional methods (B3LYP, M08-HX and M11-L) and ab initio methods (SCS-MP2, G3). Implicit solvent effects are included with a conductor-like polarizable continuum model (CPCM) and universal solvation models (SMD, SM8). G3, SCS-MP2 and M11-L methods coupled with SMD and SM8 solvation models perform well for alkanolamines with mean unsigned errors below 0.20 pKa units, in all cases. Extending this method to the pKa calculation of 35 nitrogen-containing compounds spanning 12 pKa units showed an excellent correlation between experimental and computational pKa values of these 35 amines with the computationally low-cost SM8/M11-L density functional approach. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. On the performance of quantum chemical methods to predict solvatochromic effects. The case of acrolein in aqueous solution

    DEFF Research Database (Denmark)

    Aidas, Kestutis; Møgelhøj, Andreas; Nilsson, Elna Johanna Kristina

    2008-01-01

    The performance of the Hartree–Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n¿* and ¿* electronic excitation energies of acrolein...... of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n¿* excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the ¿* electronic transition in solution, whereas...... the recent CAM-B3LYP functional performs well also in this case. The ¿* excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental...

  7. Structural characteristics and harmonic vibrational analysis of the stable conformer of 2,3-epoxypropanol by quantum chemical methods.

    Science.gov (United States)

    Arjunan, V; Rani, T; Santhanam, R; Mohan, S

    2012-10-01

    The FT-IR and FT-Raman spectra of H bond inner conformer of 2,3-epoxypropanol have been recorded in the regions 3700-400 and 3700-100 cm(-1), respectively. The spectra were interpreted in terms of fundamentals modes, combination and overtone bands. The normal coordinate analysis was carried out to confirm the precision of the assignments. The structure of the conformers H bond inner and H bond outer1 were optimised and the structural characteristics were determined by density functional theory (DFT) using B3LYP and MP2 methods with 6-31G** and 6-311++G** basis sets. The vibrational frequencies were calculated in all these methods and were compared with the experimental frequencies which yield good agreement between observed and calculated frequencies. The electronic properties HOMO and LUMO energies were measured by time-dependent TD-DFT approach. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Operator methods in quantum mechanics

    CERN Document Server

    Schechter, Martin

    2003-01-01

    This advanced undergraduate and graduate-level text introduces the power of operator theory as a tool in the study of quantum mechanics, assuming only a working knowledge of advanced calculus and no background in physics. The author presents a few simple postulates describing quantum theory, gradually introducing the mathematical techniques that help answer questions important to the physical theory; in this way, readers see clearly the purpose of the method and understand the accomplishment. The entire book is devoted to the study of a single particle moving along a straight line. By posing q

  9. Multi-scale multi-physics computational chemistry simulation based on ultra-accelerated quantum chemical molecular dynamics method for structural materials in boiling water reactor

    International Nuclear Information System (INIS)

    Miyamoto, Akira; Sato, Etsuko; Sato, Ryo; Inaba, Kenji; Hatakeyama, Nozomu

    2014-01-01

    In collaboration with experimental experts we have reported in the present conference (Hatakeyama, N. et al., “Experiment-integrated multi-scale, multi-physics computational chemistry simulation applied to corrosion behaviour of BWR structural materials”) the results of multi-scale multi-physics computational chemistry simulations applied to the corrosion behaviour of BWR structural materials. In macro-scale, a macroscopic simulator of anode polarization curve was developed to solve the spatially one-dimensional electrochemical equations on the material surface in continuum level in order to understand the corrosion behaviour of typical BWR structural material, SUS304. The experimental anode polarization behaviours of each pure metal were reproduced by fitting all the rates of electrochemical reactions and then the anode polarization curve of SUS304 was calculated by using the same parameters and found to reproduce the experimental behaviour successfully. In meso-scale, a kinetic Monte Carlo (KMC) simulator was applied to an actual-time simulation of the morphological corrosion behaviour under the influence of an applied voltage. In micro-scale, an ultra-accelerated quantum chemical molecular dynamics (UA-QCMD) code was applied to various metallic oxide surfaces of Fe 2 O 3 , Fe 3 O 4 , Cr 2 O 3 modelled as same as water molecules and dissolved metallic ions on the surfaces, then the dissolution and segregation behaviours were successfully simulated dynamically by using UA-QCMD. In this paper we describe details of the multi-scale, multi-physics computational chemistry method especially the UA-QCMD method. This method is approximately 10,000,000 times faster than conventional first-principles molecular dynamics methods based on density-functional theory (DFT), and the accuracy was also validated for various metals and metal oxides compared with DFT results. To assure multi-scale multi-physics computational chemistry simulation based on the UA-QCMD method for

  10. Recent Trends in Quantum Chemical Modeling of Enzymatic Reactions.

    Science.gov (United States)

    Himo, Fahmi

    2017-05-24

    The quantum chemical cluster approach is a powerful method for investigating enzymatic reactions. Over the past two decades, a large number of highly diverse systems have been studied and a great wealth of mechanistic insight has been developed using this technique. This Perspective reviews the current status of the methodology. The latest technical developments are highlighted, and challenges are discussed. Some recent applications are presented to illustrate the capabilities and progress of this approach, and likely future directions are outlined.

  11. Quantum mechanical calculations to chemical accuracy

    Science.gov (United States)

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

    1991-01-01

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

  12. Quantum chemical studies on the some inorganic corrosion inhibitors

    International Nuclear Information System (INIS)

    Sayin, Koray; Karakaş, Duran

    2013-01-01

    Highlights: •Some quantum chemical parameters are important to determine inhibition efficiency. •Quantum chemical calculations were performed on six inorganic inhibitors. •Five experimental reports were used to explain the theoretical results. •Atomic charges and %contributions were used to determine the atom at protonation process. •For inorganic inhibitors, the best method and basis set were investigated. -- Abstract: Some quantum chemical parameters were calculated by using Hartree–Fock (HF) approximation, Density Functional Theory (DFT/B3LYP) and Møller Plesset perturbation theory (MP3) methods at LANL2DZ, LANL2MB and SDD levels in gas phase and water for dichromate (Cr 2 O 7 2- ), chromate (CrO 4 2- ), tungstate (WO 4 2- ), molybdate (MoO 4 2- ), nitrite (NO 2 - ) and nitrate (NO 3 - ) which are used as inorganic corrosion inhibitors. All theoretical results and experimental inhibition efficiencies of inhibitors were subjected to correlation analyses. In a summary, MP3/SDD level in water was found as the best level. In this level, the inhibition efficiency ranking was found as CrO 4 2- >WO 4 2- >MoO 4 2- >Cr 2 O 7 2- >NO 2 - ≈NO 3 -

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

    DEFF Research Database (Denmark)

    Bratholm, Lars Andersen; Jensen, Jan Halborg

    2017-01-01

    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...

  14. Exploring the role of quantum chemical descriptors in modeling acute toxicity of diverse chemicals to Daphnia magna.

    Science.gov (United States)

    Reenu; Vikas

    2015-09-01

    Various quantum-mechanically computed molecular and thermodynamic descriptors along with physico-chemical, electrostatic and topological descriptors are compared while developing quantitative structure-activity relationships (QSARs) for the acute toxicity of 252 diverse organic chemicals towards Daphnia magna. QSAR models based on the quantum-chemical descriptors, computed with routinely employed advanced semi-empirical and ab-initio methods, along with the electron-correlation contribution (CORR) of the descriptors, are analyzed for the external predictivity of the acute toxicity. The models with reliable internal stability and external predictivity are found to be based on the HOMO energy along with the physico-chemical, electrostatic and topological descriptors. Besides this, the total energy and electron-correlation energy are also observed as highly reliable descriptors, suggesting that the intra-molecular interactions between the electrons play an important role in the origin of the acute toxicity, which is in fact an unexplored phenomenon. The models based on quantum-chemical descriptors such as chemical hardness, absolute electronegativity, standard Gibbs free energy and enthalpy are also observed to be reliable. A comparison of the robust models based on the quantum-chemical descriptors computed with various quantum-mechanical methods suggests that the advanced semi-empirical methods such as PM7 can be more reliable than the ab-initio methods which are computationally more expensive. Copyright © 2015 Elsevier Inc. All rights reserved.

  15. Chemical decontamination method

    International Nuclear Information System (INIS)

    Nishiwaki, Hitoshi.

    1996-01-01

    Metal wastes contaminated by radioactive materials are contained in a rotational decontamination vessel, and the metal wastes are rotated therein while being in contact with a slight amount of a decontamination liquid comprising a mineral acid. As the mineral acid, a mixed acid of nitric acid, hydrochloric acid and fluoric acid is preferably used. Alternatively, chemical decontamination can also be conducted by charging an acid resistant stirring medium in the rotational decontamination vessel. The surface of the metal wastes is uniformly covered by the slight amount of decontamination liquid to dissolve the surface layer. In addition, heat of dissolution generated in this case is accumulated in the inside of the rotational decontamination vessel, the temperature is elevated with no particular heating, thereby enabling to obtain an excellent decontamination effect substantially at the same level as in the case of heating the liquid to 70degC in a conventional immersion decontamination method. Further, although contact areas between the metal wastes and the immersion vessel are difficult to be decontaminated in the immersion decontamination method, all of areas can be dissolved uniformly in the present invention. (T.M.)

  16. Estimation of ground and excited-state dipole moments of 1, 2-diazines by solvatochromic method and quantum-chemical calculation

    DEFF Research Database (Denmark)

    Manohara, S.R.; Kumar, V. Udaya; Shivakumaraiah

    2013-01-01

    chemical calculations using the DFT method by adopting B3LYP/6-31G* level of theory (Gaussian 03) and using the AM1 method (Chem3D Ultra 8.0). It was observed that, dipole moments of diazines in the excited-state (μe) were greater than the corresponding ground-state values (μg), indicating a substantial...

  17. Quantum control with NMR methods: Application to quantum simulations

    International Nuclear Information System (INIS)

    Negrevergne, Camille

    2002-01-01

    Manipulating information according to quantum laws allows improvements in the efficiency of the way we treat certain problems. Liquid state Nuclear Magnetic Resonance methods allow us to initialize, manipulate and read the quantum state of a system of coupled spins. These methods have been used to realize an experimental small Quantum Information Processor (QIP) able to process information through around hundred elementary operations. One of the main themes of this work was to design, optimize and validate reliable RF-pulse sequences used to 'program' the QIP. Such techniques have been used to run a quantum simulation algorithm for anionic systems. Some experimental results have been obtained on the determination of Eigen energies and correlation function for a toy problem consisting of fermions on a lattice, showing an experimental proof of principle for such quantum simulations. (author) [fr

  18. Theoretical study of the electronic structure of f-element complexes by quantum chemical methods; Analyse de la structure electronique des complexes contenant des elements F par des methodes de la chimie quantique

    Energy Technology Data Exchange (ETDEWEB)

    Vetere, V

    2002-09-15

    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{sub 3}M-L species (X=F, Cl; M=La, Nd, U; L = NH{sub 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)

  19. An investigation on the structure, spectroscopy and thermodynamic aspects of Br2((-))(H2O)n clusters using a conjunction of stochastic and quantum chemical methods.

    Science.gov (United States)

    Naskar, Pulak; Chaudhury, Pinaki

    2016-06-28

    In this work we obtained global as well as local structures of Br2((-))(H2O)n clusters for n = 2 to 6 followed by the study of IR-spectral features and thermochemistry for the structures. The way adopted by us to obtain structures is not the conventional one used in most cases. Here we at first generated excellent quality pre-optimized structures by exploring the suitable empirical potential energy surface using stochastic optimizer simulated annealing. These structures are then further refined using quantum chemical calculations to obtain the final structures, and spectral and thermodynamic features. We clearly showed that our approach results in very quick and better convergence which reduces the computational cost and obviously using the strategy we are able to get one [i.e. global] or more than one [i.e. global and local(s)] energetically lower structures than those which are already reported for a given cluster size. Moreover, IR-spectral results and the evolutionary trends in interaction energy, solvation energy and vertical detachment energy for global structures of each size have also been presented to establish the utility of the procedure employed.

  20. New mixed quantum/semiclassical propagation method

    International Nuclear Information System (INIS)

    Antoniou, Dimitri; Gelman, David; Schwartz, Steven D.

    2007-01-01

    The authors developed a new method for calculating the quantum evolution of multidimensional systems, for cases in which the system can be assumed to consist of a quantum subsystem and a bath subsystem of heavier atoms. The method combines two ideas: starting from a simple frozen Gaussian description of the bath subsystem, then calculate quantum corrections to the propagation of the quantum subsystem. This follows from recent work by one of them, showing how one can calculate corrections to approximate evolution schemes, even when the Hamiltonian that corresponds to these approximate schemes is unknown. Then, they take the limit in which the width of the frozen Gaussians approaches zero, which makes the corrections to the evolution of the quantum subsystem depend only on classical bath coordinates. The test calculations they present use low-dimensional systems, in which comparison to exact quantum dynamics is feasible

  1. Spectral methods for quantum Markov chains

    Energy Technology Data Exchange (ETDEWEB)

    Szehr, Oleg

    2014-05-08

    The aim of this project is to contribute to our understanding of quantum time evolutions, whereby we focus on quantum Markov chains. The latter constitute a natural generalization of the ubiquitous concept of a classical Markov chain to describe evolutions of quantum mechanical systems. We contribute to the theory of such processes by introducing novel methods that allow us to relate the eigenvalue spectrum of the transition map to convergence as well as stability properties of the Markov chain.

  2. Spectral methods for quantum Markov chains

    International Nuclear Information System (INIS)

    Szehr, Oleg

    2014-01-01

    The aim of this project is to contribute to our understanding of quantum time evolutions, whereby we focus on quantum Markov chains. The latter constitute a natural generalization of the ubiquitous concept of a classical Markov chain to describe evolutions of quantum mechanical systems. We contribute to the theory of such processes by introducing novel methods that allow us to relate the eigenvalue spectrum of the transition map to convergence as well as stability properties of the Markov chain.

  3. From quantum chemical formation free energies to evaporation rates

    Directory of Open Access Journals (Sweden)

    I. K. Ortega

    2012-01-01

    Full Text Available Atmospheric new particle formation is an important source of atmospheric aerosols. Large efforts have been made during the past few years to identify which molecules are behind this phenomenon, but the actual birth mechanism of the particles is not yet well known. Quantum chemical calculations have proven to be a powerful tool to gain new insights into the very first steps of particle formation. In the present study we use formation free energies calculated by quantum chemical methods to estimate the evaporation rates of species from sulfuric acid clusters containing ammonia or dimethylamine. We have found that dimethylamine forms much more stable clusters with sulphuric acid than ammonia does. On the other hand, the existence of a very deep local minimum for clusters with two sulfuric acid molecules and two dimethylamine molecules hinders their growth to larger clusters. These results indicate that other compounds may be needed to make clusters grow to larger sizes (containing more than three sulfuric acid molecules.

  4. Quantum chemical approaches: semiempirical molecular orbital and hybrid quantum mechanical/molecular mechanical techniques.

    Science.gov (United States)

    Bryce, Richard A; Hillier, Ian H

    2014-01-01

    The use of computational quantum chemical methods to aid drug discovery is surveyed. An overview of the various computational models spanning ab initio, density function theory, semiempirical molecular orbital (MO), and hybrid quantum mechanical (QM)/molecular mechanical (MM) methods is given and their strengths and weaknesses are highlighted, focussing on the challenge of obtaining the accuracy essential for them to make a meaningful contribution to drug discovery. Particular attention is given to hybrid QM/MM and semiempirical MO methods which have the potential to yield the necessary accurate predictions of macromolecular structure and reactivity. These methods are shown to have advanced the study of many aspects of substrate-ligand interactions relevant to drug discovery. Thus, the successful parametrization of semiempirical MO methods and QM/MM methods can be used to model noncovalent substrate-protein interactions, and to lead to improved scoring functions. QM/MM methods can be used in crystal structure refinement and are particularly valuable for modelling covalent protein-ligand interactions and can thus aid the design of transition state analogues. An extensive collection of examples from the areas of metalloenzyme structure, enzyme inhibition, and ligand binding affinities and scoring functions are used to illustrate the power of these techniques.

  5. Quantum chemical prediction of antennae structures in lanthanide complexes

    International Nuclear Information System (INIS)

    Ottonelli, M.; Musso, G.F.; Rizzo, F.; Dellepiane, G.; Porzio, W.; Destri, S.

    2008-01-01

    In this paper the quantum chemical semiempirical procedure recently proposed by us to predict ground- and excited-state geometries of lanthanide complexes, the pseudo coordination centre method (PCC), is preliminarily compared with the semiempirical sparkle model for the calculation of lanthanide complexes (SMLC). Contrary to the SMLC method, where the rare-earth ion is replaced by a reparameterized sparkle atom, in our approach we replace it with a metal ion which is already present in the chosen semiempirical parameterization. This implies that in the optimization of the geometry of the complexes a different weight is implicitly given to the complex region including the rare-earth ion and its neighbour atoms with respect to the region of the ligands aggregate. As a consequence our approach is expected to reproduce better than the SMLC one the geometry of the ligands aggregate embedded in the complex, while the contrary happens for the coordination distances

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

    Indian Academy of Sciences (India)

    K RACKESH JAWAHER

    2018-02-15

    Feb 15, 2018 ... Quantum chemical calculations have been employed to study the molecular effects produced by. Cr2O3/SnO2 optimised structure. ... are exploited in solar cells [2], high-capacity lithium– storage [3], solid-state chemical ..... bond distance of metal–oxygen is positively (0.5 Е) deviated to oxygen–oxygen ...

  7. Lowest triplet (n, π*) electronic state of acrolein: Determination of structural parameters by cavity ringdown spectroscopy and quantum-chemical methods

    Science.gov (United States)

    Hlavacek, Nikolaus C.; McAnally, Michael O.; Drucker, Stephen

    2013-02-01

    The cavity ringdown absorption spectrum of acrolein (propenal, CH2=CH—CH=O) was recorded near 412 nm, under bulk-gas conditions at room temperature and in a free-jet expansion. The measured spectral region includes the 0^0_0 band of the T1(n, π*) ← S0 system. We analyzed the 0^0_0 rotational contour by using the STROTA computer program [R. H. Judge et al., J. Chem. Phys. 103, 5343 (1995)], 10.1063/1.470569, which incorporates an asymmetric rotor Hamiltonian for simulating and fitting singlet-triplet spectra. We used the program to fit T1(n, π*) inertial constants to the room-temperature contour. The determined values (cm-1), with 2σ confidence intervals, are A = 1.662 ± 0.003, B = 0.1485 ± 0.0006, C = 0.1363 ± 0.0004. Linewidth analysis of the jet-cooled spectrum yielded a value of 14 ± 2 ps for the lifetime of isolated acrolein molecules in the T1(n, π*), v = 0 state. We discuss the observed lifetime in the context of previous computational work on acrolein photochemistry. The spectroscopically derived inertial constants for the T1(n, π*) state were used to benchmark a variety of computational methods. One focus was on complete active space methods, such as complete active space self-consistent field (CASSCF) and second-order perturbation theory with a CASSCF reference function (CASPT2), which are applicable to excited states. We also examined the equation-of-motion coupled-cluster and time-dependent density function theory excited-state methods, and finally unrestricted ground-state techniques, including unrestricted density functional theory and unrestricted coupled-cluster theory with single and double and perturbative triple excitations. For each of the above methods, we or others [O. S. Bokareva et al., Int. J. Quantum Chem. 108, 2719 (2008)], 10.1002/qua.21803 used a triple zeta-quality basis set to optimize the T1(n, π*) geometry of acrolein. We find that the multiconfigurational methods provide the best agreement with fitted inertial

  8. A survey of quantum Lyapunov control methods.

    Science.gov (United States)

    Cong, Shuang; Meng, Fangfang

    2013-01-01

    The condition of a quantum Lyapunov-based control which can be well used in a closed quantum system is that the method can make the system convergent but not just stable. In the convergence study of the quantum Lyapunov control, two situations are classified: nondegenerate cases and degenerate cases. For these two situations, respectively, in this paper the target state is divided into four categories: the eigenstate, the mixed state which commutes with the internal Hamiltonian, the superposition state, and the mixed state which does not commute with the internal Hamiltonian. For these four categories, the quantum Lyapunov control methods for the closed quantum systems are summarized and analyzed. Particularly, the convergence of the control system to the different target states is reviewed, and how to make the convergence conditions be satisfied is summarized and analyzed.

  9. 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

    2007-01-01

    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

  10. Computational Quantum Mechanics for Materials Engineers The EMTO Method and Applications

    CERN Document Server

    Vitos, L

    2007-01-01

    Traditionally, new materials have been developed by empirically correlating their chemical composition, and the manufacturing processes used to form them, with their properties. Until recently, metallurgists have not used quantum theory for practical purposes. However, the development of modern density functional methods means that today, computational quantum mechanics can help engineers to identify and develop novel materials. Computational Quantum Mechanics for Materials Engineers describes new approaches to the modelling of disordered alloys that combine the most efficient quantum-level th

  11. Chemical control methods and tools

    Science.gov (United States)

    Steven Manning; James. Miller

    2011-01-01

    After determining the best course of action for control of an invasive plant population, it is important to understand the variety of methods available to the integrated pest management professional. A variety of methods are now widely used in managing invasive plants in natural areas, including chemical, mechanical, and cultural control methods. Once the preferred...

  12. System and method for making quantum dots

    KAUST Repository

    Bakr, Osman; Pan, Jun; El-Ballouli, Ala'a O.; Knudsen, Kristian Rahbek; Abdelhady, Ahmed L.

    2015-01-01

    Embodiments of the present disclosure provide for methods of making quantum dots (QDs) (passivated or unpassivated) using a continuous flow process, systems for making QDs using a continuous flow process, and the like. In one or more embodiments

  13. Quantum chemical evaluation for the stability of liquid sodium containing titanium nanoparticles

    International Nuclear Information System (INIS)

    Suzuki, Ai; Inaba, Kenji; Ishizawa, Yukie; Miura, Ryuji; Hatakeyama, Nozomu; Miyamoto, Akira; Saito, Jun-ichi; Ara, Kuniaki

    2015-01-01

    Recently, liquid sodium containing titanium nanoparticles (LSnanop) have attracted considerable attention. In this study, suspension state of Ti nanoparticle in liquid sodium was quantum chemically evaluated. The atomic interaction between Ti nanoparticles and sodium atoms in the liquid sodium medium was investigated. There were some literatures which gained quantum chemical insight into a nanoparticle with the surrounding sodium atom. However, liquid sodium medium itself together with a Ti nanoparticle under the realistic temperature has not yet been investigated theoretically. To overcome the problem of conventional theoretical method, we applied computationally low-load Tight Binding Quantum Chemical Molecular Dynamics (TB-QCMD) calculation method to investigate the suspension state of the Ti nanoparticle in liquid sodium metal. (author)

  14. Chemical microreactor and method thereof

    Science.gov (United States)

    Morse, Jeffrey D [Martinez, CA; Jankowski, Alan [Livermore, CA

    2011-08-09

    A method for forming a chemical microreactor includes forming at least one capillary microchannel in a substrate having at least one inlet and at least one outlet, integrating at least one heater into the chemical microreactor, interfacing the capillary microchannel with a liquid chemical reservoir at the inlet of the capillary microchannel, and interfacing the capillary microchannel with a porous membrane near the outlet of the capillary microchannel, the porous membrane being positioned beyond the outlet of the capillary microchannel, wherein the porous membrane has at least one catalyst material imbedded therein.

  15. Quantum Chemical: New name and focus for National Distillers

    Energy Technology Data Exchange (ETDEWEB)

    Reisch, M.S.

    1988-03-14

    This article explains why the National Distillers and Chemical Corporation has narrowed its focus on petrochemicals and energy. At one time the company had diversified into wine and spirits, insurance, metals, chemicals and energy. However, the company decided to reexamine where its commitments should be. It decided to stick with chemicals and energy because it could be a leader in these fields and not in its other interests. The article explains how the new company, Quantum Chemical, is doing and where it is headed in the future.

  16. Holistic methods in quantum logic

    International Nuclear Information System (INIS)

    Finkelstein, D.

    1982-01-01

    The Hilbert space of quantum mechanics and the Minkowski space of relativity are examples of two spaces that figure in many physical theories, and whose interrelation is discussed. The author calls them the truth space and time spaces respectively, in general, whatever their representation. In canonical quantization a time space is taken as basic and the truth space is a higher level construction. The author shows how a Hilbert space can be constructed from a transfer relation. The main tool for this construction is the Galois connection which constructs the lattice of predicates from the transfer relation between unit (= atomic) predicates. (Auth.)

  17. 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 ...

  18. Quantum Dots Embedded in Graphene Nanoribbons by Chemical Substitution

    DEFF Research Database (Denmark)

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

    2017-01-01

    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...

  19. 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 ...

  20. Quantum chemical investigation of levofloxacin-boron complexes: A computational approach

    Science.gov (United States)

    Sayin, Koray; Karakaş, Duran

    2018-04-01

    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.

  1. 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

    2013-01-01

    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...

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

    DEFF Research Database (Denmark)

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

    2012-01-01

    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...

  3. Quantum-Chemical Electron Densities of Proteins and of Selected Protein Sites from Subsystem Density Functional Theory

    NARCIS (Netherlands)

    Kiewisch, K.; Jacob, C.R.; Visscher, L.

    2013-01-01

    The ability to calculate accurate electron densities of full proteins or of selected sites in proteins is a prerequisite for a fully quantum-mechanical calculation of protein-protein and protein-ligand interaction energies. Quantum-chemical subsystem methods capable of treating proteins and other

  4. Mathematical optics classical, quantum, and computational methods

    CERN Document Server

    Lakshminarayanan, Vasudevan

    2012-01-01

    Going beyond standard introductory texts, Mathematical Optics: Classical, Quantum, and Computational Methods brings together many new mathematical techniques from optical science and engineering research. Profusely illustrated, the book makes the material accessible to students and newcomers to the field. Divided into six parts, the text presents state-of-the-art mathematical methods and applications in classical optics, quantum optics, and image processing. Part I describes the use of phase space concepts to characterize optical beams and the application of dynamic programming in optical wave

  5. The quantum dynamics of electronically nonadiabatic chemical reactions

    Science.gov (United States)

    Truhlar, Donald G.

    1993-01-01

    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

  6. Spectral methods in quantum field theory

    International Nuclear Information System (INIS)

    Graham, Noah; Quandt, Markus; Weigel, Herbert

    2009-01-01

    This concise text introduces techniques from quantum mechanics, especially scattering theory, to compute the effects of an external background on a quantum field in general, and on the properties of the quantum vacuum in particular. This approach can be succesfully used in an increasingly large number of situations, ranging from the study of solitons in field theory and cosmology to the determination of Casimir forces in nano-technology. The method introduced and applied in this book is shown to give an unambiguous connection to perturbation theory, implementing standard renormalization conditions even for non-perturbative backgrounds. It both gives new theoretical insights, for example illuminating longstanding questions regarding Casimir stresses, and also provides an efficient analytic and numerical tool well suited to practical calculations. Last but not least, it elucidates in a concrete context many of the subtleties of quantum field theory, such as divergences, regularization and renormalization, by connecting them to more familiar results in quantum mechanics. While addressed primarily at young researchers entering the field and nonspecialist researchers with backgrounds in theoretical and mathematical physics, introductory chapters on the theoretical aspects of the method make the book self-contained and thus suitable for advanced graduate students. (orig.)

  7. System and method for making quantum dots

    KAUST Repository

    Bakr, Osman M.

    2015-05-28

    Embodiments of the present disclosure provide for methods of making quantum dots (QDs) (passivated or unpassivated) using a continuous flow process, systems for making QDs using a continuous flow process, and the like. In one or more embodiments, the QDs produced using embodiments of the present disclosure can be used in solar photovoltaic cells, bio-imaging, IR emitters, or LEDs.

  8. Improve photocurrent quantum efficiency of carbon nanotube by chemical treatment

    International Nuclear Information System (INIS)

    Wang Hongguang; Wei Jinquan; Jia Yi; Li Zhen; Zhu Hongwei; Wang Kunlin; Wu Dehai

    2012-01-01

    Highlights: ► The QE of photocurrent for the H 2 O 2 -treated CNTs reaches to 5.28% at U bias = 0.1 V. ► Moderate chemical treatment can enhance the QE of photocurrent of CNTs. ► Excessive chemical treatment decreases the photocurrent quantum efficiency of CNTs. - Abstract: High photocurrent quantum efficiency (QE) of carbon nanotubes (CNTs) is important to their photovoltaic applications. The ability of photocurrent generation of CNTs depends on their band structure and surface state. For given CNTs, it is possible to improve the QE of photocurrent by chemical modification. Here, we study the effects of simple chemical treatment on the QE of CNTs by measuring the photocurrent of macroscopic CNT bundles. The QE of the H 2 O 2 -treated CNT bundle reaches 5.28% at 0.1 V bias voltage at a laser (λ = 473 nm) illumination, which is 85% higher than that of the pristine sample. But the QE of the CNTs treated in concentrated HNO 3 is lower than that of the pristine sample. It shows that moderate chemical treatment can enhance the photocurrent QE and excessive chemical treatment will decrease the QE because of introducing lots of structural defects.

  9. Lighting up micromotors with quantum dots for smart chemical sensing.

    Science.gov (United States)

    Jurado-Sánchez, B; Escarpa, A; Wang, J

    2015-09-25

    A new "on-the-fly" chemical optical detection strategy based on the incorporation of fluorescence CdTe quantum dots (QDs) on the surface of self-propelled tubular micromotors is presented. The motion-accelerated binding of trace Hg to the QDs selectively quenches the fluorescence emission and leads to an effective discrimination between different mercury species and other co-existing ions.

  10. Mechanical and chemical spinodal instabilities in finite quantum systems

    International Nuclear Information System (INIS)

    Colonna, M.; Chomaz, Ph.; Ayik, S.

    2001-01-01

    Self consistent quantum approaches are used to study the instabilities of finite nuclear systems. The frequencies of multipole density fluctuations are determined as a function of dilution and temperature, for several isotopes. The spinodal region of the phase diagrams is determined and it appears reduced by finite size effects. The role of surface and volume instabilities is discussed. Important chemical effects are associated with mechanical disruption and may lead to isospin fractionation. (authors)

  11. Development of constraint algorithm for the number of electrons in molecular orbitals consisting mainly 4f atomic orbitals of rare-earth elements and its introduction to tight-binding quantum chemical molecular dynamics method

    International Nuclear Information System (INIS)

    Endou, Akira; Onuma, Hiroaki; Jung, Sun-ho

    2007-01-01

    Our original tight-binding quantum chemical molecular dynamics code, Colors', has been successfully applied to the theoretical investigation of complex materials including rare-earth elements, e.g., metal catalysts supported on a CeO 2 surface. To expand our code so as to obtain a good convergence for the electronic structure of a calculation system including a rare-earth element, we developed a novel algorithm to provide a constraint condition for the number of electrons occupying the selected molecular orbitals that mainly consist of 4f atomic orbitals of the rare-earth element. This novel algorithm was introduced in Colors. Using Colors, we succeeded in obtaining the classified electronic configurations of the 4f atomic orbitals of Ce 4+ and reduced Ce ions in a CeO 2 bulk model with one oxygen defect, which makes it difficult to obtain a good convergence using a conventional first-principles quantum chemical calculation code. (author)

  12. Presentation of quantum Brownian movement in the collective coordinate method

    International Nuclear Information System (INIS)

    Oksak, A.I.; Sukhanov, A.D.

    2003-01-01

    Two explicitly solved models of quantum randomized processes described by the Langevin equation, i. e. a free quantum Brownian particle and a quantum Brownian harmonic oscillator, are considered. The Hamiltonian (string) realization of the models reveals soliton-like structure of classical solutions. Accordingly, the method of zero mode collective coordinate is an adequate means for describing the models quantum dynamics [ru

  13. Lattice Methods for Quantum Chromodynamics

    CERN Document Server

    DeGrand, Thomas

    2006-01-01

    Numerical simulation of lattice-regulated QCD has become an important source of information about strong interactions. In the last few years there has been an explosion of techniques for performing ever more accurate studies on the properties of strongly interacting particles. Lattice predictions directly impact many areas of particle and nuclear physics theory and phenomenology. This book provides a thorough introduction to the specialized techniques needed to carry out numerical simulations of QCD: a description of lattice discretizations of fermions and gauge fields, methods for actually do

  14. Quantum chemical modeling of zeolite-catalyzed methylation reactions: toward chemical accuracy for barriers.

    Science.gov (United States)

    Svelle, Stian; Tuma, Christian; Rozanska, Xavier; Kerber, Torsten; Sauer, Joachim

    2009-01-21

    The methylation of ethene, propene, and t-2-butene by methanol over the acidic microporous H-ZSM-5 catalyst has been investigated by a range of computational methods. Density functional theory (DFT) with periodic boundary conditions (PBE functional) fails to describe the experimentally determined decrease of apparent energy barriers with the alkene size due to inadequate description of dispersion forces. Adding a damped dispersion term expressed as a parametrized sum over atom pair C(6) contributions leads to uniformly underestimated barriers due to self-interaction errors. A hybrid MP2:DFT scheme is presented that combines MP2 energy calculations on a series of cluster models of increasing size with periodic DFT calculations, which allows extrapolation to the periodic MP2 limit. Additionally, errors caused by the use of finite basis sets, contributions of higher order correlation effects, zero-point vibrational energy, and thermal contributions to the enthalpy were evaluated and added to the "periodic" MP2 estimate. This multistep approach leads to enthalpy barriers at 623 K of 104, 77, and 48 kJ/mol for ethene, propene, and t-2-butene, respectively, which deviate from the experimentally measured values by 0, +13, and +8 kJ/mol. Hence, enthalpy barriers can be calculated with near chemical accuracy, which constitutes significant progress in the quantum chemical modeling of reactions in heterogeneous catalysis in general and microporous zeolites in particular.

  15. Phenomenon of quantum low temperature limit of chemical reaction rates

    International Nuclear Information System (INIS)

    Gol'danskij, V.I.

    1975-01-01

    The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerisation, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerisation reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau 0 ) required to add one new link to the polymer chain of formaldehyde during its polymerisation by radiation and during postpolymerisation and to establish that below 80K the increase of tau 0 slows down and that at T approximately equal to 10-4K the time tau 0 reaches a plateau (tau 0 approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life)

  16. Phenomenon of quantum low temperature limit of chemical reaction rates

    Energy Technology Data Exchange (ETDEWEB)

    Gol' danskii, V I [AN SSSR, Moscow. Inst. Khimicheskoj Fiziki

    1975-12-01

    The influence of quantum-mechanical effects on one of the fundamental laws of chemical kinetics - the Arrhenius Law - is considered. Criteria characterising the limits of the low-temperature region where the extent of quantum-mechanical tunnelling transitions exceeds exponentially the transitions over the barrier are quoted. Studies of the low-temperature tunnelling of electrons and hydrogen atoms are briefly mentioned and the history of research on low-temperature radiation-induced solid-phase polymerization, the development of which led to the discovery of the phenomenon of the low-temperature quantum-mechanical limit for the rates of chemical reactions in relation to the formaldehyde polymerization reaction, is briefly considered. The results of experiments using low-inertia calorimeters, whereby it is possible to determine directly the average time (tau/sub 0/) required to add one new link to the polymer chain of formaldehyde during its polymerization by radiation and during postpolymerization and to establish that below 80K the increase of tau/sub 0/ slows down and that at T approximately equal to 10-4K the time tau/sub 0/ reaches a plateau (tau/sub 0/ approximately equals 0.01s), are described. Possible explanations of the observed low-temperature limit for the rate of a chemical reaction are critically examined and a semiquantitative explanation is given for this phenomenon, which may be particularly common in combined electronic-confirmational transitions in complex biological molecules and may play a definite role in chemical and biological evolution (cold prehistory of life).

  17. 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

    2010-01-01

    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

  18. Research on Palmprint Identification Method Based on Quantum Algorithms

    Directory of Open Access Journals (Sweden)

    Hui Li

    2014-01-01

    Full Text Available Quantum image recognition is a technology by using quantum algorithm to process the image information. It can obtain better effect than classical algorithm. In this paper, four different quantum algorithms are used in the three stages of palmprint recognition. First, quantum adaptive median filtering algorithm is presented in palmprint filtering processing. Quantum filtering algorithm can get a better filtering result than classical algorithm through the comparison. Next, quantum Fourier transform (QFT is used to extract pattern features by only one operation due to quantum parallelism. The proposed algorithm exhibits an exponential speed-up compared with discrete Fourier transform in the feature extraction. Finally, quantum set operations and Grover algorithm are used in palmprint matching. According to the experimental results, quantum algorithm only needs to apply square of N operations to find out the target palmprint, but the traditional method needs N times of calculation. At the same time, the matching accuracy of quantum algorithm is almost 100%.

  19. Mathematical methods in quantum and statistical mechanics

    International Nuclear Information System (INIS)

    Fishman, L.

    1977-01-01

    The mathematical structure and closed-form solutions pertaining to several physical problems in quantum and statistical mechanics are examined in some detail. The J-matrix method, introduced previously for s-wave scattering and based upon well-established Hilbert Space theory and related generalized integral transformation techniques, is extended to treat the lth partial wave kinetic energy and Coulomb Hamiltonians within the context of square integrable (L 2 ), Laguerre (Slater), and oscillator (Gaussian) basis sets. The theory of relaxation in statistical mechanics within the context of the theory of linear integro-differential equations of the Master Equation type and their corresponding Markov processes is examined. Several topics of a mathematical nature concerning various computational aspects of the L 2 approach to quantum scattering theory are discussed

  20. Quantum chemical calculations in the structural analysis of phloretin

    Science.gov (United States)

    Gómez-Zavaglia, Andrea

    2009-07-01

    In this work, a conformational search on the molecule of phloretin [2',4',6'-Trihydroxy-3-(4-hydroxyphenyl)-propiophenone] has been performed. The molecule of phloretin has eight dihedral angles, four of them taking part in the carbon backbone and the other four, related with the orientation of the hydroxyl groups. A systematic search involving a random variation of the dihedral angles has been used to generate input structures for the quantum chemical calculations. Calculations at the DFT(B3LYP)/6-311++G(d,p) level of theory permitted the identification of 58 local minima belonging to the C 1 symmetry point group. The molecular structures of the conformers have been analyzed using hierarchical cluster analysis. This method allowed us to group conformers according to their similarities, and thus, to correlate the conformers' stability with structural parameters. The dendrogram obtained from the hierarchical cluster analysis depicted two main clusters. Cluster I included all the conformers with relative energies lower than 25 kJ mol -1 and cluster II, the remaining conformers. The possibility of forming intramolecular hydrogen bonds resulted the main factor contributing for the stability. Accordingly, all conformers depicting intramolecular H-bonds belong to cluster I. These conformations are clearly favored when the carbon backbone is as planar as possible. The values of the νC dbnd O and νOH vibrational modes were compared among all the conformers of phloretin. The redshifts associated with intramolecular H-bonds were correlated with the H-bonds distances and energies.

  1. Surface emitting ring quantum cascade lasers for chemical sensing

    Science.gov (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

    2018-01-01

    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.

  2. Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

    International Nuclear Information System (INIS)

    Khrapkovskii, Grigorii M; Shamov, Alexander G; Nikolaeva, E V; Chachkov, D V

    2009-01-01

    Data on the mechanisms of gas-phase monomolecular decomposition of nitroalkanes, nitroalkenes and nitroarenes obtained using modern quantum chemical methods are described systematically. The attention is focused on the discussion of multistage decomposition of nitro compounds to elementary experimentally observed products. Characteristic features of competition of different mechanisms and the effect of molecular structure on the change in the Arrhenius parameters of the primary reaction step are considered.

  3. Mechanisms of gas phase decomposition of C-nitro compounds from quantum chemical data

    Energy Technology Data Exchange (ETDEWEB)

    Khrapkovskii, Grigorii M; Shamov, Alexander G; Nikolaeva, E V; Chachkov, D V [Kazan State Technological University, Kazan (Russian Federation)

    2009-10-31

    Data on the mechanisms of gas-phase monomolecular decomposition of nitroalkanes, nitroalkenes and nitroarenes obtained using modern quantum chemical methods are described systematically. The attention is focused on the discussion of multistage decomposition of nitro compounds to elementary experimentally observed products. Characteristic features of competition of different mechanisms and the effect of molecular structure on the change in the Arrhenius parameters of the primary reaction step are considered.

  4. Bogolyubov axiomatic method in quantum electrodynamics

    International Nuclear Information System (INIS)

    Bazhanov, V.V.; Pron'ko, G.P.; Solov'ev, L.D.

    1979-01-01

    A number of problems of quantum electrodynamics are reviewed which permit an exact solution for both strong and electromagnetic interactions. The solutions have been obtained in the framework of the S-matrix method based on the Bogolyubov axiomatic approach supplemented with some axioms which make it possible to extended the field of application of the Bogolyubov approach for quantum electrodynamics. Infrared ''renormalization'' of axioms and fundamental equations of the S-matrix electrodynamics is discussed. Low-energy theorems for matrix elements of radiative operators have been obtained as solutions of fundamental equations. The low-energy theorems are used for describing the electrodynamic phenomena of soft photons. The bremsstrahlung amplitude is found. A generalized threshold theorem is formulated for the Compton scattering amplitude. The results of examining the infrared asymptotics of the charged particle Green functions, the small-angle scattering of charged particles and electromagnetic effects on heavy narrow resonance production are presented. The problems discussed show that the consequences of general principles of the relativistic quantum theory supplemented with requirements on gauge invariance are essentially nontrivial

  5. Principles and methods of quantum information technologies

    CERN Document Server

    Semba, Kouichi

    2016-01-01

    This book presents the research and development-related results of the “FIRST” Quantum Information Processing Project, which was conducted from 2010 to 2014 with the support of the Council for Science, Technology and Innovation of the Cabinet Office of the Government of Japan. The project supported 33 research groups and explored five areas: quantum communication, quantum metrology and sensing, coherent computing, quantum simulation, and quantum computing. The book is divided into seven main sections. Parts I through V, which consist of twenty chapters, focus on the system and architectural aspects of quantum information technologies, while Parts VI and VII, which consist of eight chapters, discuss the superconducting quantum circuit, semiconductor spin and molecular spin technologies.   Readers will be introduced to new quantum computing schemes such as quantum annealing machines and coherent Ising machines, which have now arisen as alternatives to standard quantum computers and are designed to successf...

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

    Science.gov (United States)

    Bratholm, Lars A; Jensen, Jan H

    2017-03-01

    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

  7. Development and new applications of quantum chemical simulation methodology

    International Nuclear Information System (INIS)

    Weiss, A. K. H.

    2012-01-01

    The Division of Theoretical Chemistry at the University of Innsbruck is focused on the study of chemical compounds in aqueous solution, in terms of mainly hybrid quantum mechanical / molecular mechanical molecular dynamics simulations (QM/MM MD). Besides the standard means of data analysis employed for such simulations, this study presents several advanced and capable algorithms for the description of structural and dynamic properties of the simulated species and its hydration. The first part of this thesis further presents selected exemplary simulations, in particular a comparative study of Formamide and N-methylformamide, Guanidinium, and Urea. An included review article further summarizes the major advances of these studies. The computer programs developed in the course of this thesis are by now well established in the research field. The second part of this study presents the theory and a development guide for a quantum chemical program, QuMuLuS, that is by now used as a QM program for recent QM/MM simulations at the division. In its course, this part presents newly developed algorithms for electron integral evaluation and point charge embedding. This program is validated in terms of benchmark computations. The associated theory is presented on a detailed level, to serve as a source for contemporary and future studies in the division. In the third and final part, further investigations of related topics are addressed. This covers additional schemes of molecular simulation analysis, new software, as well as a mathematical investigation of a non-standard two-electron integral. (author)

  8. Quantum chemical studies on the corrosion inhibition of some sulphonamides on mild steel in acidic medium

    International Nuclear Information System (INIS)

    Arslan, Taner; Kandemirli, Fatma; Ebenso, Eno E.; Love, Ian; Alemu, Hailemichael

    2009-01-01

    Quantum chemical calculations using the density functional theory (DFT) and some semi-empirical methods were performed on four sulphonamides (sulfaguanidine, sulfamethazine, sulfamethoxazole and sulfadiazine) used as corrosion inhibitors for mild steel in acidic medium to determine the relationship between molecular structure and their inhibition efficiencies. The results of the quantum chemical calculations and experimental %IE were subjected to correlation analysis and indicate that their inhibition effect are closely related to E HOMO , E LUMO , hardness, polarizability, dipole moment and charges. The %IE increased with increase in the E HOMO and decrease in E HOMO - E LUMO . The negative sign of the E HOMO values and other kinetic and thermodynamic parameters indicates that the data obtained support physical adsorption mechanism

  9. Quantum chemical modeling of enzymatic reactions: the case of 4-oxalocrotonate tautomerase.

    Science.gov (United States)

    Sevastik, Robin; Himo, Fahmi

    2007-12-01

    The reaction mechanism of 4-oxalocrotonate tautomerase (4-OT) is studied using the density functional theory method B3LYP. This enzyme catalyzes the isomerisation of unconjugated alpha-keto acids to their conjugated isomers. Two different quantum chemical models of the active site are devised and the potential energy curves for the reaction are computed. The calculations support the proposed reaction mechanism in which Pro-1 acts as a base to shuttle a proton from the C3 to the C5 position of the substrate. The first step (proton transfer from C3 to proline) is shown to be the rate-limiting step. The energy of the charge-separated intermediate (protonated proline-deprotonated substrate) is calculated to be quite low, in accordance with measured pKa values. The results of the two models are used to evaluate the methodology employed in modeling enzyme active sites using quantum chemical cluster models.

  10. Oxygen-vacancy defects on BaTiO3 (001) surface: a quantum chemical study

    International Nuclear Information System (INIS)

    Duque, Carlos; Stashans, Arvids

    2003-01-01

    A quantum-chemical study of technologically important BaTiO 3 crystal and oxygen-vacancy defects on its (001) surface is reported in the present work. The computations are made using a quantum-chemical method developed for periodic systems (crystals), which is based on the Hartree-Fock theory. The atomic rearrangement due to the surface creation is obtained for a pure BaTiO 3 by means of the periodic large unit cell (LUC) model and using an automated geometry optimisation procedure. The same technique is employed to study the electronic and structural properties of the material due to the presence of an O vacancy and F centre (two electrons trapped in an oxygen vacancy). The computations are carried out for both cubic and tetragonal lattices

  11. Carbon quantum dots and a method of making the same

    Science.gov (United States)

    Zidan, Ragaiy; Teprovich, Joseph A.; Washington, Aaron L.

    2017-08-22

    The present invention is directed to a method of preparing a carbon quantum dot. The carbon quantum dot can be prepared from a carbon precursor, such as a fullerene, and a complex metal hydride. The present invention also discloses a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride and a polymer containing a carbon quantum dot made by reacting a carbon precursor with a complex metal hydride.

  12. Versatile Formal Methods Applied to Quantum Information.

    Energy Technology Data Exchange (ETDEWEB)

    Witzel, Wayne [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Rudinger, Kenneth Michael [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States); Sarovar, Mohan [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States)

    2015-11-01

    Using a novel formal methods approach, we have generated computer-veri ed proofs of major theorems pertinent to the quantum phase estimation algorithm. This was accomplished using our Prove-It software package in Python. While many formal methods tools are available, their practical utility is limited. Translating a problem of interest into these systems and working through the steps of a proof is an art form that requires much expertise. One must surrender to the preferences and restrictions of the tool regarding how mathematical notions are expressed and what deductions are allowed. Automation is a major driver that forces restrictions. Our focus, on the other hand, is to produce a tool that allows users the ability to con rm proofs that are essentially known already. This goal is valuable in itself. We demonstrate the viability of our approach that allows the user great exibility in expressing state- ments and composing derivations. There were no major obstacles in following a textbook proof of the quantum phase estimation algorithm. There were tedious details of algebraic manipulations that we needed to implement (and a few that we did not have time to enter into our system) and some basic components that we needed to rethink, but there were no serious roadblocks. In the process, we made a number of convenient additions to our Prove-It package that will make certain algebraic manipulations easier to perform in the future. In fact, our intent is for our system to build upon itself in this manner.

  13. Semiclassical methods in chemical reaction dynamics

    International Nuclear Information System (INIS)

    Keshavamurthy, S.

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems

  14. Semiclassical methods in chemical reaction dynamics

    Energy Technology Data Exchange (ETDEWEB)

    Keshavamurthy, Srihari [Univ. of California, Berkeley, CA (United States)

    1994-12-01

    Semiclassical approximations, simple as well as rigorous, are formulated in order to be able to describe gas phase chemical reactions in large systems. We formulate a simple but accurate semiclassical model for incorporating multidimensional tunneling in classical trajectory simulations. This model is based on the existence of locally conserved actions around the saddle point region on a multidimensional potential energy surface. Using classical perturbation theory and monitoring the imaginary action as a function of time along a classical trajectory we calculate state-specific unimolecular decay rates for a model two dimensional potential with coupling. Results are in good comparison with exact quantum results for the potential over a wide range of coupling constants. We propose a new semiclassical hybrid method to calculate state-to-state S-matrix elements for bimolecular reactive scattering. The accuracy of the Van Vleck-Gutzwiller propagator and the short time dynamics of the system make this method self-consistent and accurate. We also go beyond the stationary phase approximation by doing the resulting integrals exactly (numerically). As a result, classically forbidden probabilties are calculated with purely real time classical trajectories within this approach. Application to the one dimensional Eckart barrier demonstrates the accuracy of this approach. Successful application of the semiclassical hybrid approach to collinear reactive scattering is prevented by the phenomenon of chaotic scattering. The modified Filinov approach to evaluating the integrals is discussed, but application to collinear systems requires a more careful analysis. In three and higher dimensional scattering systems, chaotic scattering is suppressed and hence the accuracy and usefulness of the semiclassical method should be tested for such systems.

  15. Evaluation of binding energies by using quantum mechanical methods

    International Nuclear Information System (INIS)

    Postolache, Cristian; Matei, Lidia; Postolache, Carmen

    2002-01-01

    Evaluation of binding energies (BE) in molecular structure is needed for modelling chemical and radiochemical processes by quantum-chemical methods. An important field of application is evaluation of radiolysis and autoradiolysis stability of organic and inorganic compounds as well as macromolecular structures. The current methods of calculation do not allow direct determination of BE but only of total binding energies (TBE) and enthalpies. BEs were evaluated indirectly by determining the homolytic dissociation energies. The molecular structures were built and geometrically optimized by the molecular mechanics methods MM+ and AMBER. The energy minimizations were refined by semi-empirical methods. Depending on the chosen molecular structure, the CNDO, INDO, PM3 and AM1 methods were used. To reach a high confidence level the minimizations were done for gradients lower than 10 -3 RMS. The energy values obtained by the difference of the fragment TBLs, of the transition states and initial molecular structures, respectively, were associated to the hemolytic fragmentation energy and BE, respectively. In order to evaluate the method's accuracy and to establish the application fields of the evaluation methods, the obtained values of BEs were compared with the experimental data taken from literature. To this goal there were built, geometrically optimized by semi-empirical methods and evaluated the BEs for 74 organic and inorganic compounds (alkanes, alkene, alkynes, halogenated derivatives, alcohols, aldehydes, ketones, carboxylic acids, nitrogen and sulfur compounds, water, hydrogen peroxide, ammonia, hydrazine, etc. (authors)

  16. Quantum defect theory and asymptotic methods

    International Nuclear Information System (INIS)

    Seaton, M.J.

    1982-01-01

    It is shown that quantum defect theory provides a basis for the development of various analytical methods for the examination of electron-ion collision phenomena, including di-electronic recombination. Its use in conjuction with ab initio calculations is shown to be restricted by problems which arise from the presence of long-range non-Coulomb potentials. Empirical fitting to some formulae can be efficient in the use of computer time but extravagant in the use of person time. Calculations at a large number of energy points which make no use of analytical formulae for resonance structures may be made less extravagant in computer time by the development of more efficient asymptotic methods. (U.K.)

  17. Method for producing chemical energy

    Science.gov (United States)

    Jorgensen, Betty S.; Danen, Wayne C.

    2004-09-21

    Fluoroalkylsilane-coated metal particles having a central metal core, a buffer layer surrounding the core, and a fluoroalkylsilane layer attached to the buffer layer are prepared by combining a chemically reactive fluoroalkylsilane compound with an oxide coated metal particle having a hydroxylated surface. The resulting fluoroalkylsilane layer that coats the particles provides them with excellent resistance to aging. The particles can be blended with oxidant particles to form energetic powder that releases chemical energy when the buffer layer is physically disrupted so that the reductant metal core can react with the oxidant.

  18. Characterization of heterocyclic rings through quantum chemical topology.

    Science.gov (United States)

    Griffiths, Mark Z; Popelier, Paul L A

    2013-07-22

    Five-membered rings are found in a myriad of molecules important in a wide range of areas such as catalysis, nutrition, and drug and agrochemical design. Systematic insight into their largely unexplored chemical space benefits from first principle calculations presented here. This study comprehensively investigates a grand total of 764 different rings, all geometry optimized at the B3LYP/6-311+G(2d,p) level, from the perspective of Quantum Chemical Topology (QCT). For the first time, a 3D space of local topological properties was introduced, in order to characterize rings compactly. This space is called RCP space, after the so-called ring critical point. This space is analogous to BCP space, named after the bond critical point, which compactly and successfully characterizes a chemical bond. The relative positions of the rings in RCP space are determined by the nature of the ring scaffold, such as the heteroatoms within the ring or the number of π-bonds. The summed atomic QCT charges of the five ring atoms revealed five features (number and type of heteroatom, number of π-bonds, substituent and substitution site) that dictate a ring's net charge. Each feature independently contributes toward a ring's net charge. Each substituent has its own distinct and systematic effect on the ring's net charge, irrespective of the ring scaffold. Therefore, this work proves the possibility of designing a ring with specific properties by fine-tuning it through manipulation of these five features.

  19. Quantum-chemical consideration of extermal valent forms of actinides

    International Nuclear Information System (INIS)

    Ionova, G.V.; Pershina, V.G.; Spitsyn, V.I.

    1982-01-01

    Stability of valent forms of actinides that has not yet studied experimentally, is considered within the framework of quantum-chemical considerations. Oxidizing potentials E 0 for actinide elements are determined theoretically. A dependence of the definite valent state stability on relativistic effect is shown. A conclusion is made that oxidizing potential E 0 (4-5) for americium should be higher than E 0 (4-5) for plutonium. A relatively small oxidizing potential E 0 (4-5) for curium speaks about principle possibility of production of five-valent curium in solution, though it is less stable than the six-valent one. Oxidizing potential corresponding to transition of three-valent californium into the four-valent state should be less than the value adopted in literature. A relatively small oxidizing potential of californium E 0 (4-5) speaks about possible existence of five-valent californium in solution

  20. Quantum Chemical Modeling of Enzymatic Reactions: The Case of Decarboxylation.

    Science.gov (United States)

    Liao, Rong-Zhen; Yu, Jian-Guo; Himo, Fahmi

    2011-05-10

    We present a systematic study of the decarboxylation step of the enzyme aspartate decarboxylase with the purpose of assessing the quantum chemical cluster approach for modeling this important class of decarboxylase enzymes. Active site models ranging in size from 27 to 220 atoms are designed, and the barrier and reaction energy of this step are evaluated. To model the enzyme surrounding, homogeneous polarizable medium techniques are used with several dielectric constants. The main conclusion is that when the active site model reaches a certain size, the solvation effects from the surroundings saturate. Similar results have previously been obtained from systematic studies of other classes of enzymes, suggesting that they are of a quite general nature.

  1. Recommender engine for continuous-time quantum Monte Carlo methods

    Science.gov (United States)

    Huang, Li; Yang, Yi-feng; Wang, Lei

    2017-03-01

    Recommender systems play an essential role in the modern business world. They recommend favorable items such as books, movies, and search queries to users based on their past preferences. Applying similar ideas and techniques to Monte Carlo simulations of physical systems boosts their efficiency without sacrificing accuracy. Exploiting the quantum to classical mapping inherent in the continuous-time quantum Monte Carlo methods, we construct a classical molecular gas model to reproduce the quantum distributions. We then utilize powerful molecular simulation techniques to propose efficient quantum Monte Carlo updates. The recommender engine approach provides a general way to speed up the quantum impurity solvers.

  2. A simple method for generating exactly solvable quantum mechanical potentials

    CERN Document Server

    Williams, B W

    1993-01-01

    A simple transformation method permitting the generation of exactly solvable quantum mechanical potentials from special functions solving second-order differential equations is reviewed. This method is applied to Gegenbauer polynomials to generate an attractive radial potential. The relationship of this method to the determination of supersymmetric quantum mechanical superpotentials is discussed, and the superpotential for the radial potential is also derived. (author)

  3. Benchmarking quantum mechanical calculations with experimental NMR chemical shifts of 2-HADNT

    Science.gov (United States)

    Liu, Yuemin; Junk, Thomas; Liu, Yucheng; Tzeng, Nianfeng; Perkins, Richard

    2015-04-01

    In this study, both GIAO-DFT and GIAO-MP2 calculations of nuclear magnetic resonance (NMR) spectra were benchmarked with experimental chemical shifts. The experimental chemical shifts were determined experimentally for carbon-13 (C-13) of seven carbon atoms for the TNT degradation product 2-hydroxylamino-4,6-dinitrotoluene (2-HADNT). Quantum mechanics GIAO calculations were implemented using Becke-3-Lee-Yang-Parr (B3LYP) and other six hybrid DFT methods (Becke-1-Lee-Yang-Parr (B1LYP), Becke-half-and-half-Lee-Yang-Parr (BH and HLYP), Cohen-Handy-3-Lee-Yang-Parr (O3LYP), Coulomb-attenuating-B3LYP (CAM-B3LYP), modified-Perdew-Wang-91-Lee-Yang-Parr (mPW1LYP), and Xu-3-Lee-Yang-Parr (X3LYP)) which use the same correlation functional LYP. Calculation results showed that the GIAO-MP2 method gives the most accurate chemical shift values, and O3LYP method provides the best prediction of chemical shifts among the B3LYP and other five DFT methods. Three types of atomic partial charges, Mulliken (MK), electrostatic potential (ESP), and natural bond orbital (NBO), were also calculated using MP2/aug-cc-pVDZ method. A reasonable correlation was discovered between NBO partial charges and experimental chemical shifts of carbon-13 (C-13).

  4. Quantum Chemical Studies of Actinides and Lanthanides: From Small Molecules to Nanoclusters

    Science.gov (United States)

    Vlaisavljevich, Bess

    Research into actinides is of high interest because of their potential applications as an energy source and for the environmental implications therein. Global concern has arisen since the development of the actinide concept in the 1940s led to the industrial scale use of the commercial nuclear energy cycle and nuclear weapons production. Large quantities of waste have been generated from these processes inspiring efforts to address fundamental questions in actinide science. In this regard, the objective of this work is to use theory to provide insight and predictions into actinide chemistry, where experimental work is extremely challenging because of the intrinsic difficulties of the experiments themselves and the safety issues associated with this type of chemistry. This thesis is a collection of theoretical studies of actinide chemistry falling into three categories: quantum chemical and matrix isolation studies of small molecules, the electronic structure of organoactinide systems, and uranyl peroxide nanoclusters and other solid state actinide compounds. The work herein not only spans a wide range of systems size but also investigates a range of chemical problems. Various quantum chemical approaches have been employed. Wave function-based methods have been used to study the electronic structure of actinide containing molecules of small to middle-size. Among these methods, the complete active space self consistent field (CASSCF) approach with corrections from second-order perturbation theory (CASPT2), the generalized active space SCF (GASSCF) approach, and Moller-Plesset second-order perturbation theory (MP2) have been employed. Likewise, density functional theory (DFT) has been used along with analysis tools like bond energy decomposition, bond orders, and Bader's Atoms in Molecules. From these quantum chemical results, comparison with experimentally obtained structures and spectra are made.

  5. Chemical methods of rock analysis

    National Research Council Canada - National Science Library

    Jeffery, P. G; Hutchison, D

    1981-01-01

    .... Such methods include those based upon spectrophotometry, flame emission spectrometry and atomic absorption spectroscopy, as well as gravimetry, titrimetry and the use of ion-selective electrodes...

  6. Field theoretical methods in chemical physics

    International Nuclear Information System (INIS)

    Paul, R.

    1982-01-01

    Field theory will become an important tool for the chemist, and this book presents a clear and thorough account of the theory itself and its applications for solving a wide variety of chemical problems. The author has brought together the foundations upon which the many and varied applications of field theory have been built, giving more intermediate steps than is usual in the derivations. This makes the book easily accessible to anyone with a background of calculus, statistical thermodynamics and elementary quantum chemistry. (orig./HK)

  7. Chemical Potential for the Interacting Classical Gas and the Ideal Quantum Gas Obeying a Generalized Exclusion Principle

    Science.gov (United States)

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

    2012-01-01

    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…

  8. Vibrational, electronic and quantum chemical studies of 1,2,4-benzenetricarboxylic-1,2-anhydride.

    Science.gov (United States)

    Arjunan, V; Raj, Arushma; Subramanian, S; Mohan, S

    2013-06-01

    The FTIR and FT-Raman spectra of 1,2,4-benzenetricarboxylic-1,2-anhydride (BTCA) have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. The complete vibrational assignments and analysis of BTCA have been performed. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP, MP2, B3PW91) method using 6-311++G(**), 6-31G(**) and cc-pVTZ basis sets. The structural parameters, energies, thermodynamic parameters, vibrational frequencies and the NBO charges of BTCA were determined by the DFT method. The (1)H and (13)C isotropic chemical shifts (δ ppm) of BTCA with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. The delocalization energies of different types of interactions were determined. Copyright © 2013 Elsevier B.V. All rights reserved.

  9. Survey of Nuclear Methods in Chemical Technology

    International Nuclear Information System (INIS)

    Broda, E.

    1966-01-01

    An attempt is made to classify nuclear methods on a logical basis to facilitate assimilation by the technologist. The three main groups are: (I) Tracer methods, (II) Methods based on the influence of absorbers on radiations to be measured, and (III) Radiation chemical methods. The variants of the first two groups are discussed in some detail, and typical examples are given. Group I can be subdivided into (1) Indicator methods, (2) Emanation methods, (3) Radioreagent methods, and (4) Isotope dilution methods, Group II into (5) Activation methods, (6) Absorption methods, (7) Induced Nuclear Reaction methods, (8) Scattering methods, and (9) Fluorescence methods. While the economic benefits due to nuclear methods already run into hundreds of millions of dollars annually, owing to radiation protection problems radiochemical methods in the strict sense are not widely used in actual production. It is suggested that more use should be made of pilot plant tracer studies of chemical processes as used in industry. (author)

  10. Chemical methods of rock analysis

    National Research Council Canada - National Science Library

    Jeffery, P. G; Hutchison, D

    1981-01-01

    A practical guide to the methods in general use for the complete analysis of silicate rock material and for the determination of all those elements present in major, minor or trace amounts in silicate...

  11. On the resolvents methods in quantum perturbation calculations

    International Nuclear Information System (INIS)

    Burzynski, A.

    1979-01-01

    This paper gives a systematic review of resolvent methods in quantum perturbation calculations. The case of discrete spectrum of hamiltonian is considered specially (in the literature this is the fewest considered case). The topics of calculations of quantum transitions by using of the resolvent formalism, quantum transitions between states from particular subspaces, the shifts of energy levels, are shown. The main ideas of stationary perturbation theory developed by Lippmann and Schwinger are considered too. (author)

  12. Chemical Tracer Methods: Chapter 7

    Science.gov (United States)

    Healy, Richard W.

    2017-01-01

    Tracers have a wide variety of uses in hydrologic studies: providing quantitative or qualitative estimates of recharge, identifying sources of recharge, providing information on velocities and travel times of water movement, assessing the importance of preferential flow paths, providing information on hydrodynamic dispersion, and providing data for calibration of water flow and solute-transport models (Walker, 1998; Cook and Herczeg, 2000; Scanlon et al., 2002b). Tracers generally are ions, isotopes, or gases that move with water and that can be detected in the atmosphere, in surface waters, and in the subsurface. Heat also is transported by water; therefore, temperatures can be used to trace water movement. This chapter focuses on the use of chemical and isotopic tracers in the subsurface to estimate recharge. Tracer use in surface-water studies to determine groundwater discharge to streams is addressed in Chapter 4; the use of temperature as a tracer is described in Chapter 8.Following the nomenclature of Scanlon et al. (2002b), tracers are grouped into three categories: natural environmental tracers, historical tracers, and applied tracers. Natural environmental tracers are those that are transported to or created within the atmosphere under natural processes; these tracers are carried to the Earth’s surface as wet or dry atmospheric deposition. The most commonly used natural environmental tracer is chloride (Cl) (Allison and Hughes, 1978). Ocean water, through the process of evaporation, is the primary source of atmospheric Cl. Other tracers in this category include chlorine-36 (36Cl) and tritium (3H); these two isotopes are produced naturally in the Earth’s atmosphere; however, there are additional anthropogenic sources of them.

  13. Some approaches to the quantum-chemical theory of heterogeneous catalysis

    Energy Technology Data Exchange (ETDEWEB)

    Zhidomirov, G M

    1977-09-01

    A discussion of mathematical methods, models, and parameters used in various quantum-chemical descriptions of chemisorption and reaction at silica and aluminosilicate surfaces covers the continuous-surface model, the cluster model of the surface, the variation of pseudo-atom parameters to reduce the magnitude of boundary effects in the cluster model, the calculation of individual bond strengths in chemisorbed molecules, dissociative adsorption, applications to adsorption on silica and aluminosilicates, the mechanisms of hydrogen-deuterium exchange, etc. Diagrams, graphs, and 42 references.

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

    Energy Technology Data Exchange (ETDEWEB)

    Fujiwara, Y [Department of Mathematical and Life Sciences, Graduate School of Science, Hiroshima University, Higashi-Hiroshima, Hiroshima 739-8526 (Japan); Tanimoto, Y [Faculty of Pharmacy, Osaka Ohtani University, Nishikiorikita, Tondabayashi 584-8540 (Japan)], E-mail: fuji0710@sci.hiroshima-u.ac.jp

    2009-03-01

    On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 {+-} 0.005) x (calculated) - (1.22 {+-} 0.60) x 10{sup -6} in a unit of cm{sup 3} mol{sup -1} and good cost performance.

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

    International Nuclear Information System (INIS)

    Fujiwara, Y; Tanimoto, Y

    2009-01-01

    On magnetic force evaluation necessary for magnetically levitated diamagnetic substances, isotropic diamagnetic susceptibility estimation by the ab initio quantum chemical calculation using Gaussian03W was verified for more than 300 molecules in a viewpoint of the accuracy in the absolute value and the calculation level affording good cost performance. From comparison, the method of B3PW91 / 6-311+G(d,p) was found to give the adequate absolute value by the relation of (observed) = (1.03 ± 0.005) x (calculated) - (1.22 ± 0.60) x 10 -6 in a unit of cm 3 mol -1 and good cost performance.

  16. Quantum Chemical Prediction of Equilibrium Acidities of Ureas, Deltamides, Squaramides, and Croconamides.

    Science.gov (United States)

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

    2017-10-06

    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.

  17. 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....

  18. Functional renormalization group methods in quantum chromodynamics

    International Nuclear Information System (INIS)

    Braun, J.

    2006-01-01

    We apply functional Renormalization Group methods to Quantum Chromodynamics (QCD). First we calculate the mass shift for the pion in a finite volume in the framework of the quark-meson model. In particular, we investigate the importance of quark effects. As in lattice gauge theory, we find that the choice of quark boundary conditions has a noticeable effect on the pion mass shift in small volumes. A comparison of our results to chiral perturbation theory and lattice QCD suggests that lattice QCD has not yet reached volume sizes for which chiral perturbation theory can be applied to extrapolate lattice results for low-energy observables. Phase transitions in QCD at finite temperature and density are currently very actively researched. We study the chiral phase transition at finite temperature with two approaches. First, we compute the phase transition temperature in infinite and in finite volume with the quark-meson model. Though qualitatively correct, our results suggest that the model does not describe the dynamics of QCD near the finite-temperature phase boundary accurately. Second, we study the approach to chiral symmetry breaking in terms of quarks and gluons. We compute the running QCD coupling for all temperatures and scales. We use this result to determine quantitatively the phase boundary in the plane of temperature and number of quark flavors and find good agreement with lattice results. (orig.)

  19. Functional renormalization group methods in quantum chromodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Braun, J.

    2006-12-18

    We apply functional Renormalization Group methods to Quantum Chromodynamics (QCD). First we calculate the mass shift for the pion in a finite volume in the framework of the quark-meson model. In particular, we investigate the importance of quark effects. As in lattice gauge theory, we find that the choice of quark boundary conditions has a noticeable effect on the pion mass shift in small volumes. A comparison of our results to chiral perturbation theory and lattice QCD suggests that lattice QCD has not yet reached volume sizes for which chiral perturbation theory can be applied to extrapolate lattice results for low-energy observables. Phase transitions in QCD at finite temperature and density are currently very actively researched. We study the chiral phase transition at finite temperature with two approaches. First, we compute the phase transition temperature in infinite and in finite volume with the quark-meson model. Though qualitatively correct, our results suggest that the model does not describe the dynamics of QCD near the finite-temperature phase boundary accurately. Second, we study the approach to chiral symmetry breaking in terms of quarks and gluons. We compute the running QCD coupling for all temperatures and scales. We use this result to determine quantitatively the phase boundary in the plane of temperature and number of quark flavors and find good agreement with lattice results. (orig.)

  20. Effects of xenon insertion into hydrogen bromide. Comparison of the electronic structure of the HBr···CO2 and HXeBr···CO2 complexes using quantum chemical topology methods: electron localization function, atoms in molecules and symmetry adapted perturbation theory.

    Science.gov (United States)

    Makarewicz, Emilia; Gordon, Agnieszka J; Mierzwicki, Krzysztof; Latajka, Zdzislaw; Berski, Slawomir

    2014-06-05

    Quantum chemistry methods have been applied to study the influence of the Xe atom inserted into the hydrogen-bromine bond (HBr → HXeBr), particularly on the nature of atomic interactions in the HBr···CO2 and HXeBr···CO2 complexes. Detailed analysis of the nature of chemical bonds has been carried out using topological analysis of the electron localization function, while topological analysis of electron density was used to gain insight into the nature of weak nonbonding interactions. Symmetry-adapted perturbation theory within the orbital approach was applied for greater understanding of the physical contributions to the total interaction energy.

  1. Tuning the Emission Energy of Chemically Doped Graphene Quantum Dots

    Directory of Open Access Journals (Sweden)

    Noor-Ul-Ain

    2016-11-01

    Full Text Available Tuning the emission energy of graphene quantum dots (GQDs and understanding the reason of tunability is essential for the GOD function in optoelectronic devices. Besides material-based challenges, the way to realize chemical doping and band gap tuning also pose a serious challenge. In this study, we tuned the emission energy of GQDs by substitutional doping using chlorine, nitrogen, boron, sodium, and potassium dopants in solution form. Photoluminescence data obtained from (Cl- and N-doped GQDs and (B-, Na-, and K-doped GQDs, respectively exhibited red- and blue-shift with respect to the photoluminescence of the undoped GQDs. X-ray photoemission spectroscopy (XPS revealed that oxygen functional groups were attached to GQDs. We qualitatively correlate red-shift of the photoluminescence with the oxygen functional groups using literature references which demonstrates that more oxygen containing groups leads to the formation of more defect states and is the reason of observed red-shift of luminescence in GQDs. Further on, time resolved photoluminescence measurements of Cl- and N-GQDs demonstrated that Cl substitution in GQDs has effective role in radiative transition whereas in N-GQDs leads to photoluminescence (PL quenching with non-radiative transition to ground state. Presumably oxidation or reduction processes cause a change of effective size and the bandgap.

  2. Quantum statistical Monte Carlo methods and applications to spin systems

    International Nuclear Information System (INIS)

    Suzuki, M.

    1986-01-01

    A short review is given concerning the quantum statistical Monte Carlo method based on the equivalence theorem that d-dimensional quantum systems are mapped onto (d+1)-dimensional classical systems. The convergence property of this approximate tansformation is discussed in detail. Some applications of this general appoach to quantum spin systems are reviewed. A new Monte Carlo method, ''thermo field Monte Carlo method,'' is presented, which is an extension of the projection Monte Carlo method at zero temperature to that at finite temperatures

  3. Applicability of transfer tensor method for open quantum system dynamics.

    Science.gov (United States)

    Gelzinis, Andrius; Rybakovas, Edvardas; Valkunas, Leonas

    2017-12-21

    Accurate simulations of open quantum system dynamics is a long standing issue in the field of chemical physics. Exact methods exist, but are costly, while perturbative methods are limited in their applicability. Recently a new black-box type method, called transfer tensor method (TTM), was proposed [J. Cerrillo and J. Cao, Phys. Rev. Lett. 112, 110401 (2014)]. It allows one to accurately simulate long time dynamics with a numerical cost of solving a time-convolution master equation, provided many initial system evolution trajectories are obtained from some exact method beforehand. The possible time-savings thus strongly depend on the ratio of total versus initial evolution lengths. In this work, we investigate the parameter regimes where an application of TTM would be most beneficial in terms of computational time. We identify several promising parameter regimes. Although some of them correspond to cases when perturbative theories could be expected to perform well, we find that the accuracy of such approaches depends on system parameters in a more complex way than it is commonly thought. We propose that the TTM should be applied whenever system evolution is expected to be long and accuracy of perturbative methods cannot be ensured or in cases when the system under consideration does not correspond to any single perturbative regime.

  4. Comparison of Chemical and Physical-chemical Wastewater Discoloring Methods

    Directory of Open Access Journals (Sweden)

    Durašević, V.

    2007-11-01

    Full Text Available Today's chemical and physical-chemical wastewater discoloration methods do not completely meet demands regarding degree of discoloration. In this paper discoloration was performed using Fenton (FeSO4 . 7 H2O + H2O2 + H2SO4 and Fenton-like (FeCl3 . 6 H2O + H2O2 + HCOOH chemical methods and physical-chemical method of coagulation/flocculation (using poly-electrolyte (POEL combining anion active coagulant (modified poly-acrylamides and cationic flocculant (product of nitrogen compounds in combination with adsorption on activated carbon. Suitability of aforementioned methods was investigated on reactive and acid dyes, regarding their most common use in the textile industry. Also, investigations on dyes of different chromogen (anthraquinone, phthalocyanine, azo and xanthene were carried out in order to determine the importance of molecular spatial structure. Oxidative effect of Fenton and Fenton-like reagents resulted in decomposition of colored chromogen and high degree of discoloration. However, the problem is the inability of adding POEL in stechiometrical ratio (also present in physical-chemical methods, when the phenomenon of overdosing coagulants occurs in order to obtain a higher degree of discoloration, creating a potential danger of burdening water with POEL. Input and output water quality was controlled through spectrophotometric measurements and standard biological parameters. In addition, part of the investigations concerned industrial wastewaters obtained from dyeing cotton materials using reactive dye (C. I. Reactive Blue 19, a process that demands the use of vast amounts of electrolytes. Also, investigations of industrial wastewaters was labeled as a crucial step carried out in order to avoid serious misassumptions and false conclusions, which may arise if dyeing processes are only simulated in the laboratory.

  5. Quantum-chemical study of hydride transfer in catalytic transformation of paraffins on zeolites

    NARCIS (Netherlands)

    Kazansky, V.B.; Frash, M.V.; Santen, van R.A.; Chon, H.; Ihm, S.-K.; Uh, Y.S.

    1997-01-01

    Ab initio quantum-chemical cluster calculations demonstrate that the activated complexes of hydride transfer reaction in catalytic transformation of paraffins on zeolites very much resembles adsorbed nonclassical carbonium ions. The calculated activation energies for reactions involving propane and

  6. 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 ... CdSe quantum dots; chemical bath deposition; capping; green chemistry; nanomaterials. 1. .... at high concentration of nanoparticles.

  7. Quantum dynamic imaging theoretical and numerical methods

    CERN Document Server

    Ivanov, Misha

    2011-01-01

    Studying and using light or "photons" to image and then to control and transmit molecular information is among the most challenging and significant research fields to emerge in recent years. One of the fastest growing areas involves research in the temporal imaging of quantum phenomena, ranging from molecular dynamics in the femto (10-15s) time regime for atomic motion to the atto (10-18s) time scale of electron motion. In fact, the attosecond "revolution" is now recognized as one of the most important recent breakthroughs and innovations in the science of the 21st century. A major participant in the development of ultrafast femto and attosecond temporal imaging of molecular quantum phenomena has been theory and numerical simulation of the nonlinear, non-perturbative response of atoms and molecules to ultrashort laser pulses. Therefore, imaging quantum dynamics is a new frontier of science requiring advanced mathematical approaches for analyzing and solving spatial and temporal multidimensional partial differ...

  8. 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

    2013-01-01

    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)

  9. Twenty-first century quantum mechanics Hilbert space to quantum computers mathematical methods and conceptual foundations

    CERN Document Server

    Fano, Guido

    2017-01-01

    This book is designed to make accessible to nonspecialists the still evolving concepts of quantum mechanics and the terminology in which these are expressed. The opening chapters summarize elementary concepts of twentieth century quantum mechanics and describe the mathematical methods employed in the field, with clear explanation of, for example, Hilbert space, complex variables, complex vector spaces and Dirac notation, and the Heisenberg uncertainty principle. After detailed discussion of the Schrödinger equation, subsequent chapters focus on isotropic vectors, used to construct spinors, and on conceptual problems associated with measurement, superposition, and decoherence in quantum systems. Here, due attention is paid to Bell’s inequality and the possible existence of hidden variables. Finally, progression toward quantum computation is examined in detail: if quantum computers can be made practicable, enormous enhancements in computing power, artificial intelligence, and secure communication will result...

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

    International Nuclear Information System (INIS)

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

    2015-01-01

    We investigate possible improvements in the accuracy of semiempirical quantum chemistry (SQC) methods through the use of machine learning (ML) models for the parameters. For a given class of compounds, ML techniques require sufficiently large training sets to develop ML models that can be used for adapting SQC parameters to reflect changes in molecular composition and geometry. The ML-SQC approach allows the automatic tuning of SQC parameters for individual molecules, thereby improving the accuracy without deteriorating transferability to molecules with molecular descriptors very different from those in the training set. The performance of this approach is demonstrated for the semiempirical OM2 method using a set of 6095 constitutional isomers 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

  11. Spectroscopic Chemical Analysis Methods and Apparatus

    Science.gov (United States)

    Hug, William F. (Inventor); Reid, Ray D. (Inventor); Bhartia, Rohit (Inventor); Lane, Arthur L. (Inventor)

    2018-01-01

    Spectroscopic chemical analysis methods and apparatus are disclosed which employ deep ultraviolet (e.g. in the 200 nm to 300 nm spectral range) electron beam pumped wide bandgap semiconductor lasers, incoherent wide bandgap semiconductor light emitting devices, and hollow cathode metal ion lasers to perform non-contact, non-invasive detection of unknown chemical analytes. These deep ultraviolet sources enable dramatic size, weight and power consumption reductions of chemical analysis instruments. In some embodiments, Raman spectroscopic detection methods and apparatus use ultra-narrow-band angle tuning filters, acousto-optic tuning filters, and temperature tuned filters to enable ultra-miniature analyzers for chemical identification. In some embodiments Raman analysis is conducted along with photoluminescence spectroscopy (i.e. fluorescence and/or phosphorescence spectroscopy) to provide high levels of sensitivity and specificity in the same instrument.

  12. Zeta function methods and quantum fluctuations

    International Nuclear Information System (INIS)

    Elizalde, Emilio

    2008-01-01

    A review of some recent advances in zeta function techniques is given, in problems of pure mathematical nature but also as applied to the computation of quantum vacuum fluctuations in different field theories, and specially with a view to cosmological applications

  13. VBSCF Methods: Classical Chemical Concepts and Beyond

    NARCIS (Netherlands)

    Rashid, Z.

    2013-01-01

    The aim of this research has been to extend the ab initio Valence Bond Self-Consistent Field (VBSCF) methodology and to apply this method to the electronic structure of molecules. The valence bond method directly deals with the chemical structure of molecules in a pictorial language, which chemists

  14. Efficient method for transport simulations in quantum cascade lasers

    Directory of Open Access Journals (Sweden)

    Maczka Mariusz

    2017-01-01

    Full Text Available An efficient method for simulating quantum transport in quantum cascade lasers is presented. The calculations are performed within a simple approximation inspired by Büttiker probes and based on a finite model for semiconductor superlattices. The formalism of non-equilibrium Green’s functions is applied to determine the selected transport parameters in a typical structure of a terahertz laser. Results were compared with those obtained for a infinite model as well as other methods described in literature.

  15. Fast synthesize ZnO quantum dots via ultrasonic method.

    Science.gov (United States)

    Yang, Weimin; Zhang, Bing; Ding, Nan; Ding, Wenhao; Wang, Lixi; Yu, Mingxun; Zhang, Qitu

    2016-05-01

    Green emission ZnO quantum dots were synthesized by an ultrasonic sol-gel method. The ZnO quantum dots were synthesized in various ultrasonic temperature and time. Photoluminescence properties of these ZnO quantum dots were measured. Time-resolved photoluminescence decay spectra were also taken to discover the change of defects amount during the reaction. Both ultrasonic temperature and time could affect the type and amount of defects in ZnO quantum dots. Total defects of ZnO quantum dots decreased with the increasing of ultrasonic temperature and time. The dangling bonds defects disappeared faster than the optical defects. Types of optical defects first changed from oxygen interstitial defects to oxygen vacancy and zinc interstitial defects. Then transformed back to oxygen interstitial defects again. The sizes of ZnO quantum dots would be controlled by both ultrasonic temperature and time as well. That is, with the increasing of ultrasonic temperature and time, the sizes of ZnO quantum dots first decreased then increased. Moreover, concentrated raw materials solution brought larger sizes and more optical defects of ZnO quantum dots. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. 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

    2006-01-01

    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

  17. Advanced undergraduate quantum mechanics methods and applications

    CERN Document Server

    Deych, Lev I

    2018-01-01

    This introduction to quantum mechanics is intended for undergraduate students of physics, chemistry, and engineering with some previous exposure to quantum ideas. Following in Heisenberg’s and Dirac’s footsteps, this book is centered on the concept of the quantum state as an embodiment of all experimentally available information about a system, and its representation as a vector in an abstract Hilbert space. This conceptual framework and formalism are introduced immediately, and developed throughout the first four chapters, while the standard Schrödinger equation does not appear until Chapter 5. The book grew out of lecture notes developed by the author over fifteen years of teaching at the undergraduate level. In response to numerous requests by students, material is presented with an unprecedented level of detail in both derivation of technical results and discussion of their physical significance.  The book is written for students to enjoy reading it, rather than to use only as a source of formulas a...

  18. Random Forest Approach to QSPR Study of Fluorescence Properties Combining Quantum Chemical Descriptors and Solvent Conditions.

    Science.gov (United States)

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

    2018-04-22

    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.

  19. Adaptive Neuro-Fuzzy Inference System Applied QSAR with Quantum Chemical Descriptors for Predicting Radical Scavenging Activities of Carotenoids.

    Science.gov (United States)

    Jhin, Changho; Hwang, Keum Taek

    2015-01-01

    One of the physiological characteristics of carotenoids is their radical scavenging activity. In this study, the relationship between radical scavenging activities and quantum chemical descriptors of carotenoids was determined. Adaptive neuro-fuzzy inference system (ANFIS) applied quantitative structure-activity relationship models (QSAR) were also developed for predicting and comparing radical scavenging activities of carotenoids. Semi-empirical PM6 and PM7 quantum chemical calculations were done by MOPAC. Ionisation energies of neutral and monovalent cationic carotenoids and the product of chemical potentials of neutral and monovalent cationic carotenoids were significantly correlated with the radical scavenging activities, and consequently these descriptors were used as independent variables for the QSAR study. The ANFIS applied QSAR models were developed with two triangular-shaped input membership functions made for each of the independent variables and optimised by a backpropagation method. High prediction efficiencies were achieved by the ANFIS applied QSAR. The R-square values of the developed QSAR models with the variables calculated by PM6 and PM7 methods were 0.921 and 0.902, respectively. The results of this study demonstrated reliabilities of the selected quantum chemical descriptors and the significance of QSAR models.

  20. Adaptive Neuro-Fuzzy Inference System Applied QSAR with Quantum Chemical Descriptors for Predicting Radical Scavenging Activities of Carotenoids.

    Directory of Open Access Journals (Sweden)

    Changho Jhin

    Full Text Available One of the physiological characteristics of carotenoids is their radical scavenging activity. In this study, the relationship between radical scavenging activities and quantum chemical descriptors of carotenoids was determined. Adaptive neuro-fuzzy inference system (ANFIS applied quantitative structure-activity relationship models (QSAR were also developed for predicting and comparing radical scavenging activities of carotenoids. Semi-empirical PM6 and PM7 quantum chemical calculations were done by MOPAC. Ionisation energies of neutral and monovalent cationic carotenoids and the product of chemical potentials of neutral and monovalent cationic carotenoids were significantly correlated with the radical scavenging activities, and consequently these descriptors were used as independent variables for the QSAR study. The ANFIS applied QSAR models were developed with two triangular-shaped input membership functions made for each of the independent variables and optimised by a backpropagation method. High prediction efficiencies were achieved by the ANFIS applied QSAR. The R-square values of the developed QSAR models with the variables calculated by PM6 and PM7 methods were 0.921 and 0.902, respectively. The results of this study demonstrated reliabilities of the selected quantum chemical descriptors and the significance of QSAR models.

  1. Chemical decontaminating method for stainless steel

    International Nuclear Information System (INIS)

    Onuma, Tsutomu; Akimoto, Hidetoshi.

    1990-01-01

    Radioactive metal wastes comprising passivated stainless steels are chemically decontaminated to such a radioactivity level as that of usual wastes. The present invention for chemically decontaminating stainless steels comprises a first step of immersing decontaminates into a sulfuric acid solution and a second step of immersing them into an aqueous solution prepared by adding oxidative metal salts to sulfuric acid, in which a portion of the surface of stainless steels as decontaminates are chemically ground to partially expose substrate materials and then the above-mentioned decontamination steps are applied. More than 90% of radioactive materials are removed in this method by the dissolution of the exposed substrate materials and peeling of cruds secured to the surface of the materials upon dissolution. This method is applicable to decontamination of articles having complicate shapes, can reduce the amount of secondary wastes after decontamination and also remarkably shorten the time required for decontamination. (T.M.)

  2. A multidimensional pseudospectral method for optimal control of quantum ensembles

    International Nuclear Information System (INIS)

    Ruths, Justin; Li, Jr-Shin

    2011-01-01

    In our previous work, we have shown that the pseudospectral method is an effective and flexible computation scheme for deriving pulses for optimal control of quantum systems. In practice, however, quantum systems often exhibit variation in the parameters that characterize the system dynamics. This leads us to consider the control of an ensemble (or continuum) of quantum systems indexed by the system parameters that show variation. We cast the design of pulses as an optimal ensemble control problem and demonstrate a multidimensional pseudospectral method with several challenging examples of both closed and open quantum systems from nuclear magnetic resonance spectroscopy in liquid. We give particular attention to the ability to derive experimentally viable pulses of minimum energy or duration.

  3. Structural and vibrational spectral investigations of melaminium maleate monohydrate by FTIR, FT-Raman and quantum chemical calculations

    Science.gov (United States)

    Arjunan, V.; Kalaivani, M.; Marchewka, M. K.; Mohan, S.

    2013-04-01

    The structural investigations of the molecular complex of melamine with maleic acid, namely melaminium maleate monohydrate have been carried out by quantum chemical methods in addition to FTIR, FT-Raman and far-infrared spectral studies. The quantum chemical studies were performed with DFT (B3LYP) method using 6-31G**, cc-pVDZ and 6-311++G** basis sets to determine the energy, structural and thermodynamic parameters of melaminium maleate monohydrate. The hydrogen atom from maleic acid was transferred to the melamine molecule giving the singly protonated melaminium cation. The ability of ions to form spontaneous three-dimensional structure through weak Osbnd H⋯O and Nsbnd H⋯O hydrogen bonds shows notable vibrational effects.

  4. Structural and vibrational spectral investigations of melaminium maleate monohydrate by FTIR, FT-Raman and quantum chemical calculations.

    Science.gov (United States)

    Arjunan, V; Kalaivani, M; Marchewka, M K; Mohan, S

    2013-04-15

    The structural investigations of the molecular complex of melamine with maleic acid, namely melaminium maleate monohydrate have been carried out by quantum chemical methods in addition to FTIR, FT-Raman and far-infrared spectral studies. The quantum chemical studies were performed with DFT (B3LYP) method using 6-31G(**), cc-pVDZ and 6-311++G(**) basis sets to determine the energy, structural and thermodynamic parameters of melaminium maleate monohydrate. The hydrogen atom from maleic acid was transferred to the melamine molecule giving the singly protonated melaminium cation. The ability of ions to form spontaneous three-dimensional structure through weak OH···O and NH···O hydrogen bonds shows notable vibrational effects. Copyright © 2013 Elsevier B.V. All rights reserved.

  5. Jump probabilities in the non-Markovian quantum jump method

    International Nuclear Information System (INIS)

    Haerkoenen, Kari

    2010-01-01

    The dynamics of a non-Markovian open quantum system described by a general time-local master equation is studied. The propagation of the density operator is constructed in terms of two processes: (i) deterministic evolution and (ii) evolution of a probability density functional in the projective Hilbert space. The analysis provides a derivation for the jump probabilities used in the recently developed non-Markovian quantum jump (NMQJ) method (Piilo et al 2008 Phys. Rev. Lett. 100 180402).

  6. Simulation of quantum systems by the tomography Monte Carlo method

    International Nuclear Information System (INIS)

    Bogdanov, Yu I

    2007-01-01

    A new method of statistical simulation of quantum systems is presented which is based on the generation of data by the Monte Carlo method and their purposeful tomography with the energy minimisation. The numerical solution of the problem is based on the optimisation of the target functional providing a compromise between the maximisation of the statistical likelihood function and the energy minimisation. The method does not involve complicated and ill-posed multidimensional computational procedures and can be used to calculate the wave functions and energies of the ground and excited stationary sates of complex quantum systems. The applications of the method are illustrated. (fifth seminar in memory of d.n. klyshko)

  7. Recent developments of the quantum chemical cluster approach for modeling enzyme reactions.

    Science.gov (United States)

    Siegbahn, Per E M; Himo, Fahmi

    2009-06-01

    The quantum chemical cluster approach for modeling enzyme reactions is reviewed. Recent applications have used cluster models much larger than before which have given new modeling insights. One important and rather surprising feature is the fast convergence with cluster size of the energetics of the reactions. Even for reactions with significant charge separation it has in some cases been possible to obtain full convergence in the sense that dielectric cavity effects from outside the cluster do not contribute to any significant extent. Direct comparisons between quantum mechanics (QM)-only and QM/molecular mechanics (MM) calculations for quite large clusters in a case where the results differ significantly have shown that care has to be taken when using the QM/MM approach where there is strong charge polarization. Insights from the methods used, generally hybrid density functional methods, have also led to possibilities to give reasonable error limits for the results. Examples are finally given from the most extensive study using the cluster model, the one of oxygen formation at the oxygen-evolving complex in photosystem II.

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

    Directory of Open Access Journals (Sweden)

    Casper Steinmann

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

  9. Method for adding nodes to a quantum key distribution system

    Science.gov (United States)

    Grice, Warren P

    2015-02-24

    An improved quantum key distribution (QKD) system and method are provided. The system and method introduce new clients at intermediate points along a quantum channel, where any two clients can establish a secret key without the need for a secret meeting between the clients. The new clients perform operations on photons as they pass through nodes in the quantum channel, and participate in a non-secret protocol that is amended to include the new clients. The system and method significantly increase the number of clients that can be supported by a conventional QKD system, with only a modest increase in cost. The system and method are compatible with a variety of QKD schemes, including polarization, time-bin, continuous variable and entanglement QKD.

  10. Quantum chemical approach for condensed-phase thermochemistry (V): Development of rigid-body type harmonic solvation model

    Science.gov (United States)

    Tarumi, Moto; Nakai, Hiromi

    2018-05-01

    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.

  11. Quantum chemical analysis of potential anti-Parkinson agents

    Indian Academy of Sciences (India)

    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 split valence basis set (Def2-SVP) were applied to estimate the ligand-residue binding energies in the MAO-B active site. Moreover ...

  12. Performance test of multicomponent quantum mechanical calculation with polarizable continuum model for proton chemical shift.

    Science.gov (United States)

    Kanematsu, Yusuke; Tachikawa, Masanori

    2015-05-21

    Multicomponent quantum mechanical (MC_QM) calculations with polarizable continuum model (PCM) have been tested against liquid (1)H NMR chemical shifts for a test set of 80 molecules. Improvement from conventional quantum mechanical calculations was achieved for MC_QM calculations. The advantage of the multicomponent scheme could be attributed to the geometrical change from the equilibrium geometry by the incorporation of the hydrogen nuclear quantum effect, while that of PCM can be attributed to the change of the electronic structure according to the polarization by solvent effects.

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

    Science.gov (United States)

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

    2018-03-01

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

  14. Degradation of Perfluorinated Ether Lubricants on Pure Aluminum Surfaces: Semiempirical Quantum Chemical Modeling

    Science.gov (United States)

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

    1997-01-01

    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.

  15. 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.

    1989-01-01

    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

  16. Chemically functionalized ZnS quantum dots as new optical nanosensor of herbicides

    Science.gov (United States)

    Masteri-Farahani, M.; Mahdavi, S.; Khanmohammadi, H.

    2018-03-01

    Surface chemical functionalization of ZnS quantum dots (ZnS-QDs) with cysteamine hydrochloride resulted in the preparation of an optical nanosensor for detection of herbicides. Characterization of the functionalized ZnS-QDs was performed with physicochemical methods such as x-ray diffraction (XRD), transmission electron microscopy (TEM), Fourier transform infrared (FT-IR) spectroscopy, energy dispersive x-ray (EDX) analysis, ultraviolet-visible (UV–vis) and photoluminescence (PL) spectroscopies. The optical band gap of the functionalized ZnS-QDs was determined by using Tauc plot as 4.1 eV. Addition of various herbicides resulted in the linearly fluorescence quenching of the functionalized ZnS-QDs according to the Stern-Volmer equation. The functionalized ZnS-QDs can be used as simple, rapid, and inexpensive nanosensor for practical detection and measurement of various herbicides.

  17. Quantum chemical modeling of the inhibition mechanism of monoamine oxidase by oxazolidinone and analogous heterocyclic compounds.

    Science.gov (United States)

    Erdem, Safiye Sağ; Özpınar, Gül Altınbaş; Boz, Ümüt

    2014-02-01

    Monoamine oxidase (MAO, EC 1.4.3.4) is responsible from the oxidation of a variety of amine neurotransmitters. MAO inhibitors are used for the treatment of depression or Parkinson's disease. They also inhibit the catabolism of dietary amines. According to one hypothesis, inactivation results from the formation of a covalent adduct to a cysteine residue in the enzyme. If the adduct is stable enough, the enzyme is inhibited for a long time. After a while, enzyme can turn to its active form as a result of adduct breakdown by β-elimination. In this study, the proposed inactivation mechanism was modeled and tested by quantum chemical calculations. Eight heterocyclic methylthioamine derivatives were selected to represent the proposed covalent adducts. Activation energies related to their β-elimination reactions were calculated using ab initio and density functional theory methods. Calculated activation energies were in good agreement with the relative stabilities of the hypothetical adducts predicted in the literature by enzyme inactivation measurements.

  18. Molecular interactions in ethyl acetate-chlorobenzene binary solution: Dielectric, spectroscopic studies and quantum chemical calculations

    Science.gov (United States)

    Karthick, N. K.; Kumbharkhane, A. C.; Joshi, Y. S.; Mahendraprabu, A.; Shanmugam, R.; Elangovan, A.; Arivazhagan, G.

    2017-05-01

    Dielectric studies using Time Domain Reflectometry method has been carried out on the binary solution of Ethyl acetate (EA) with Chlorobenzene (CBZ) over the entire composition range. Spectroscopic (FTIR and 13C NMR) signatures of neat EA, CBZ and their equimolar binary solution have also been recorded. The results of the spectroscopic studies favour the presence of (CBZ) Csbnd H ⋯ Odbnd C (EA), (EA) methylene Csbnd H ⋯ π electrons (CBZ) and (EA) methyl Csbnd H ⋯ Cl (CBZ) contacts which have been validated using quantum chemical calculations. Dimerization of CBZ has been identified. Presence of β-clusters has been identified in all the solutions. Although EA and CBZ molecules have nearly equal molar volumes, CBZ molecules experience larger hindrance for the rotation than EA molecules. Very small excess dielectric constant (εE) values may be correlated with weak heteromolecular forces and/or closed heteromolecular association.

  19. Semiempirical Quantum Chemical Calculations Accelerated on a Hybrid Multicore CPU-GPU Computing Platform.

    Science.gov (United States)

    Wu, Xin; Koslowski, Axel; Thiel, Walter

    2012-07-10

    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.

  20. Vibrational spectroscopic studies of Isoleucine by quantum chemical calculations.

    Science.gov (United States)

    Moorthi, P P; Gunasekaran, S; Ramkumaar, G R

    2014-04-24

    In this work, we reported a combined experimental and theoretical study on molecular structure, vibrational spectra and NBO analysis of Isoleucine (2-Amino-3-methylpentanoic acid). The optimized molecular structure, vibrational frequencies, corresponding vibrational assignments, thermodynamics properties, NBO analyses, NMR chemical shifts and ultraviolet-visible spectral interpretation of Isoleucine have been studied by performing MP2 and DFT/cc-pVDZ level of theory. The FTIR, FT-Raman spectra were recorded in the region 4000-400 cm(-1) and 3500-50 cm(-1) respectively. The UV-visible absorption spectra of the compound were recorded in the range of 200-800 nm. Computational calculations at MP2 and B3LYP level with basis set of cc-pVDZ is employed in complete assignments of Isoleucine molecule on the basis of the potential energy distribution (PED) of the vibrational modes, calculated using VEDA-4 program. The calculated wavenumbers are compared with the experimental values. The difference between the observed and calculated wavenumber values of most of the fundamentals is very small. (13)C and (1)H nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method and compared with experimental results. The formation of hydrogen bond was investigated in terms of the charge density by the NBO calculations. Based on the UV spectra and TD-DFT calculations, the electronic structure and the assignments of the absorption bands were carried out. Besides, molecular electrostatic potential (MEP) were investigated using theoretical calculations. Copyright © 2014 Elsevier B.V. All rights reserved.

  1. Electron-beam generated porous dextran gels: experimental and quantum chemical studies.

    Science.gov (United States)

    Naumov, Sergej; Knolle, Wolfgang; Becher, Jana; Schnabelrauch, Matthias; Reichelt, Senta

    2014-06-01

    The aim of this work was to investigate the reaction mechanism of electron-beam generated macroporous dextran cryogels by quantum chemical calculation and electron paramagnetic resonance measurements. Electron-beam radiation was used to initiate the cross-linking reaction of methacrylated dextran in semifrozen aqueous solutions. The pore morphology of the resulting cryogels was visualized by scanning electron microscopy. Quantum chemical calculations and electron paramagnetic resonance studies provided information on the most probable reaction pathway and the chain growth radicals. The most probable reaction pathway was a ring opening reaction and the addition of a C-atom to the double-bond of the methacrylated dextran molecule. First detailed quantum chemical calculation on the reaction mechanism of electron-beam initiated cross-linking reaction of methacrylated dextran are presented.

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

    Directory of Open Access Journals (Sweden)

    Irina Pustolaikina

    2016-12-01

    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.

  3. A general intermolecular force field based on tight-binding quantum chemical calculations

    Science.gov (United States)

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

    2017-10-01

    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.

  4. Synthesis, vibrational and quantum chemical investigations of hydrogen bonded complex betaine dihydrogen selenite

    Science.gov (United States)

    Arjunan, V.; Marchewka, Mariusz K.; Kalaivani, M.

    2012-10-01

    The molecular complex of betaine with selenious acid namely, betaine dihydrogen selenite (C5H13NO5Se, BDHSe) was synthesised by the reaction of betaine and SeO2 in a 1:1:1 solution of isopropanol, methanol and water. Crystals were grown from this solution by cooling to 253 K for few days. The complex was formed without accompanying proton transfer from selenious acid molecule to betaine. The complete vibrational assignments and analysis of BDHSe have been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings was added from the quantum chemical studies performed with DFT (B3LYP) method using 6-311++G∗∗, 6-31G∗∗, cc-pVDZ and 3-21G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of BDHSe were determined by the DFT method. The 1H and 13C isotropic chemical shifts (δ ppm) of BDHSe with respect to TMS were also calculated using the gauge independent atomic orbital (GIAO) method and compared with the experimental data. SHG experiment was carried out using Kurtz-Perry powder technique. The efficiency of second harmonic generation for BDHSe was estimated relatively to KDP: deff = 0.97 deff (KDP).

  5. On the factorization method in quantum mechanics

    OpenAIRE

    Rosas-Ortiz, J. Oscar

    1998-01-01

    New exactly solvable problems have already been studied by using a modification of the factorization method introduced by Mielnik. We review this method and its connection with the traditional factorization method. The survey includes the discussion on a generalization of the factorization energies used in the traditional Infeld and Hull method.

  6. Differential multiple quantum relaxation caused by chemical exchange outside the fast exchange limit

    International Nuclear Information System (INIS)

    Wang Chunyu; Palmer, Arthur G.

    2002-01-01

    Differential relaxation of multiple quantum coherences is a signature for chemical exchange processes in proteins. Previous analyses of experimental data have used theoretical descriptions applicable only in the limit of fast exchange. Theoretical expressions for differential relaxation rate constants that are accurate outside fast exchange are presented for two-spin-system subject to two-site chemical exchange. The theoretical expressions are validated using experimental results for 15 N- 1 H relaxation in basic pancreatic trypsin inhibitor. The new theoretical expression is valuable for identification and characterization of exchange processes in proteins using differential relaxation of multiple quantum coherences

  7. Functional methods and mappings of dissipative quantum systems

    International Nuclear Information System (INIS)

    Baur, H.

    2006-01-01

    In the first part of this work we extract the algebraic structure behind the method of the influence functional in the context of dissipative quantum mechanics. Special emphasis was put on the transition from a quantum mechanical description to a classical one, since it allows a deeper understanding of the measurement-process. This is tightly connected with the transition from a microscopic to a macroscopic world where the former one is described by the rules of quantum mechanics whereas the latter follows the rules of classical mechanics. In addition we show how the results of the influence functional method can be interpreted as a stochastical process, which in turn allows an easy comparison with the well known time development of a quantum mechanical system by use of the Schroedinger equation. In the following we examine the tight-binding approximation of models of which their hamiltionian shows discrete eigenstates in position space and where transitions between those states are suppressed so that propagation either is described by tunneling or by thermal activation. In the framework of dissipative quantum mechanics this leads to a tremendous simplification of the effective description of the system since instead of looking at the full history of all paths in the path integral description, we only have to look at all possible jump times and the possible corresponding set of weights for the jump direction, which is much easier to handle both analytically and numerically. In addition we deal with the mapping and the connection of dissipative quantum mechanical models with ones in quantum field theory and in particular models in statistical field theory. As an example we mention conformal invariance in two dimensions which always becomes relevant if a statistical system only has local interaction and is invariant under scaling. (orig.)

  8. Theoretical physics 7 quantum mechanics : methods and applications

    CERN Document Server

    Nolting, Wolfgang

    2017-01-01

    This textbook offers a clear and comprehensive introduction to methods and applications in quantum mechanics, one of the core components of undergraduate physics courses. It follows on naturally from the previous volumes in this series, thus developing the understanding of quantized states further on. The first part of the book introduces the quantum theory of angular momentum and approximation methods. More complex themes are covered in the second part of the book, which describes multiple particle systems and scattering theory. Ideally suited to undergraduate students with some grounding in the basics of quantum mechanics, the book is enhanced throughout with learning features such as boxed inserts and chapter summaries, with key mathematical derivations highlighted to aid understanding. The text is supported by numerous worked examples and end of chapter problem sets.  About the Theoretical Physics series Translated from the renowned and highly successful German editions, the eight volumes of this seri...

  9. Mathematical methods of many-body quantum field theory

    CERN Document Server

    Lehmann, Detlef

    2004-01-01

    Mathematical Methods of Many-Body Quantum Field Theory offers a comprehensive, mathematically rigorous treatment of many-body physics. It develops the mathematical tools for describing quantum many-body systems and applies them to the many-electron system. These tools include the formalism of second quantization, field theoretical perturbation theory, functional integral methods, bosonic and fermionic, and estimation and summation techniques for Feynman diagrams. Among the physical effects discussed in this context are BCS superconductivity, s-wave and higher l-wave, and the fractional quantum Hall effect. While the presentation is mathematically rigorous, the author does not focus solely on precise definitions and proofs, but also shows how to actually perform the computations.Presenting many recent advances and clarifying difficult concepts, this book provides the background, results, and detail needed to further explore the issue of when the standard approximation schemes in this field actually work and wh...

  10. Chemically reducing decontamination method for radioactive metal

    International Nuclear Information System (INIS)

    Tanaka, Akio; Onuma, Tsutomu; Sato, Hitoshi.

    1994-01-01

    The present invention concerns a decontamination method of electrolytically reducing radioactive metal wastes, then chemically dissolving the surface thereof with a strong acid decontaminating solution. This method utilizes dissolving characteristics of stainless steels in the strong acid solution. That is, in the electrolytic reduction operation, a portion of the metal wastes is brought into contact with a strong acid decontaminating solution, and voltage and current are applied to the portion and keep it for a long period of time so as to make the potential of the immersed portion of the metal wastes to an active soluble region. Then, the electrolytic reduction operation is stopped, and the metal wastes are entirely immersed in the decontaminating solution to decontaminate by chemical dissolution. As the decontaminating solution, strong acid such as sulfuric acid, nitric acid is used. Since DC current power source capacity required for causing reaction in the active soluble region can be decreased, the decontamination facility can be minimized and simplified, and necessary electric power can be saved even upon decontamination of radioactive metal wastes made of stainless steels and having a great area. Further, chemical dissolution can be conducted without adding an expensive oxidizing agent. (N.H.)

  11. Chemical analysis by nuclear methods. v. 2

    International Nuclear Information System (INIS)

    Alfassi, Z.B.

    1998-01-01

    'Chemical analysis by Nuclear Methods' is an effort of some renowned authors in field of nuclear chemistry and radiochemistry which is compiled by Alfassi, Z.B. and translated into Farsi version collected in two volumes. The second volume consists of the following chapters: Detecting ion recoil scattering and elastic scattering are dealt in the eleventh chapter, the twelfth chapter is devoted to nuclear reaction analysis using charged particles, X-ray emission is discussed at thirteenth chapter, the fourteenth chapter is about using ion microprobes, X-ray fluorescence analysis is discussed in the fifteenth chapter, alpha, beta and gamma ray scattering in chemical analysis are dealt in chapter sixteen, Moessbauer spectroscopy and positron annihilation are discussed in chapter seventeen and eighteen; The last two chapters are about isotope dilution analysis and radioimmunoassay

  12. Principles of quantum chemistry

    CERN Document Server

    George, David V

    2013-01-01

    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

  13. Method of chemical decontamination of stainless steel

    International Nuclear Information System (INIS)

    Onuma, Tsutomu; Akimoto, Hidetoshi.

    1989-01-01

    The present invention concerns a decontamination method of chemically decontaminating radioactive metal wastes of passivated stainless steels to a radioactivity level identical with usual wastes, in which the amount of oxidizable metal salts used is decreased. Metal wastes of stainless steels contaminated at their surface with radioactive materials are immersed in a sulfuric acid solution. In this case, a voltage is applied for a certain period of time so that the potential of the stainless steels comes to an active region. Then, oxidizable metal salt (tetravalent cerium) is added into the sulfuric acid solution. According to this method, since most of radioactive materials are removed in the immersing step to the sulfuric acid solution, the amount of the tetravalent cerium used is as less as 1/700 and the decontamination time is as short as 1/4 as compared with those in the conventional method. (K.M.)

  14. A multiscale quantum mechanics/electromagnetics method for device simulations.

    Science.gov (United States)

    Yam, ChiYung; Meng, Lingyi; Zhang, Yu; Chen, GuanHua

    2015-04-07

    Multiscale modeling has become a popular tool for research applying to different areas including materials science, microelectronics, biology, chemistry, etc. In this tutorial review, we describe a newly developed multiscale computational method, incorporating quantum mechanics into electronic device modeling with the electromagnetic environment included through classical electrodynamics. In the quantum mechanics/electromagnetics (QM/EM) method, the regions of the system where active electron scattering processes take place are treated quantum mechanically, while the surroundings are described by Maxwell's equations and a semiclassical drift-diffusion model. The QM model and the EM model are solved, respectively, in different regions of the system in a self-consistent manner. Potential distributions and current densities at the interface between QM and EM regions are employed as the boundary conditions for the quantum mechanical and electromagnetic simulations, respectively. The method is illustrated in the simulation of several realistic systems. In the case of junctionless field-effect transistors, transfer characteristics are obtained and a good agreement between experiments and simulations is achieved. Optical properties of a tandem photovoltaic cell are studied and the simulations demonstrate that multiple QM regions are coupled through the classical EM model. Finally, the study of a carbon nanotube-based molecular device shows the accuracy and efficiency of the QM/EM method.

  15. Advances in computational methods for Quantum Field Theory calculations

    NARCIS (Netherlands)

    Ruijl, B.J.G.

    2017-01-01

    In this work we describe three methods to improve the performance of Quantum Field Theory calculations. First, we simplify large expressions to speed up numerical integrations. Second, we design Forcer, a program for the reduction of four-loop massless propagator integrals. Third, we extend the R*

  16. Linear-scaling quantum mechanical methods for excited states.

    Science.gov (United States)

    Yam, ChiYung; Zhang, Qing; Wang, Fan; Chen, GuanHua

    2012-05-21

    The poor scaling of many existing quantum mechanical methods with respect to the system size hinders their applications to large systems. In this tutorial review, we focus on latest research on linear-scaling or O(N) quantum mechanical methods for excited states. Based on the locality of quantum mechanical systems, O(N) quantum mechanical methods for excited states are comprised of two categories, the time-domain and frequency-domain methods. The former solves the dynamics of the electronic systems in real time while the latter involves direct evaluation of electronic response in the frequency-domain. The localized density matrix (LDM) method is the first and most mature linear-scaling quantum mechanical method for excited states. It has been implemented in time- and frequency-domains. The O(N) time-domain methods also include the approach that solves the time-dependent Kohn-Sham (TDKS) equation using the non-orthogonal localized molecular orbitals (NOLMOs). Besides the frequency-domain LDM method, other O(N) frequency-domain methods have been proposed and implemented at the first-principles level. Except one-dimensional or quasi-one-dimensional systems, the O(N) frequency-domain methods are often not applicable to resonant responses because of the convergence problem. For linear response, the most efficient O(N) first-principles method is found to be the LDM method with Chebyshev expansion for time integration. For off-resonant response (including nonlinear properties) at a specific frequency, the frequency-domain methods with iterative solvers are quite efficient and thus practical. For nonlinear response, both on-resonance and off-resonance, the time-domain methods can be used, however, as the time-domain first-principles methods are quite expensive, time-domain O(N) semi-empirical methods are often the practical choice. Compared to the O(N) frequency-domain methods, the O(N) time-domain methods for excited states are much more mature and numerically stable, and

  17. Algebraic methods in statistical mechanics and quantum field theory

    CERN Document Server

    Emch, Dr Gérard G

    2009-01-01

    This systematic algebraic approach concerns problems involving a large number of degrees of freedom. It extends the traditional formalism of quantum mechanics, and it eliminates conceptual and mathematical difficulties common to the development of statistical mechanics and quantum field theory. Further, the approach is linked to research in applied and pure mathematics, offering a reflection of the interplay between formulation of physical motivations and self-contained descriptions of the mathematical methods.The four-part treatment begins with a survey of algebraic approaches to certain phys

  18. Central limit theorems for large graphs: Method of quantum decomposition

    International Nuclear Information System (INIS)

    Hashimoto, Yukihiro; Hora, Akihito; Obata, Nobuaki

    2003-01-01

    A new method is proposed for investigating spectral distribution of the combinatorial Laplacian (adjacency matrix) of a large regular graph on the basis of quantum decomposition and quantum central limit theorem. General results are proved for Cayley graphs of discrete groups and for distance-regular graphs. The Coxeter groups and the Johnson graphs are discussed in detail by way of illustration. In particular, the limit distributions obtained from the Johnson graphs are characterized by the Meixner polynomials which form a one-parameter deformation of the Laguerre polynomials

  19. Chemical deposition methods using supercritical fluid solutions

    Science.gov (United States)

    Sievers, Robert E.; Hansen, Brian N.

    1990-01-01

    A method for depositing a film of a desired material on a substrate comprises dissolving at least one reagent in a supercritical fluid comprising at least one solvent. Either the reagent is capable of reacting with or is a precursor of a compound capable of reacting with the solvent to form the desired product, or at least one additional reagent is included in the supercritical solution and is capable of reacting with or is a precursor of a compound capable of reacting with the first reagent or with a compound derived from the first reagent to form the desired material. The supercritical solution is expanded to produce a vapor or aerosol and a chemical reaction is induced in the vapor or aerosol so that a film of the desired material resulting from the chemical reaction is deposited on the substrate surface. In an alternate embodiment, the supercritical solution containing at least one reagent is expanded to produce a vapor or aerosol which is then mixed with a gas containing at least one additional reagent. A chemical reaction is induced in the resulting mixture so that a film of the desired material is deposited.

  20. Physico-chemical mechanism for the vapors sensitivity of photoluminescent InP quantum dots

    Science.gov (United States)

    Prosposito, P.; De Angelis, R.; De Matteis, F.; Hatami, F.; Masselink, W. T.; Zhang, H.; Casalboni, M.

    2016-03-01

    InP/InGaP surface quantum dots are interesting materials for optical chemical sensors since they present an intense emission at room temperature, whose intensity changes rapidly and reversibly depending on the composition of the environmental atmosphere. We present here their emission properties by time resolved photoluminescence spectroscopy investigation and we discuss the physico-chemical mechanism behind their sensitivity to the surrounding atmosphere. Photoluminescence transients in inert atmosphere (N2) and in solvent vapours of methanol, clorophorm, acetone and water were measured. The presence of vapors of clorophorm, acetone and water showed a very weak effect on the transient times, while an increase of up to 15% of the decay time was observed for methanol vapour exposure. On the basis of the vapor molecule nature (polarity, proticity, steric hindrance, etc.) and of the interaction of the vapor molecules with the quantum dots surface a sensing mechanism involving quantum dots non-radiative surface states is proposed.

  1. Physico-chemical mechanism for the vapors sensitivity of photoluminescent InP quantum dots

    International Nuclear Information System (INIS)

    Prosposito, P.; De Angelis, R.; De Matteis, F.; Casalboni, M.; Hatami, F.; Masselink, W.T.; Zhang, H.

    2016-01-01

    InP/InGaP surface quantum dots are interesting materials for optical chemical sensors since they present an intense emission at room temperature, whose intensity changes rapidly and reversibly depending on the composition of the environmental atmosphere. We present here their emission properties by time resolved photoluminescence spectroscopy investigation and we discuss the physico-chemical mechanism behind their sensitivity to the surrounding atmosphere. Photoluminescence transients in inert atmosphere (N 2 ) and in solvent vapours of methanol, chloroform, acetone and water were measured. The presence of vapors of chloroform, acetone and water showed a very weak effect on the transient times, while an increase of up to 15% of the decay time was observed for methanol vapour exposure. On the basis of the vapor molecule nature (polarity, proticity, steric hindrance, etc.) and of the interaction of the vapor molecules with the quantum dots surface a sensing mechanism involving quantum dots non-radiative surface states is proposed. (paper)

  2. Predicting allergic contact dermatitis: a hierarchical structure activity relationship (SAR) approach to chemical classification using topological and quantum chemical descriptors

    Science.gov (United States)

    Basak, Subhash C.; Mills, Denise; Hawkins, Douglas M.

    2008-06-01

    A hierarchical classification study was carried out based on a set of 70 chemicals—35 which produce allergic contact dermatitis (ACD) and 35 which do not. This approach was implemented using a regular ridge regression computer code, followed by conversion of regression output to binary data values. The hierarchical descriptor classes used in the modeling include topostructural (TS), topochemical (TC), and quantum chemical (QC), all of which are based solely on chemical structure. The concordance, sensitivity, and specificity are reported. The model based on the TC descriptors was found to be the best, while the TS model was extremely poor.

  3. The use of quantum chemically derived descriptors for QSAR modelling of reductive dehalogenation of aromatic compounds

    NARCIS (Netherlands)

    Rorije E; Richter J; Peijnenburg WJGM; ECO; IHE Delft

    1994-01-01

    In this study, quantum-chemically derived parameters are developed for a limited number of halogenated aromatic compounds to model the anaerobic reductive dehalogenation reaction rate constants of these compounds. It is shown that due to the heterogeneity of the set of compounds used, no single

  4. 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

    2016-01-01

    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

  5. Superalgebras, their quantum deformations and the induced representation method

    International Nuclear Information System (INIS)

    Nguyen Anh Ky.

    1996-08-01

    In this paper some introductory concepts and basic definitions of the Lie superalgebras and their quantum deformations are exposed. Especially the induced representation methods in both cases are described. Up to now, based on the Kac representation theory we have succeeded in constructing representations of several higher rank superalgebras. When representations of quantum superalgebras are concerned, we develop a method which can be applied not only to the one-parametric quantum deformations but also to the multi-parametric ones. Here, being illustrations of the above-mentioned methods, the superalgebra gl(2/1) and its (one-parametric) quantum deformation U q [gl(2/1)] are considered as their finite-dimensional representations are investigated in detail and constructed explicitly. Also, it is shown that the finite-dimensional representations obtained constitute classes of all irreducible (typical and non-typical) finite-dimensional representations of gl(2/1) and U q [gl(2/1)]. Some of the detailed results may be simple but they are given for the first time. (author). 64 refs

  6. Molecular structure, vibrational analysis (IR and Raman) and quantum chemical investigations of 1-aminoisoquinoline

    Science.gov (United States)

    Sivaprakash, S.; Prakash, S.; Mohan, S.; Jose, Sujin P.

    2017-12-01

    Quantum chemical calculations of energy and geometrical parameters of 1-aminoisoquinoline [1-AIQ] were carried out by using DFT/B3LYP method using 6-311G (d,p), 6-311G++(d,p) and cc-pVTZ basis sets. The vibrational wavenumbers were computed for the energetically most stable, optimized geometry. The vibrational assignments were performed on the basis of potential energy distribution (PED) using VEDA program. The NBO analysis was done to investigate the intra molecular charge transfer of the molecule. The frontier molecular orbital (FMO) analysis was carried out and the chemical reactivity descriptors of the molecule were studied. The Mulliken charge analysis, molecular electrostatic potential (MEP), HOMO-LUMO energy gap and the related properties were also investigated at B3LYP level. The absorption spectrum of the molecule was studied from UV-Visible analysis by using time-dependent density functional theory (TD-DFT). Fourier Transform Infrared spectrum (FT-IR) and Raman spectrum of 1-AIQ compound were analyzed and recorded in the range 4000-400 cm-1 and 3500-100 cm-1 respectively. The experimentally determined wavenumbers were compared with those calculated theoretically and they complement each other.

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

    Science.gov (United States)

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

    2015-04-05

    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.

  8. DFT simulation, quantum chemical electronic structure, spectroscopic and structure-activity investigations of 2-benzothiazole acetonitrile.

    Science.gov (United States)

    Arjunan, V; Thillai Govindaraja, S; Jose, Sujin P; Mohan, S

    2014-07-15

    The Fourier transform infrared and FT-Raman spectra of 2-benzothiazole acetonitrile (BTAN) have been recorded in the range 4000-450 and 4000-100 cm(-1) respectively. The conformational analysis of the compound has been carried out to obtain the stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers derived theoretically by B3LYP gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The (1)H (400 MHz; CDCl3) and (13)C (100 MHz;CDCl3) nuclear magnetic resonance (NMR) spectra are also recorded. The electronic properties, the energies of the highest occupied and lowest unoccupied molecular orbitals are measured by DFT approach. The kinetic stability of the molecule has been determined from the frontier molecular orbital energy gap. The charges of the atoms and the structure-chemical reactivity relations of the compound are determined by its chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods. The non-linear optical properties of the compound have been discussed by measuring the polarisability and hyperpolarisability tensors. Copyright © 2014 Elsevier B.V. All rights reserved.

  9. Method for the deconvolution of incompletely resolved CARS spectra in chemical dynamics experiments

    International Nuclear Information System (INIS)

    Anda, A.A.; Phillips, D.L.; Valentini, J.J.

    1986-01-01

    We describe a method for deconvoluting incompletely resolved CARS spectra to obtain quantum state population distributions. No particular form for the rotational and vibrational state distribution is assumed, the population of each quantum state is treated as an independent quantity. This method of analysis differs from previously developed approaches for the deconvolution of CARS spectra, all of which assume that the population distribution is Boltzmann, and thus are limited to the analysis of CARS spectra taken under conditions of thermal equilibrium. The method of analysis reported here has been developed to deconvolute CARS spectra of photofragments and chemical reaction products obtained in chemical dynamics experiments under nonequilibrium conditions. The deconvolution procedure has been incorporated into a computer code. The application of that code to the deconvolution of CARS spectra obtained for samples at thermal equilibrium and not at thermal equilibrium is reported. The method is accurate and computationally efficient

  10. Chemical decontamination method for radioactive metal waste

    International Nuclear Information System (INIS)

    Tanaka, Akio; Onuma, Tsutomu; Yamazaki, Sei; Miura, Haruki.

    1993-01-01

    The present invention provides a chemical decontamination method for radioactive metal wastes, which are generated from radioactive material handling facilities and the surfaces of which are contaminated by radioactive materials. That is, it has a feature of applying acid dissolution simultaneously with mechanical grinding. The radioactive metal wastes are contained in a vessel such as a barrel together with abrasives in a sulfuric acid solution and rotated at several tens rotation per minute. By such procedures for the radioactive metal wastes, (1) cruds and passive membranes are mechanically removed, (2) exposed mother metal materials are uniformly brought into contact with sulfuric acid and further (3) the mother metal materials dissolve the cruds and the passive membranes also chemically by a reducing dissolution (so-called local cell effect). According to the method of the present invention, stainless steel metal wastes having cruds and passive membranes can rapidly and efficiently be decontaminated to a radiation level equal with that of ordinary wastes. (I.S.)

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

    International Nuclear Information System (INIS)

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

    2008-01-01

    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

  12. Introduction to quantum calculation methods in high resolution NMR

    International Nuclear Information System (INIS)

    Goldman, M.

    1996-01-01

    New techniques as for instance the polarization transfer, the coherence with several quanta and the double Fourier transformation have appeared fifteen years ago. These techniques constitute a considerable advance in NMR. Indeed, they allow to study more complex molecules than it was before possible. But with these advances, the classical description of the NMR is not enough to understand precisely the physical phenomena induced by these methods. It is then necessary to resort to quantum calculation methods. The aim of this work is to present these calculation methods. After some recalls of quantum mechanics, the author describes the NMR with the density matrix, reviews the main methods of double Fourier transformation and then gives the principle of the relaxation times calculation. (O.M.)

  13. Geometric methods in multiparticle quantum systems

    International Nuclear Information System (INIS)

    Simon, B.

    1977-01-01

    Technically simple proofs are given of the HVZ theorem on the bottom of the essential spectrum of multiparticle systems and of Combes' result on completeness below the lowest three body threshold. The first proof is a variant of a proof of Enss and a decendent of Zhislin's original proof. Finally, we apply our methods to the bound state spectrum. (orig.) [de

  14. Scattering theory in quantum mechanics. Physical principles and mathematical methods

    International Nuclear Information System (INIS)

    Amrein, W.O.; Jauch, J.M.; Sinha, K.B.

    1977-01-01

    A contemporary approach is given to the classical topics of physics. The purpose is to explain the basic physical concepts of quantum scattering theory, to develop the necessary mathematical tools for their description, to display the interrelation between the three methods (the Schroedinger equation solutions, stationary scattering theory, and time dependence) to derive the properties of various quantities of physical interest with mathematically rigorous methods

  15. New numerical methods for quantum field theories on the continuum

    Energy Technology Data Exchange (ETDEWEB)

    Emirdag, P.; Easter, R.; Guralnik, G.S.; Hahn, S.C

    2000-03-01

    The Source Galerkin Method is a new numerical technique that is being developed to solve Quantum Field Theories on the continuum. It is not based on Monte Carlo techniques and has a measure to evaluate relative errors. It promises to increase the accuracy and speed of calculations, and takes full advantage of symmetries of the theory. The application of this method to the non-linear {sigma} model is outlined.

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

    Indian Academy of Sciences (India)

    the metal surface and form barrier film. .... with time may be attributed to the formation of a barrier film, which prevents the ..... high chemical activity and low kinetic stability and is termed ... Physical adsorption of the organic inhibitor on the metal.

  17. Isolation, characterization, spectroscopic properties and quantum chemical computations of an important phytoalexin resveratrol as antioxidant component from Vitis labrusca L. and their chemical compositions

    Science.gov (United States)

    Güder, Aytaç; Korkmaz, Halil; Gökce, Halil; Alpaslan, Yelda Bingöl; Alpaslan, Gökhan

    2014-12-01

    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.

  18. Quantum mechanical model for the anticarcinogenic effect of extremely-low-frequency electromagnetic fields on early chemical hepatocarcinogenesis

    Science.gov (United States)

    Godina-Nava, Juan José; Torres-Vega, Gabino; López-Riquelme, Germán Octavio; López-Sandoval, Eduardo; Samana, Arturo Rodolfo; García Velasco, Fermín; Hernández-Aguilar, Claudia; Domínguez-Pacheco, Arturo

    2017-02-01

    Using the conventional Haberkorn approach, it is evaluated the recombination of the radical pair (RP) singlet spin state to study theoretically the cytoprotective effect of an extremely-low-frequency electromagnetic field (ELF-EMF) on early stages of hepatic cancer chemically induced in rats. The proposal is that ELF-EMF modulates the interconversion rate of singlet and triplet spin states of the RP populations modifying the products from the metabolization of carcinogens. Previously, we found that the daily treatment with ELF-EMF 120 Hz inhibited the number and area of preneoplastic lesions in chemical carcinogenesis. The singlet spin population is evaluated diagonalizing the spin density matrix through the Lanczos method in a radical pair mechanism (RPM). Using four values of the interchange energy, we have studied the variations over the singlet population. The low magnetic field effect as a test of the influence over the enzymatic chemical reaction is evaluated calculating the quantum yield. Through a bootstrap technique the range is found for the singlet decay rate for the process. Applying the quantum measurements concept, we addressed the impact toward hepatic cells. The result contributes to improving our understanding of the chemical carcinogenesis process affected by charged particles that damage the DNA.

  19. Chemical Compounds and Extraction Methods of "Maollahm".

    Science.gov (United States)

    Sadeghpoor, Omid; Dayeni, Manijeh; Razi, Samane

    2016-05-01

    Maollahm or meat juice, a by-product of meat, is a traditional remedy in Persian medicine. This product was used as a nourishment or treatment substance for sick people. According to the ancient Persian medicine, animal meat has more affinity with the human body and the body easily absorbs its nutrition. Therefore, one could resort to maollahm for patients requiring urgent nourishment to boost and strengthen their body. In this work, different ways of preparing maollahm from poultry, goat, cow, and sheep meat are studied. Most of these methods are based on distillation or barbecue before distillation, as prescribed by traditional medicine books. The reactions, chemical processes, and volatile compounds related to different types of cooked meat are also compared with the outcome of recent research studies. The difference between various types of meat is related to their compounds. Different cooking processes such as barbecuing, roasting, cooking, and boiling have an effect on the taste, smell and the chemical constituents of maollahm. Additionally, the type of meat, animal feed, as well as using or removing the fat during the cooking process, have an effect on the produced volatile compounds. Cooking process and the type of meat have a direct effect on the compounds of maollahm. Possible reactions in the preparation process of maollahm are investigated and presented according to the new research studies.

  20. A novel quantum LSB-based steganography method using the Gray code for colored quantum images

    Science.gov (United States)

    Heidari, Shahrokh; Farzadnia, Ehsan

    2017-10-01

    As one of the prevalent data-hiding techniques, steganography is defined as the act of concealing secret information in a cover multimedia encompassing text, image, video and audio, imperceptibly, in order to perform interaction between the sender and the receiver in which nobody except the receiver can figure out the secret data. In this approach a quantum LSB-based steganography method utilizing the Gray code for quantum RGB images is investigated. This method uses the Gray code to accommodate two secret qubits in 3 LSBs of each pixel simultaneously according to reference tables. Experimental consequences which are analyzed in MATLAB environment, exhibit that the present schema shows good performance and also it is more secure and applicable than the previous one currently found in the literature.

  1. Quantum chemistry

    CERN Document Server

    Lowe, John P

    1993-01-01

    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,

  2. Fast New Method for Temporary Chemical Passivation

    Directory of Open Access Journals (Sweden)

    Marek Solčanský

    2012-12-01

    Full Text Available The main material parameter of silicon, that influences the effectiveness of photovoltaic cells, is the minority carrier bulk lifetime.It may change in the technological process especially during high temperature operations. Monitoring of the carrier bulk-lifetimeis necessary for modifying the whole technological process of production. For the measurement of the minority carrier bulk-lifetimethe characterization method MW PCD (Microwave Photoconductance Decay is used, where the result of measurement is the effectivecarrier lifetime, which is very dependent on the surface recombination velocity and therefore on the quality of a silicon surfacepassivation.This work deals with an examination of a different solution types for the chemical passivation of a silicon surface. Varioussolutions are tested on silicon wafers for their consequent comparison. The main purpose of this work is to find optimal solution, whichsuits the requirements of a time stability and start-up velocity of passivation, reproducibility of the measurements and a possibilityof a perfect cleaning of a passivating solution remains from a silicon surface. Another purpose of this work is to identify the parametersof other quinhydrone solutions with different concentrations as compared with the quinhydrone solution in methanol witha concentration of 0.07 mol/dm³ marked QM007 (referential solution.The method of an effective chemical passivation with a quinhydrone in methanol solution was suggested. The solution witha concentration of 0.07 mol /dm3 fulfills all required criteria. The work also confirms the influence of increased concentrationquinhydrone on the temporal stability of the passivation layer and the effect for textured silicon wafers. In conclusion, the influenceof an illumination and the temperature on the properties of the passivating solution QM007 is discussed.

  3. Chemical Methods for Peptide and Protein Production

    Directory of Open Access Journals (Sweden)

    Istvan Toth

    2013-04-01

    Full Text Available Since the invention of solid phase synthetic methods by Merrifield in 1963, the number of research groups focusing on peptide synthesis has grown exponentially. However, the original step-by-step synthesis had limitations: the purity of the final product decreased with the number of coupling steps. After the development of Boc and Fmoc protecting groups, novel amino acid protecting groups and new techniques were introduced to provide high quality and quantity peptide products. Fragment condensation was a popular method for peptide production in the 1980s, but unfortunately the rate of racemization and reaction difficulties proved less than ideal. Kent and co-workers revolutionized peptide coupling by introducing the chemoselective reaction of unprotected peptides, called native chemical ligation. Subsequently, research has focused on the development of novel ligating techniques including the famous click reaction, ligation of peptide hydrazides, and the recently reported a-ketoacid-hydroxylamine ligations with 5-oxaproline. Several companies have been formed all over the world to prepare high quality Good Manufacturing Practice peptide products on a multi-kilogram scale. This review describes the advances in peptide chemistry including the variety of synthetic peptide methods currently available and the broad application of peptides in medicinal chemistry.

  4. Chemical methods for peptide and protein production.

    Science.gov (United States)

    Chandrudu, Saranya; Simerska, Pavla; Toth, Istvan

    2013-04-12

    Since the invention of solid phase synthetic methods by Merrifield in 1963, the number of research groups focusing on peptide synthesis has grown exponentially. However, the original step-by-step synthesis had limitations: the purity of the final product decreased with the number of coupling steps. After the development of Boc and Fmoc protecting groups, novel amino acid protecting groups and new techniques were introduced to provide high quality and quantity peptide products. Fragment condensation was a popular method for peptide production in the 1980s, but unfortunately the rate of racemization and reaction difficulties proved less than ideal. Kent and co-workers revolutionized peptide coupling by introducing the chemoselective reaction of unprotected peptides, called native chemical ligation. Subsequently, research has focused on the development of novel ligating techniques including the famous click reaction, ligation of peptide hydrazides, and the recently reported α-ketoacid-hydroxylamine ligations with 5-oxaproline. Several companies have been formed all over the world to prepare high quality Good Manufacturing Practice peptide products on a multi-kilogram scale. This review describes the advances in peptide chemistry including the variety of synthetic peptide methods currently available and the broad application of peptides in medicinal chemistry.

  5. Chemical decontamination method for radioactive metal waste

    International Nuclear Information System (INIS)

    Onuma, Tsutomu; Akimoto, Hidetoshi

    1991-01-01

    The invention relates to a decontamination method for radioactive metal waste products derived from equipment that handles radioactive materials whose surfaces have been contaminated; in particular it concerns a decontamination method that reduces the amount of radioactive waste by decontaminating radioactive waste substances to a level of radioactivity in line with normal waste products. In order to apply chemical decontamination to metal waste products whose surfaces are divided into carbon steel waste and stainless steel waste; the carbon steel waste is treated using only a primary process in which the waste is immersed in a sulfuric acid solution, while the stainless steel waste must be treated with both the primary process and then electrolytically reduces it for a specific length of time and a secondary process that uses a solution of sulfuric acid mixed with oxidizing metal salts. The method used to categorize metal waste into carbon steel waste and stainless steel waste involves determining the presence, or absence, of magnetism. Voltage is applied for a fixed duration; once that has stopped, electrolytic reduction repeats the operative cycle of applying, then stopping voltage until the potential of the radioactive metal waste is retained in the active region. 1 fig. 2 tabs

  6. Split kinetic energy method for quantum systems with competing potentials

    International Nuclear Information System (INIS)

    Mineo, H.; Chao, Sheng D.

    2012-01-01

    For quantum systems with competing potentials, the conventional perturbation theory often yields an asymptotic series and the subsequent numerical outcome becomes uncertain. To tackle such a kind of problems, we develop a general solution scheme based on a new energy dissection idea. Instead of dividing the potential energy into “unperturbed” and “perturbed” terms, a partition of the kinetic energy is performed. By distributing the kinetic energy term in part into each individual potential, the Hamiltonian can be expressed as the sum of the subsystem Hamiltonians with respective competing potentials. The total wavefunction is expanded by using a linear combination of the basis sets of respective subsystem Hamiltonians. We first illustrate the solution procedure using a simple system consisting of a particle under the action of double δ-function potentials. Next, this method is applied to the prototype systems of a charged harmonic oscillator in strong magnetic field and the hydrogen molecule ion. Compared with the usual perturbation approach, this new scheme converges much faster to the exact solutions for both eigenvalues and eigenfunctions. When properly extended, this new solution scheme can be very useful for dealing with strongly coupling quantum systems. - Highlights: ► A new basis set expansion method is proposed. ► Split kinetic energy method is proposed to solve quantum eigenvalue problems. ► Significant improvement has been obtained in converging to exact results. ► Extension of such methods is promising and discussed.

  7. Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy.

    Science.gov (United States)

    Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T; Musgrave, Charles B

    2018-01-25

    We propose a method to approximate the kinetic properties of hydride donor species by relating the nucleophilicity (N) of a hydride to the activation free energy ΔG ⧧ of its corresponding hydride transfer reaction. N is a kinetic parameter related to the hydride transfer rate constant that quantifies a nucleophilic hydridic species' tendency to donate. Our method estimates N using quantum chemical calculations to compute ΔG ⧧ for hydride transfers from hydride donors to CO 2 in solution. A linear correlation for each class of hydrides is then established between experimentally determined N values and the computationally predicted ΔG ⧧ ; this relationship can then be used to predict nucleophilicity for different hydride donors within each class. This approach is employed to determine N for four different classes of hydride donors: two organic (carbon-based and benzimidazole-based) and two inorganic (boron and silicon) hydride classes. We argue that silicon and boron hydrides are driven by the formation of the more stable Si-O or B-O bond. In contrast, the carbon-based hydrides considered herein are driven by the stability acquired upon rearomatization, a feature making these species of particular interest, because they both exhibit catalytic behavior and can be recycled.

  8. Synthesis, structural characterization and quantum chemical studies of silicon-containing benzoic acid derivatives

    Science.gov (United States)

    Zaltariov, Mirela-Fernanda; Cojocaru, Corneliu; Shova, Sergiu; Sacarescu, Liviu; Cazacu, Maria

    2016-09-01

    The present paper is concerned with the synthesis and molecular structure investigation of two new benzoic acid derivatives having trimethylsilyl tails, 4-((trimethylsilyl)methoxy) and 4-(3-(trimethylsilyl)propoxy)benzoic acids. The structures of the novel compounds have been confirmed by X-ray crystallography, Fourier-transform infrared spectroscopy (FTIR) and nuclear magnetic resonance (1H and 13C NMR). The theoretical studies of molecules were conducted by using the quantum chemical methods, such as Density Functional Theory (DFT B3LYP/6-31 + G**), Hartree-Fock (HF/6-31 + G**) and semiempirical computations (PM3, PM6 and PM7). The optimized molecular geometries have been found to be in good agreement with experimental structures resulted from the X-ray diffraction. The maximum electronic absorption bands observed at 272-287 nm (UV-vis spectra) have been assigned to π → π* transitions, which were in reasonable agreement with the time dependent density functional theory (TD-DFT) calculations. The computed vibrational frequencies by DFT method were assigned and compared with the experimental FTIR spectra. The mapped electrostatic potentials revealed the reactive sites, which corroborated the observation of the dimer supramolecular structures formed in the crystals by hydrogen-bonding. The energies of frontier molecular orbitals (HOMO and LUMO), energy gap, dipole moment and molecular descriptors for the new compounds were calculated and discussed.

  9. Detailed solvent, structural, quantum chemical study and antimicrobial activity of isatin Schiff base

    Science.gov (United States)

    Brkić, Dominik R.; Božić, Aleksandra R.; Marinković, Aleksandar D.; Milčić, Miloš K.; Prlainović, Nevena Ž.; Assaleh, Fathi H.; Cvijetić, Ilija N.; Nikolić, Jasmina B.; Drmanić, Saša Ž.

    2018-05-01

    The ratios of E/Z isomers of sixteen synthesized 1,3-dihydro-3-(substituted phenylimino)-2H-indol-2-one were studied using experimental and theoretical methodology. Linear solvation energy relationships (LSER) rationalized solvent influence of the solvent-solute interactions on the UV-Vis absorption maxima shifts (νmax) of both geometrical isomers using the Kamlet-Taft equation. Linear free energy relationships (LFER) in the form of single substituent parameter equation (SSP) was used to analyze substituent effect on pKa, NMR chemical shifts and νmax values. Electron charge density was obtained by the use of Quantum Theory of Atoms in Molecules, i.e. Bader's analysis. The substituent and solvent effect on intramolecular charge transfer (ICT) were interpreted with the aid of time-dependent density functional (TD-DFT) method. Additionally, the results of TD-DFT calculations quantified the efficiency of ICT from the calculated charge-transfer distance (DCT) and amount of transferred charge (QCT). The antimicrobial activity was evaluated using broth microdilution method. 3D QSAR modeling was used to demonstrate the influence of substituents effect as well as molecule geometry on antimicrobial activity.

  10. Facile synthetic method for pristine graphene quantum dots and graphene oxide quantum dots: origin of blue and green luminescence.

    Science.gov (United States)

    Liu, Fei; Jang, Min-Ho; Ha, Hyun Dong; Kim, Je-Hyung; Cho, Yong-Hoon; Seo, Tae Seok

    2013-07-19

    Pristine graphene quantum dots and graphene oxide quantum dots are synthesized by chemical exfoliation from the graphite nanoparticles with high uniformity in terms of shape (circle), size (less than 4 nm), and thickness (monolayer). The origin of the blue and green photoluminescence of GQDs and GOQDs is attributed to intrinsic and extrinsic energy states, respectively. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  11. 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

    2005-01-01

    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

  12. Quantum method of the inverse scattering problem. Pt. 1

    International Nuclear Information System (INIS)

    Sklyamin, E.K.; Takhtadzhyan, L.A.; Faddeev, L.D.

    1978-12-01

    In this work the authors use a formulation for the method of the inverse scattering problem for quantum-mechanical models of the field theory, that can be found in a quantization of these fully integrable systems. As the most important example serves the system (sinγ) 2 with the movement equation: γtt -γxx + m 2 /β sinβγ = 0 that is known under the specification Sine-Gordon-equation. (orig.) [de

  13. CRITIC2: A program for real-space analysis of quantum chemical interactions in solids

    Science.gov (United States)

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

    2014-03-01

    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:http://cpc.cs.qub.ac.uk/summaries/AECB_v2_0.html 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

  14. An orientation analysis method for protein immobilized on quantum dot particles

    Energy Technology Data Exchange (ETDEWEB)

    Aoyagi, Satoka, E-mail: aoyagi@life.shimane-u.ac.jp [Faculty of Life and Environmental Science, Shimane University, 1060 Matsue-shi, Shimane 690-8504 (Japan); Inoue, Masae [Toyota Central R and D Labs., Inc., Nagakute, Aichi 480-1192 (Japan)

    2009-11-30

    The evaluation of orientation of biomolecules immobilized on nanodevices is crucial for the development of high performance devices. Such analysis requires ultra high sensitivity so as to be able to detect less than one molecular layer on a device. Time-of-flight secondary ion mass spectrometry (TOF-SIMS) has sufficient sensitivity to evaluate the uppermost surface structure of a single molecular layer. The objective of this study is to develop an orientation analysis method for proteins immobilized on nanomaterials such as quantum dot particles, and to evaluate the orientation of streptavidin immobilized on quantum dot particles by means of TOF-SIMS. In order to detect fragment ions specific to the protein surface, a monoatomic primary ion source (Ga{sup +}) and a cluster ion source (Au{sub 3}{sup +}) were employed. Streptavidin-immobilized quantum dot particles were immobilized on aminosilanized ITO glass plates at amino groups by covalent bonding. The reference samples streptavidin directly immobilized on ITO plates were also prepared. All samples were dried with a freeze dryer before TOF-SIMS measurement. The positive secondary ion spectra of each sample were obtained using TOF-SIMS with Ga{sup +} and Au{sub 3}{sup +}, respectively, and then they were compared so as to characterize each sample and detect the surface structure of the streptavidin immobilized with the biotin-immobilized quantum dots. The chemical structures of the upper surface of the streptavidin molecules immobilized on the quantum dot particles were evaluated with TOF-SIMS spectra analysis. The indicated surface side of the streptavidin molecules immobilized on the quantum dots includes the biotin binding site.

  15. 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.

    2012-01-01

    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.

  16. Method for preparation and readout of polyatomic molecules in single quantum states

    Science.gov (United States)

    Patterson, David

    2018-03-01

    Polyatomic molecular ions contain many desirable attributes of a useful quantum system, including rich internal degrees of freedom and highly controllable coupling to the environment. To date, the vast majority of state-specific experimental work on molecular ions has concentrated on diatomic species. The ability to prepare and read out polyatomic molecules in single quantum states would enable diverse experimental avenues not available with diatomics, including new applications in precision measurement, sensitive chemical and chiral analysis at the single-molecule level, and precise studies of Hz-level molecular tunneling dynamics. While cooling the motional state of a polyatomic ion via sympathetic cooling with a laser-cooled atomic ion is straightforward, coupling this motional state to the internal state of the molecule has proven challenging. Here we propose a method for readout and projective measurement of the internal state of a trapped polyatomic ion. The method exploits the rich manifold of technically accessible rotational states in the molecule to realize robust state preparation and readout with far less stringent engineering than quantum logic methods recently demonstrated on diatomic molecules. The method can be applied to any reasonably small (≲10 atoms) polyatomic ion with an anisotropic polarizability.

  17. Quantum chemical modeling of antioxidant activity of glutathione interacting with hydroxyl- and superoxide anion radicals

    Directory of Open Access Journals (Sweden)

    N. V. Solovyova

    2015-04-01

    Full Text Available Following the analysis of the results of quantum chemical simulation of interaction between a GSH molecule and oxygen radicals •ОН and •ООˉ, it was found that it takes place through the acid-base mechanism, where GSH acts as a base towards •ОН, and as an acid towards •ООˉ. The results of quantum chemical calculations (electron density redistribution, energy characteristics were correlated at the time of interaction of a GSH molecule with •ОН and •ООˉ with a change of macroscopic parameters of the process of free oxygen radical electroreduction in the presence of GSH (potential and maximum current of reduction waves, which is a direct experimental macroscale evidence of results of the conducted nanoscale theoretical simulation.

  18. Learning and retention of quantum concepts with different teaching methods

    Science.gov (United States)

    Deslauriers, Louis; Wieman, Carl

    2011-06-01

    We measured mastery and retention of conceptual understanding of quantum mechanics in a modern physics course. This was studied for two equivalent cohorts of students taught with different pedagogical approaches using the Quantum Mechanics Conceptual Survey. We measured the impact of pedagogical approach both on the original conceptual learning and on long-term retention. The cohort of students who had a very highly rated traditional lecturer scored 19% lower than the equivalent cohort that was taught using interactive engagement methods. However, the amount of retention was very high for both cohorts, showing only a few percent decrease in scores when retested 6 and 18 months after completion of the course and with no exposure to the material in the interim period. This high level of retention is in striking contrast to the retention measured for more factual learning from university courses and argues for the value of emphasizing conceptual learning.

  19. Chemical potentials and thermodynamic characteristics of ideal Bose- and Fermi-gases in the region of quantum degeneracy

    Science.gov (United States)

    Sotnikov, A. G.; Sereda, K. V.; Slyusarenko, Yu. V.

    2017-01-01

    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.

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

    Czech Academy of Sciences Publication Activity Database

    Šponer, Jiří; Hobza, Pavel

    2003-01-01

    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

  1. Quantum chemical modeling of enzymatic reactions: the case of histone lysine methyltransferase.

    Science.gov (United States)

    Georgieva, Polina; Himo, Fahmi

    2010-06-01

    Quantum chemical cluster models of enzyme active sites are today an important and powerful tool in the study of various aspects of enzymatic reactivity. This methodology has been applied to a wide spectrum of reactions and many important mechanistic problems have been solved. Herein, we report a systematic study of the reaction mechanism of the histone lysine methyltransferase (HKMT) SET7/9 enzyme, which catalyzes the methylation of the N-terminal histone tail of the chromatin structure. In this study, HKMT SET7/9 serves as a representative case to examine the modeling approach for the important class of methyl transfer enzymes. Active site models of different sizes are used to evaluate the methodology. In particular, the dependence of the calculated energies on the model size, the influence of the dielectric medium, and the particular choice of the dielectric constant are discussed. In addition, we examine the validity of some technical aspects, such as geometry optimization in solvent or with a large basis set, and the use of different density functional methods. Copyright 2010 Wiley Periodicals, Inc.

  2. Interactions of ionic liquids and acetone: thermodynamic properties, quantum-chemical calculations, and NMR analysis.

    Science.gov (United States)

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

    2013-06-20

    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.

  3. From pirazoloquinolines to annulated azulene dyes: UV-VIS spectroscopy and quantum chemical study

    International Nuclear Information System (INIS)

    Gasiorski, P.; Danel, K.S.; Matusiewicz, M.; Uchacz, T.; Kityk, A.V.

    2010-01-01

    Paper reports UV-Vis absorption and photoluminescence spectra of 6-R derivatives (R=CH 3 , O-CH 3 , C(C 6 H 5 ) 3 , C 6 H 5 -N-C 10 H 7 ) of 4-(2-chlorophenyl)-1,3-diphenyl-1H-pyrazolo[3,4-b]quinoline, belonging to pyrazoloquinoline (PQ) family, likewise its regioisomeric products 10-R derivatives of 6-phenyl-6H-5,6,7-triazadibenzo[f,h]naphtho[3,2,1-cd]azulene representing cyclized seven-membered annulated azulene (AA) dyes. Cyclization of PQs into AAs is accompanied by a significant red shift of the first optical absorption band. This finding agrees with the results of quantum-chemical calculations performed by means of the semiempirical method PM3. As the solvent polarity rises all the dyes exhibit a blue shift of the first absorption band and a red shift of the fluorescence band. Such opposite trends in solvatochromic behavior have been reproduced within the semiempirical calculations in combination with the Lippert-Mataga dielectric polarization model. Depending on solvent polarity AA dyes emit light in the green, green-yellow or orange range of the visible spectrum what may be of interest for potential luminescent or electroluminescent applications.

  4. ExcelAutomat: a tool for systematic processing of files as applied to quantum chemical calculations

    Science.gov (United States)

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

    2017-07-01

    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.

  5. Dissipative dynamics with the corrected propagator method. Numerical comparison between fully quantum and mixed quantum/classical simulations

    International Nuclear Information System (INIS)

    Gelman, David; Schwartz, Steven D.

    2010-01-01

    The recently developed quantum-classical method has been applied to the study of dissipative dynamics in multidimensional systems. The method is designed to treat many-body systems consisting of a low dimensional quantum part coupled to a classical bath. Assuming the approximate zeroth order evolution rule, the corrections to the quantum propagator are defined in terms of the total Hamiltonian and the zeroth order propagator. Then the corrections are taken to the classical limit by introducing the frozen Gaussian approximation for the bath degrees of freedom. The evolution of the primary part is governed by the corrected propagator yielding the exact quantum dynamics. The method has been tested on two model systems coupled to a harmonic bath: (i) an anharmonic (Morse) oscillator and (ii) a double-well potential. The simulations have been performed at zero temperature. The results have been compared to the exact quantum simulations using the surrogate Hamiltonian approach.

  6. Quantum Chemical Calculations and Experimental Investigations of Molecular Actinide Oxides

    NARCIS (Netherlands)

    Kovács, Attila; Konings, Rudy J. M.; Gibson, John K.; Infante, Ivan; Gagliardi, Laura

    2015-01-01

    The available experimental and theoretical information on gaseous actinide oxides covering both the neutral and the ionic species are reviewed. The ground-state electronic structures of the oxides of An = Th-Cm have been obtained by the well-tested SOCASPT2 method, and therefore they are very likely

  7. Investigating hydrogel dosimeter decomposition by chemical methods

    International Nuclear Information System (INIS)

    Jordan, Kevin

    2015-01-01

    The chemical oxidative decomposition of leucocrystal violet micelle hydrogel dosimeters was investigated using the reaction of ferrous ions with hydrogen peroxide or sodium bicarbonate with hydrogen peroxide. The second reaction is more effective at dye decomposition in gelatin hydrogels. Additional chemical analysis is required to determine the decomposition products

  8. Quantum chemical and spectroscopic analysis of calcium hydroxyapatite and related materials

    International Nuclear Information System (INIS)

    Khavryuchenko, V.D.; Khavryuchenko, O.V.; Lisnyak, V.V.

    2007-01-01

    Amorphous calcium hydroxyapatite was examined by vibrational spectroscopy (Raman and infra-red (IR)) and quantum chemical simulation techniques. The structures and vibrational (IR, Raman and inelastic neutron scattering) spectra of PO 4 3- ion, Ca 3 (PO 4 ) 2 , [Ca 3 (PO 4 ) 2 ] 3 , Ca 5 (PO 4 ) 3 OH, CaHPO 4 , [CaHPO 4 ] 2 , Ca 3 (PO 4 ) 2 .H 2 O, Ca 3 (PO 4 ) 2 .2H 2 O and Ca 3 (PO 4 ) 2 .3H 2 O clusters were quantum chemically simulated at ab initio and semiempirical levels of approximation. A complete coordinate analysis of the vibrational spectra was performed. The comparison of the theoretically simulated spectra with the experimental ones allows to identify correctly the phase composition of the amorphous calcium hydroxyapatite and related materials. The shape of the bands in the IR spectra of the hydroxoapatite can be used in order to characterize the structural properties of the material, e.g., the PO 4 3- ion status, the degree of hydrolysis of the material and the presence of hydrolysis products. - Graphical abstract: The structure of the quantum chemically optimized Ca 5 (PO 4 ) 3 (OH) cluster, which was used for vibrations spectra simulation

  9. Metal compounds in zeolites as active components of chemisorption and catalysis. Quantum chemical approach

    International Nuclear Information System (INIS)

    Zhidomirov, G.M.

    1996-01-01

    A short review of possible catalitic active sites associated with various types of metal species in zoolite is presented. The structural and electronic peculiarity of aluminum ions in zeolite lattice and their distribution in the lattice are discussed on the basis of quantum chemical calculations in connection with the formation of Broensted activity of zeolites. Various molecular models of Lewis Acid Sites associated the extra-lattice oxide-hydroxide aluminum species have been investigated by means of density functional model cluster calculations using CO molecule as a probe. Probable ways of formation of the selective oxidation center in FeZSM-5 by decomposition of dinitrogen monoxide have been studied by ab-initio quantum chemical calculations. The immediate oxidizing site is reasonably represented by the binuclear iron-hydroxide cluster with peroxo-like fragment located between iron atoms. Various probable intermediates of the selective oxidation center formation resulted from interaction of a hydroperoxide molecule with a lattice titanium ion in titanium silicalite have been investigated by quantum chemical calculations. It was concluded that this reaction requires essential structural reconstruction in the vicinity of the titanium ion. Probability of this structural reconstruction is discussed. Possible reasons of an electron-deficient and electron-enriched state of metal particles entrapped in zoolite cavities are discussed. Also, various probable molecular models of such modified metal particles in zeolite are considered

  10. Sub-nanometrically resolved chemical mappings of quantum-cascade laser active regions

    International Nuclear Information System (INIS)

    Pantzas, Konstantinos; Beaudoin, Grégoire; Patriarche, Gilles; Largeau, Ludovic; Mauguin, Olivia; Sagnes, Isabelle; Pegolotti, Giulia; Vasanelli, Angela; Calvar, Ariane; Amanti, Maria; Sirtori, Carlo

    2016-01-01

    A procedure that produces sub-nanometrically resolved chemical mappings of MOCVD-grown InGaAs/InAlAs/InP quantum cascade lasers is presented. The chemical mappings reveal that, although the structure is lattice-matched to InP, the InAlAs barriers do not attain the nominal aluminum content—48%—and are, in fact, InGaAlAs quaternaries. This information is used to adjust the aluminum precursor flow and fine-tune the composition of the barriers, resulting in a significant improvement of the fabricated lasers. (paper)

  11. Transport Studies of Quantum Magnetism: Physics and Methods

    Energy Technology Data Exchange (ETDEWEB)

    Lee, Minhyea [Univ. of Colorado, Boulder, CO (United States)

    2017-03-30

    The main goal of this project was to understand novel ground states of spin systems probed by thermal and electrical transport measurements. They are well-suited to characterize the nature of low-energy excitations as unique property of the ground state. More specifically, it was aimed to study the transverse electrical conductivity in the presence of non-collinear and non-coplanar spin ordering and the effects of gauge field as well as novel spin excitations as a coherent heat transport channel in insulating quantum magnets. Most of works done during the grant period focused on these topics. As a natural extension of the project's initial goals, the scope was broadened to include transport studies on the spin systems with strong spin-orbit coupling. One particular focus was an exploration of systems with strong magnetic anisotropy combined with non-trivial spin configuration. Magnetic anisotropy is directly related to implement the non-collinear spin ordering to the existing common geometry of planar devices and thus poses a significant potential. Work in this direction includes the comparison of the topological Hall signal under hydrostatic pressure and chemical doping, as well as the angular dependence dependence of the non-collinear spin ordered phase and their evolution up on temperature and field strength. Another focus was centered around the experimental identification of spin-originated heat carrying excitation in quasi two dimensional honeycomb lattice, where Kitaev type of quantum spin liquid phase is expected to emerge. In fact, when its long range magnetic order is destroyed by the applied field, we discovered anomalously large enhancement of thermal conductivity, for which proximate Kitaev excitations in field-induced spin liquid state are responsible for. This work, combined with further investigations in materials in the similar class may help establish the experimental characterization of new quantum spin liquid and their unique low energy

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

    KAUST Repository

    Risko, Chad; McGehee, Michael D.; Bré das, Jean-Luc

    2011-01-01

    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

  13. Quantum-chemical study of antioxidant additives for jet fuels

    Energy Technology Data Exchange (ETDEWEB)

    Poletaeva, O.Yu. [Ufa State Petroleum Technological Univ., Ufa (Russian Federation); Karimova, R.I. [Bashkir State Agrarian Univ., Ufa (Russian Federation); Movsumzade, E.M. [Institute of Education of Indigenous Small-Numbered Peoples of the North RAE, Moscow (Russian Federation)

    2012-07-01

    To obtain the necessary quality of jet fuels it can be used technological methods (hydrocracking, deep hydration, hydrogenation) that increases the cost of the finished product. The second way is to use less purified raw materials with the introduction of effective additives. Fuels obtained by direct distillation, in ambient air are oxidized with great difficulty and oxidation products accumulate in them is very slow. Fuels derived by hydrogenation processes, have high susceptibility to oxidation, as a result in 1-2 years of storage considerably reduced their quality. Antioxidant additives play an important role in improving the quality of jet fuel. (orig.)

  14. Quantum chemical study of penicillin: Reactions after acylation

    Science.gov (United States)

    Li, Rui; Feng, Dacheng; Zhu, Feng

    The density functional theory methods were used on the model molecules of penicillin to determine the possible reactions after their acylation on ?-lactamase, and the results were compared with sulbactam we have studied. The results show that, the acylated-enzyme tetrahedral intermediate can evolves with opening of ?-lactam ring as well as the thiazole ring; the thiazole ring-open products may be formed via ?-lactam ring-open product or from tetrahedral intermediate directly. Those products, in imine or enamine form, can tautomerize via hydrogen migration. In virtue of the water-assisted, their energy barriers are obviously reduced.

  15. Vibration spectroscopic analysis and quantum chemical calculation of thymine

    Directory of Open Access Journals (Sweden)

    FU Yichen

    2014-02-01

    Full Text Available In this paper,Raman and IR spectra of thymine(Th were measured respectively in this paper.Molecular structure of Th was optimized and it’s Raman and IR bands were calculated using B3LYP/6-311G(contain Density functional theory,DFT method.It was found that the calculated values match well with the experimental ones.The vibratinal frequencies of Th molecules were completely assigned with the assistance of Gauss View visualization software.

  16. Empirical, thermodynamic and quantum-chemical investigations of inclusion complexation between flavanones and (2-hydroxypropyl)-cyclodextrins.

    Science.gov (United States)

    Liu, Benguo; Li, Wei; Nguyen, Tien An; Zhao, Jian

    2012-09-15

    The inclusion complexation of (2-hydroxypropyl)-cyclodextrins with flavanones was investigated by phase solubility measurements, as well as thermodynamic and quantum chemical methods. Inclusion complexes were formed between (2-hydroxypropyl)-α-cyclodextrin (HP-α-CD), (2-hydroxypropyl)-β-cyclodextrin (HP-β-CD), (2-hydroxypropyl)-γ-cyclodextrin (HP-γ-CD) and β-cyclodextrin (β-CD) and four flavanones (naringenin, naringin, hesperetin and dihydromyricetin) in aqueous solutions and their phase solubility was determined. For all the flavanones, the stability constants of their complexes formed with different CDs followed the rank order: HP-β-CD (MW 1540)>HP-β-CD (MW 1460)>HP-β-CD (MW 1380)>β-CD>HP-γ-CD>HP-α-CD. Experimental results and quantum chemical calculations showed that the ability of flavanones to form inclusion complex with (2-hydroxypropyl)-cyclodextrins was determined by both the steric effect and hydrophobicity of the flavanones. For flavanones that have similar molecular volumes, the hydrophobicity of the molecule was the main determining factor of its ability to form inclusion complexes with HP-β-CD, and the hydrophobicity parameter Log P is highly correlated with the stability constant of the complexes. Results of thermodynamic study demonstrated that hydrophobic interaction is the main driving force for the formation process of the flavanone-CD inclusion complexes. Quantum chemical analysis of the most active hydroxyl groups and HOMO (the highest occupied molecular orbital) showed that the B ring of the flavanones was most likely involved in hydrogen bonding with the side groups in the cavity of the CDs, through which the inclusion complex was stabilised. Copyright © 2012 Elsevier Ltd. All rights reserved.

  17. Proton chemical shift tensors determined by 3D ultrafast MAS double-quantum NMR spectroscopy

    International Nuclear Information System (INIS)

    Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy

    2015-01-01

    Proton NMR spectroscopy in the solid state has recently attracted much attention owing to the significant enhancement in spectral resolution afforded by the remarkable advances in ultrafast magic angle spinning (MAS) capabilities. In particular, proton chemical shift anisotropy (CSA) has become an important tool for obtaining specific insights into inter/intra-molecular hydrogen bonding. However, even at the highest currently feasible spinning frequencies (110–120 kHz), 1 H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong 1 H– 1 H homonuclear dipolar couplings and narrow 1 H chemical shift (CS) ranges, which render it difficult to determine the CSA of specific proton sites in the standard CSA/single-quantum (SQ) chemical shift correlation experiment. Herein, we propose a three-dimensional (3D) 1 H double-quantum (DQ) chemical shift/CSA/SQ chemical shift correlation experiment to extract the CS tensors of proton sites whose signals are not well resolved along the single-quantum chemical shift dimension. As extracted from the 3D spectrum, the F1/F3 (DQ/SQ) projection provides valuable information about 1 H– 1 H proximities, which might also reveal the hydrogen-bonding connectivities. In addition, the F2/F3 (CSA/SQ) correlation spectrum, which is similar to the regular 2D CSA/SQ correlation experiment, yields chemical shift anisotropic line shapes at different isotropic chemical shifts. More importantly, since the F2/F1 (CSA/DQ) spectrum correlates the CSA with the DQ signal induced by two neighboring proton sites, the CSA spectrum sliced at a specific DQ chemical shift position contains the CSA information of two neighboring spins indicated by the DQ chemical shift. If these two spins have different CS tensors, both tensors can be extracted by numerical fitting. We believe that this robust and elegant single-channel proton-based 3D experiment provides useful atomistic-level structural and dynamical

  18. Analytic continuation of quantum Monte Carlo data. Stochastic sampling method

    Energy Technology Data Exchange (ETDEWEB)

    Ghanem, Khaldoon; Koch, Erik [Institute for Advanced Simulation, Forschungszentrum Juelich, 52425 Juelich (Germany)

    2016-07-01

    We apply Bayesian inference to the analytic continuation of quantum Monte Carlo (QMC) data from the imaginary axis to the real axis. Demanding a proper functional Bayesian formulation of any analytic continuation method leads naturally to the stochastic sampling method (StochS) as the Bayesian method with the simplest prior, while it excludes the maximum entropy method and Tikhonov regularization. We present a new efficient algorithm for performing StochS that reduces computational times by orders of magnitude in comparison to earlier StochS methods. We apply the new algorithm to a wide variety of typical test cases: spectral functions and susceptibilities from DMFT and lattice QMC calculations. Results show that StochS performs well and is able to resolve sharp features in the spectrum.

  19. 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

    2012-01-01

    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)

  20. Quantum chemical study of the mechanism of action of vitamin K epoxide reductase (VKOR)

    Science.gov (United States)

    Deerfield, David, II; Davis, Charles H.; Wymore, Troy; Stafford, Darrel W.; Pedersen, Lee G.

    Possible model, but simplistic, mechanisms for the action of vitamin K epoxide reductase (VKOR) are investigated with quantum mechanical methods (B3LYP/6-311G**). The geometries of proposed model intermediates in the mechanisms are energy optimized. Finally, the energetics of the proposed (pseudo-enzymatic) pathways are compared. We find that the several pathways are all energetically feasible. These results will be useful for designing quantum mechanical/molecular mechanical method (QM/MM) studies of the enzymatic pathway once three-dimensional structural data are determined and available for VKOR.

  1. The method of boson expansions in quantum theory

    International Nuclear Information System (INIS)

    Garbaczewski, P.

    1977-06-01

    A review is presented of boson expansion methods applied in quantum theory, e.g. expansions of spin, bifermion and fermion operators in cases of finite and infinite number of degrees of freedom. The basic purpose of the paper is to formulate the most general criterion allowing one to obtain the so-called finite spin approximation of any given Bose field theory and the class of fermion theories associated with it. On the other hand, we also need to be able to reconstruct the primary Bose field theory, when any finite spin or Fermi systems are given

  2. Foundations of quantum chromodynamics: Perturbative methods in gauge theories

    International Nuclear Information System (INIS)

    Muta, T.

    1986-01-01

    This volume develops the techniques of perturbative QCD in great detail starting with field theory. Aside from extensive treatments of the renormalization group technique, the operator product expansion formalism and their applications to short-distance reactions, this book provides a comprehensive introduction to gauge field theories. Examples and exercises are provided to amplify the discussions on important topics. Contents: Introduction; Elements of Quantum Chromodynamics; The Renormalization Group Method; Asymptotic Freedom; Operator Product Expansion Formalism; Applications; Renormalization Scheme Dependence; Factorization Theorem; Further Applications; Power Corrections; Infrared Problem. Power Correlations; Infrared Problem

  3. Automated chemical kinetic modeling via hybrid reactive molecular dynamics and quantum chemistry simulations.

    Science.gov (United States)

    Döntgen, Malte; Schmalz, Felix; Kopp, Wassja A; Kröger, Leif C; Leonhard, Kai

    2018-06-13

    An automated scheme for obtaining chemical kinetic models from scratch using reactive molecular dynamics and quantum chemistry simulations is presented. This methodology combines the phase space sampling of reactive molecular dynamics with the thermochemistry and kinetics prediction capabilities of quantum mechanics. This scheme provides the NASA polynomial and modified Arrhenius equation parameters for all species and reactions that are observed during the simulation and supplies them in the ChemKin format. The ab initio level of theory for predictions is easily exchangeable and the presently used G3MP2 level of theory is found to reliably reproduce hydrogen and methane oxidation thermochemistry and kinetics data. Chemical kinetic models obtained with this approach are ready-to-use for, e.g., ignition delay time simulations, as shown for hydrogen combustion. The presented extension of the ChemTraYzer approach can be used as a basis for methodologically advancing chemical kinetic modeling schemes and as a black-box approach to generate chemical kinetic models.

  4. 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

    International Nuclear Information System (INIS)

    Ahuactzin-Pérez, Miriam; Tlecuitl-Beristain, Saúl; García-Dávila, Jorge; González-Pérez, Manuel; Gutiérrez-Ruíz, María Concepción; Sánchez, Carmen

    2016-01-01

    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_m_a_x), biodegradation constant of DEHP (k), half-life (t_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_m_a_x 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_1_/_2 were 0.024 h"−"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.

  5. 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: sanher6@hotmail.com [Laboratory of Biotechnology, Research Centre for Biological Sciences, Universidad Autónoma de Tlaxcala, Ixtacuixtla, Tlaxcala CP. 90062 (Mexico)

    2016-10-01

    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.

  6. The variational method in quantum mechanics: an elementary introduction

    Science.gov (United States)

    Borghi, Riccardo

    2018-05-01

    Variational methods in quantum mechanics are customarily presented as invaluable techniques to find approximate estimates of ground state energies. In the present paper a short catalogue of different celebrated potential distributions (both 1D and 3D), for which an exact and complete (energy and wavefunction) ground state determination can be achieved in an elementary way, is illustrated. No previous knowledge of calculus of variations is required. Rather, in all presented cases the exact energy functional minimization is achieved by using only a couple of simple mathematical tricks: ‘completion of square’ and integration by parts. This makes our approach particularly suitable for undergraduates. Moreover, the key role played by particle localization is emphasized through the entire analysis. This gentle introduction to the variational method could also be potentially attractive for more expert students as a possible elementary route toward a rather advanced topic on quantum mechanics: the factorization method. Such an unexpected connection is outlined in the final part of the paper.

  7. Sensitivity of ab Initio vs Empirical Methods in Computing Structural Effects on NMR Chemical Shifts for the Example of Peptides.

    Science.gov (United States)

    Sumowski, Chris Vanessa; Hanni, Matti; Schweizer, Sabine; Ochsenfeld, Christian

    2014-01-14

    The structural sensitivity of NMR chemical shifts as computed by quantum chemical methods is compared to a variety of empirical approaches for the example of a prototypical peptide, the 38-residue kaliotoxin KTX comprising 573 atoms. Despite the simplicity of empirical chemical shift prediction programs, the agreement with experimental results is rather good, underlining their usefulness. However, we show in our present work that they are highly insensitive to structural changes, which renders their use for validating predicted structures questionable. In contrast, quantum chemical methods show the expected high sensitivity to structural and electronic changes. This appears to be independent of the quantum chemical approach or the inclusion of solvent effects. For the latter, explicit solvent simulations with increasing number of snapshots were performed for two conformers of an eight amino acid sequence. In conclusion, the empirical approaches neither provide the expected magnitude nor the patterns of NMR chemical shifts determined by the clearly more costly ab initio methods upon structural changes. This restricts the use of empirical prediction programs in studies where peptide and protein structures are utilized for the NMR chemical shift evaluation such as in NMR refinement processes, structural model verifications, or calculations of NMR nuclear spin relaxation rates.

  8. Quantum-chemical study of the geometric and electronic structure of the chromate anion CrO42- and a chromate group on the surface of finely divided silica by the CNDO/2 method

    International Nuclear Information System (INIS)

    Plyuto, I.V.; Shpak, A.P.; Plyuto, Yu.V.; Chuiko, A.A.

    1989-01-01

    A comparative study of the geometric and electronic structure of the chromate anion CrO 4 2- and a chromate group on the surface of finely divided silica (≡Si-O) 2 - CrO 2 , which was simulated by a CrO 9 Si 6 H 12 cluster, has been carried out by the SCF-MO-LCAO method in the all-valence-electron CNDO/2 approximation. The data obtained on the equilibrium geometry of the chromate group attest to the formation of a double bond between the Cr atom and each O atom (which is not bonded to Si). It has been shown that the support has a significant stabilizing in fluence on the energy of the MO's of the chromate group. The chromate group on an SiO 2 surface is characterized by partial delocalization of the frontier MO's among the skeletal bonds; however, the dominant contribution to the HOMO is made by the 2p AO of the oxygen atoms in the coordination shell of the Cr atom (∼70%), and the dominant contribution to the LUMO is made by the 3d AO of the chromium atom (∼50%). The positions and composition of the lowest unoccupied molecular orbitals point out the possibility of the display of electron-acceptor properties by a chromate group of an SiO 2 surface

  9. 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)

    2015-02-02

    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.

  10. A Quantum Chemical Exploration of the Horner-Wadsworth-Emmons Reaction

    DEFF Research Database (Denmark)

    Brandt, Peter; Norrby, Per-Ola; Martin, Ivar

    1998-01-01

    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 ...

  11. [Mass spectrometric and quantum chemical study of dimeric associates of nucleosides].

    Science.gov (United States)

    Sukhodub, L F; Aksenov, S A; Boldeskul, A I

    1995-01-01

    Deoxyribonucleosides H-bonded pairs were investigated using fast atom bombardment mass spectrometry and MNDO/H quantum chemistry method. It was shown that "rare" (enol or imin) forms of the nitrogen bases could form pairs with energy comparable with "canonical" base pair energy. It was shown that pair stability rows, which are measured using different experimental techniques, were in conformity each with other.

  12. SUCCESS AND PITFALLS OF THE DIELECTRIC CONTINUUM MODEL IN QUANTUM-CHEMICAL CALCULATIONS

    NARCIS (Netherlands)

    DEVRIES, AH; VANDUIJNEN, PT; JUFFER, AH

    1993-01-01

    Recently we presented an extension of the direct reaction field (DRF) method, in which a quantum system and a set of point charges and interacting polarizabilities are embedded in a continuum that is characterized by a dielectric constant epsilon and a finite ionic strength. The reaction field of

  13. Prediction of radical scavenging activities of anthocyanins applying adaptive neuro-fuzzy inference system (ANFIS) with quantum chemical descriptors.

    Science.gov (United States)

    Jhin, Changho; Hwang, Keum Taek

    2014-08-22

    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.

  14. Prediction of Radical Scavenging Activities of Anthocyanins Applying Adaptive Neuro-Fuzzy Inference System (ANFIS with Quantum Chemical Descriptors

    Directory of Open Access Journals (Sweden)

    Changho Jhin

    2014-08-01

    Full Text Available 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.

  15. Conformational, structural, vibrational and quantum chemical analysis on 4-aminobenzohydrazide and 4-hydroxybenzohydrazide--a comparative study.

    Science.gov (United States)

    Arjunan, V; Jayaprakash, A; Carthigayan, K; Periandy, S; Mohan, S

    2013-05-01

    Experimental and theoretical quantum chemical studies were carried out on 4-hydroxybenzohydrazide (4HBH) and 4-aminobenzohydrazide (4ABH) using FTIR and FT-Raman spectral data. The structural characteristics and vibrational spectroscopic analysis were carried performed by quantum chemical methods with the hybrid exchange-correlation functional B3LYP using 6-31G(**), 6-311++G(**) and aug-cc-pVDZ basis sets. The most stable conformer of the title compounds have been determined from the analysis of potential energy surface. The stable molecular geometries, electronic and thermodynamic parameters, IR intensities, harmonic vibrational frequencies, depolarisation ratio and Raman intensities have been computed. Molecular electrostatic potential and frontier molecular orbitals were constructed to understand the electronic properties. The potential energy distributions (PEDs) were calculated to explain the mixing of fundamental modes. The theoretical geometrical parameters and the fundamental frequencies were compared with the experimental. The interactions of hydroxy and amino group substitutions on the characteristic vibrations of the ring and hydrazide group have been analysed. Copyright © 2013 Elsevier B.V. All rights reserved.

  16. Assessment of chemical exposures: calculation methods for environmental professionals

    National Research Council Canada - National Science Library

    Daugherty, Jack E

    1997-01-01

    ... on by scientists, businessmen, and policymakers. Assessment of Chemical Exposures: Calculation Methods for Environmental Professionals addresses the expanding scope of exposure assessments in both the workplace and environment...

  17. Device for collecting chemical compounds and related methods

    Science.gov (United States)

    Scott, Jill R.; Groenewold, Gary S.; Rae, Catherine

    2013-01-01

    A device for sampling chemical compounds from fixed surfaces and related methods are disclosed. The device may include a vacuum source, a chamber and a sorbent material. The device may utilize vacuum extraction to volatilize the chemical compounds from the fixed surfaces so that they may be sorbed by the sorbent material. The sorbent material may then be analyzed using conventional thermal desorption/gas chromatography/mass spectrometry (TD/GC/MS) instrumentation to determine presence of the chemical compounds. The methods may include detecting release and presence of one or more chemical compounds and determining the efficacy of decontamination. The device may be useful in collection and analysis of a variety of chemical compounds, such as residual chemical warfare agents, chemical attribution signatures and toxic industrial chemicals.

  18. Safety in the Chemical Laboratory: Tested Disposal Methods for Chemical Wastes from Academic Laboratories.

    Science.gov (United States)

    Armour, M. A.; And Others

    1985-01-01

    Describes procedures for disposing of dichromate cleaning solution, picric acid, organic azides, oxalic acid, chemical spills, and hydroperoxides in ethers and alkenes. These methods have been tested under laboratory conditions and are specific for individual chemicals rather than for groups of chemicals. (JN)

  19. Conformational analysis, spectroscopic, structure-activity relations and quantum chemical simulation studies of 4-(trifluoromethyl)benzylamine

    Science.gov (United States)

    Arjunan, V.; Devi, L.; Mohan, S.

    2018-05-01

    The FT-IR and FT-Raman spectra of 4-trifluoromethylbenzylamine (TFMBA) have been recorded in the range 4000-450 and 4000-100 cm-1 respectively. The conformational analysis of the compound has been carried out to attain stable geometry of the compound. The complete vibrational assignment and analysis of the fundamental modes of the compound are carried out using the experimental FTIR and FT-Raman data and quantum chemical studies. The experimental vibrational frequencies are compared with the wavenumbers obtained theoretically from the B3LYP gradient calculations employing the standard high level 6-311++G** and cc-pVTZ basis sets for the optimised geometry of the compound. The structural parameters, thermodynamic properties and vibrational frequencies of the normal modes obtained from the B3LYP methods are in good agreement with the experimental data. The 1H (400 MHz; CDCl3) and 13C (100 MHz; CDCl3) nuclear magnetic resonance (NMR) spectra were also recorded. The electronic properties, highest occupied molecular orbital and lowest unoccupied molecular orbital energies are measured by DFT approach. The charges of the atoms by natural bond orbital (NBO) analysis are determined by B3LYP/cc-pVTZ method. The structure-chemical reactivity relations of the compound are determined through chemical potential, global hardness, global softness, electronegativity, electrophilicity and local reactivity descriptors by conceptual DFT methods.

  20. Diagrammatical methods within the path integral representation for quantum systems

    International Nuclear Information System (INIS)

    Alastuey, A

    2014-01-01

    The path integral representation has been successfully applied to the study of equilibrium properties of quantum systems for a long time. In particular, such a representation allowed Ginibre to prove the convergence of the low-fugacity expansions for systems with short-range interactions. First, I will show that the crucial trick underlying Ginibre's proof is the introduction of an equivalent classical system made with loops. Within the Feynman-Kac formula for the density matrix, such loops naturally emerge by collecting together the paths followed by particles exchanged in a given cyclic permutation. Two loops interact via an average of two- body genuine interactions between particles belonging to different loops, while the interactions between particles inside a given loop are accounted for in a loop fugacity. It turns out that the grand-partition function of the genuine quantum system exactly reduces to its classical counterpart for the gas of loops. The corresponding so-called magic formula can be combined with standard Mayer diagrammatics for the classical gas of loops. This provides low-density representations for the quantum correlations or thermodynamical functions, which are quite useful when collective effects must be taken into account properly. Indeed, resummations and or reorganizations of Mayer graphs can be performed by exploiting their remarkable topological and combinatorial properties, while statistical weights and bonds are purely c-numbers. The interest of that method will be illustrated through a brief description of its application to two long-standing problems, namely recombination in Coulomb systems and condensation in the interacting Bose gas.

  1. Include dispersion in quantum chemical modeling of enzymatic reactions: the case of isoaspartyl dipeptidase.

    Science.gov (United States)

    Zhang, Hai-Mei; Chen, Shi-Lu

    2015-06-09

    The lack of dispersion in the B3LYP functional has been proposed to be the main origin of big errors in quantum chemical modeling of a few enzymes and transition metal complexes. In this work, the essential dispersion effects that affect quantum chemical modeling are investigated. With binuclear zinc isoaspartyl dipeptidase (IAD) as an example, dispersion is included in the modeling of enzymatic reactions by two different procedures, i.e., (i) geometry optimizations followed by single-point calculations of dispersion (approach I) and (ii) the inclusion of dispersion throughout geometry optimization and energy evaluation (approach II). Based on a 169-atom chemical model, the calculations show a qualitative consistency between approaches I and II in energetics and most key geometries, demonstrating that both approaches are available with the latter preferential since both geometry and energy are dispersion-corrected in approach II. When a smaller model without Arg233 (147 atoms) was used, an inconsistency was observed, indicating that the missing dispersion interactions are essentially responsible for determining equilibrium geometries. Other technical issues and mechanistic characteristics of IAD are also discussed, in particular with respect to the effects of Arg233.

  2. Chemical Method of Urine Volume Measurement

    Science.gov (United States)

    Petrack, P.

    1967-01-01

    A system has been developed and qualified as flight hardware for the measurement of micturition volumes voided by crewmen during Gemini missions. This Chemical Urine Volume Measurement System (CUVMS) is used for obtaining samples of each micturition for post-flight volume determination and laboratory analysis for chemical constituents of physiological interest. The system is versatile with respect to volumes measured, with a capacity beyond the largest micturition expected to be encountered, and with respect to mission duration of inherently indefinite length. The urine sample is used for the measurement of total micturition volume by a tracer dilution technique, in which a fixed, predetermined amount of tritiated water is introduced and mixed into the voided urine, and the resulting concentration of the tracer in the sample is determined with a liquid scintillation spectrometer. The tracer employed does not interfere with the analysis for the chemical constituents of the urine. The CUVMS hardware consists of a four-way selector valve in which an automatically operated tracer metering pump is incorporated, a collection/mixing bag, and tracer storage accumulators. The assembled system interfaces with a urine receiver at the selector valve inlet, sample bags which connect to the side of the selector valve, and a flexible hose which carries the excess urine to the overboard drain connection. Results of testing have demonstrated system volume measurement accuracy within the specification limits of +/-5%, and operating reliability suitable for system use aboard the GT-7 mission, in which it was first used.

  3. Accuracy of Quantum Chemical Methods for Large Noncovalent Complexes

    Czech Academy of Sciences Publication Activity Database

    Sedlák, Robert; Janowski, T.; Pitoňák, M.; Řezáč, Jan; Pulay, P.; Hobza, Pavel

    2013-01-01

    Roč. 9, č. 8 (2013), s. 3364-3374 ISSN 1549-9618 R&D Projects: GA ČR GBP208/12/G016 Grant - others:Operational Program Research and Development for Innovations(XE) CZ1.05/2.1.00/03/0058 Institutional support: RVO:61388963 Keywords : density functional theory * intermolecular interaction energies * correlated molecular calculations Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.310, year: 2013

  4. Random sampling of quantum states: a survey of methods and some issues regarding the Overparametrized Method

    International Nuclear Information System (INIS)

    Maziero, Jonas

    2015-01-01

    The numerical generation of random quantum states (RQS) is an important procedure for investigations in quantum information science. Here, we review some methods that may be used for performing that task. We start by presenting a simple procedure for generating random state vectors, for which the main tool is the random sampling of unbiased discrete probability distributions (DPD). Afterwards, the creation of random density matrices is addressed. In this context, we first present the standard method, which consists in using the spectral decomposition of a quantum state for getting RQS from random DPDs and random unitary matrices. In the sequence, the Bloch vector parametrization method is described. This approach, despite being useful in several instances, is not in general convenient for RQS generation. In the last part of the article, we regard the overparametrized method (OPM) and the related Ginibre and Bures techniques. The OPM can be used to create random positive semidefinite matrices with unit trace from randomly produced general complex matrices in a simple way that is friendly for numerical implementations. We consider a physically relevant issue related to the possible domains that may be used for the real and imaginary parts of the elements of such general complex matrices. Subsequently, a too fast concentration of measure in the quantum state space that appears in this parametrization is noticed. (author)

  5. Reassigning the Structures of Natural Products Using NMR Chemical Shifts Computed with Quantum Mechanics: A Laboratory Exercise

    Science.gov (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.

    2015-01-01

    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…

  6. Quality Control Guidelines for SAM Chemical Methods

    Science.gov (United States)

    Learn more about quality control guidelines and recommendations for the analysis of samples using the chemistry methods listed in EPA's Selected Analytical Methods for Environmental Remediation and Recovery (SAM).

  7. Compensation effects in molecular interactions and the quantum chemical le Chatelier principle.

    Science.gov (United States)

    Mezey, Paul G

    2015-05-28

    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.

  8. On the origin of the gauche effect. A quantum chemical study of 1,2-difluoroethane

    Science.gov (United States)

    Engkvist, O.; Karlström, G.; Widmark, P.-O.

    1997-01-01

    The conformational equilibrium of 1,2-difluoroethane has been investigated using ab initio quantum chemical calculations at the SCF, MP2 and CCSD(T) levels, with ANO basis sets. The relative stability of the gauche-conformation of 1,2-difluoroethane is found to be a consequence of the nodal structure of the singly occupied orbital in the CFH 2 radical. It is also shown that the nodal structure of the singly occupied orbitals in the CFH biradical can explain the stability of the cis conformation of 1,2-difluoroethene.

  9. Classical and quantum aspects of topological solitons (using numerical methods)

    International Nuclear Information System (INIS)

    Weidig, T.

    1999-08-01

    In Introduction, we review integrable and topological solitons. In Numerical Methods, we describe how to minimise functionals, time-integrate configurations and solve eigenvalue problems. We also present the Simulated Annealing scheme for minimisation in solitonic systems. In Classical Aspects, we analyse the effect of the potential term on the structure of minimal-energy solutions for any topological charge n. The simplest holomorphic baby Skyrme model has no known stable minimal-energy solution for n > 1. The one-vacuum baby Skyrme model possesses non-radially symmetric multi-skyrmions that look like 'skyrmion lattices' formed by skyrmions with n = 2. The two-vacua baby Skyrme model has radially symmetric multi-skyrmions. We implement Simulated Annealing and it works well for higher order terms. We find that the spatial part of the six-derivative term is zero. In Quantum Aspects, we find the first order quantum mass correction for the φ 4 kink using the semi-classical expansion. We derive a trace formula which gives the mass correction by using the eigenmodes and values of the soliton and vacuum perturbations. We show that the zero mode is the most important contribution. We compute the mass correction of φ 4 kink and Sine-Gordon numerically by solving the eigenvalue equations and substituting into the trace formula. (author)

  10. Non-unitary probabilistic quantum computing circuit and method

    Science.gov (United States)

    Williams, Colin P. (Inventor); Gingrich, Robert M. (Inventor)

    2009-01-01

    A quantum circuit performing quantum computation in a quantum computer. A chosen transformation of an initial n-qubit state is probabilistically obtained. The circuit comprises a unitary quantum operator obtained from a non-unitary quantum operator, operating on an n-qubit state and an ancilla state. When operation on the ancilla state provides a success condition, computation is stopped. When operation on the ancilla state provides a failure condition, computation is performed again on the ancilla state and the n-qubit state obtained in the previous computation, until a success condition is obtained.

  11. Elucidation of Mechanisms and Selectivities of Metal-Catalyzed Reactions using Quantum Chemical Methodology.

    Science.gov (United States)

    Santoro, Stefano; Kalek, Marcin; Huang, Genping; Himo, Fahmi

    2016-05-17

    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

  12. High quantum yield ZnO quantum dots synthesizing via an ultrasonication microreactor method.

    Science.gov (United States)

    Yang, Weimin; Yang, Huafang; Ding, Wenhao; Zhang, Bing; Zhang, Le; Wang, Lixi; Yu, Mingxun; Zhang, Qitu

    2016-11-01

    Green emission ZnO quantum dots were synthesized by an ultrasonic microreactor. Ultrasonic radiation brought bubbles through ultrasonic cavitation. These bubbles built microreactor inside the microreactor. The photoluminescence properties of ZnO quantum dots synthesized with different flow rate, ultrasonic power and temperature were discussed. Flow rate, ultrasonic power and temperature would influence the type and quantity of defects in ZnO quantum dots. The sizes of ZnO quantum dots would be controlled by those conditions as well. Flow rate affected the reaction time. With the increasing of flow rate, the sizes of ZnO quantum dots decreased and the quantum yields first increased then decreased. Ultrasonic power changed the ultrasonic cavitation intensity, which affected the reaction energy and the separation of the solution. With the increasing of ultrasonic power, sizes of ZnO quantum dots first decreased then increased, while the quantum yields kept increasing. The effect of ultrasonic temperature on the photoluminescence properties of ZnO quantum dots was influenced by the flow rate. Different flow rate related to opposite changing trend. Moreover, the quantum yields of ZnO QDs synthesized by ultrasonic microreactor could reach 64.7%, which is higher than those synthesized only under ultrasonic radiation or only by microreactor. Copyright © 2016 Elsevier B.V. All rights reserved.

  13. Method for solving quantum field theory in the Heisenberg picture

    International Nuclear Information System (INIS)

    Nakanishi, Noboru

    2004-01-01

    This paper is a review of the method for solving quantum field theory in the Heisenberg picture, developed by Abe and Nakanishi since 1991. Starting from field equations and canonical (anti) commutation relations, one sets up a (q-number) Cauchy problem for the totality of d-dimensional (anti) commutators between the fundamental fields, where d is the number of spacetime dimensions. Solving this Cauchy problem, one obtains the operator solution of the theory. Then one calculates all multiple commutators. A representation of the operator solution is obtained by constructing the set of all Wightman functions for the fundamental fields; the truncated Wightman functions are constructed so as to be consistent with all vacuum expectation values of the multiple commutators mentioned above and with the energy-positivity condition. By applying the method described above, exact solutions to various 2-dimensional gauge-theory and quantum-gravity models are found explicitly. The validity of these solutions is confirmed by comparing them with the conventional perturbation-theoretical results. However, a new anomalous feature, called the ''field-equation anomaly'', is often found to appear, and its perturbation-theoretical counterpart, unnoticed previously, is discussed. The conventional notion of an anomaly with respect to symmetry is reconsidered on the basis of the field-equation anomaly, and the derivation of the critical dimension in the BRS-formulated bosonic string theory is criticized. The method outlined above is applied to more realistic theories by expanding everything in powers of the relevant parameter, but this expansion is not equivalent to the conventional perturbative expansion. The new expansion is BRS-invariant at each order, in contrast to that in the conventional perturbation theory. Higher-order calculations are generally extremely laborious to perform explicitly. (author)

  14. Chemical decontamination method in nuclear facility system

    International Nuclear Information System (INIS)

    Takahashi, Ryota; Sakai, Hitoshi; Oka, Shigehiro.

    1996-01-01

    Pumps and valves in a closed recycling loop system incorporating materials to be chemically decontaminated are decomposed, a guide plate having the decomposed parts as an exit/inlet of a decontaminating liquid is formed, and a decontaminating liquid recycling loop comprising a recycling pump and a heater is connected to the guide plate. Decontaminating liquid from a decontaminating liquid storage tank is supplied to the decontaminating liquid recycling loop. With such constitutions, the decontaminating liquid is filled in the recycling closed loop system incorporating materials to be decontaminated, and the materials to be decontaminated are chemically decontaminated. The decontaminating liquid after the decontamination is discharged and flows, if necessary, in a recycling system channel for repeating supply and discharge. After the decontamination, the guide plate is removed and returned to the original recycling loop. When pipelines of a reactor recycling system are decontaminated, the amount of decontaminations can be decreased, and reforming construction for assembling the recycling loop again, which requires cutting for pipelines in the system is no more necessary. Accordingly, the amount of wastes can be decreased, and therefore, the decontamination operation is facilitated and radiation dose can be reduced. (T.M.)

  15. An Improved Filtering Method for Quantum Color Image in Frequency Domain

    Science.gov (United States)

    Li, Panchi; Xiao, Hong

    2018-01-01

    In this paper we investigate the use of quantum Fourier transform (QFT) in the field of image processing. We consider QFT-based color image filtering operations and their applications in image smoothing, sharpening, and selective filtering using quantum frequency domain filters. The underlying principle used for constructing the proposed quantum filters is to use the principle of the quantum Oracle to implement the filter function. Compared with the existing methods, our method is not only suitable for color images, but also can flexibly design the notch filters. We provide the quantum circuit that implements the filtering task and present the results of several simulation experiments on color images. The major advantages of the quantum frequency filtering lies in the exploitation of the efficient implementation of the quantum Fourier transform.

  16. Quantum chemical studies on electronic structure and photodynamics of ruthenium complexes

    International Nuclear Information System (INIS)

    Freitag, L.

    2015-01-01

    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

  17. Study of CdTe quantum dots grown using a two-step annealing method

    Science.gov (United States)

    Sharma, Kriti; Pandey, Praveen K.; Nagpal, Swati; Bhatnagar, P. K.; Mathur, P. C.

    2006-02-01

    High size dispersion, large average radius of quantum dot and low-volume ratio has been a major hurdle in the development of quantum dot based devices. In the present paper, we have grown CdTe quantum dots in a borosilicate glass matrix using a two-step annealing method. Results of optical characterization and the theoretical model of absorption spectra have shown that quantum dots grown using two-step annealing have lower average radius, lesser size dispersion, higher volume ratio and higher decrease in bulk free energy as compared to quantum dots grown conventionally.

  18. Spectral analysis and quantum chemical studies of chair and twist-boat conformers of cycloheximide in gas and solution phases

    Science.gov (United States)

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

    2018-02-01

    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.

  19. The Alexandria library, a quantum-chemical database of molecular properties for force field development.

    Science.gov (United States)

    Ghahremanpour, Mohammad M; van Maaren, Paul J; van der Spoel, David

    2018-04-10

    Data quality as well as library size are crucial issues for force field development. In order to predict molecular properties in a large chemical space, the foundation to build force fields on needs to encompass a large variety of chemical compounds. The tabulated molecular physicochemical properties also need to be accurate. Due to the limited transparency in data used for development of existing force fields it is hard to establish data quality and reusability is low. This paper presents the Alexandria library as an open and freely accessible database of optimized molecular geometries, frequencies, electrostatic moments up to the hexadecupole, electrostatic potential, polarizabilities, and thermochemistry, obtained from quantum chemistry calculations for 2704 compounds. Values are tabulated and where available compared to experimental data. This library can assist systematic development and training of empirical force fields for a broad range of molecules.

  20. The Alexandria library, a quantum-chemical database of molecular properties for force field development

    Science.gov (United States)

    Ghahremanpour, Mohammad M.; van Maaren, Paul J.; van der Spoel, David

    2018-04-01

    Data quality as well as library size are crucial issues for force field development. In order to predict molecular properties in a large chemical space, the foundation to build force fields on needs to encompass a large variety of chemical compounds. The tabulated molecular physicochemical properties also need to be accurate. Due to the limited transparency in data used for development of existing force fields it is hard to establish data quality and reusability is low. This paper presents the Alexandria library as an open and freely accessible database of optimized molecular geometries, frequencies, electrostatic moments up to the hexadecupole, electrostatic potential, polarizabilities, and thermochemistry, obtained from quantum chemistry calculations for 2704 compounds. Values are tabulated and where available compared to experimental data. This library can assist systematic development and training of empirical force fields for a broad range of molecules.

  1. Quantum chemical molecular dynamical investigation of alkyl nitrite photo-dissociated on copper surfaces

    International Nuclear Information System (INIS)

    Wang Xiaojing; Wang Wei; Han Peilin; Kubo, Momoji; Miyamoto, Akira

    2008-01-01

    An accelerated quantum chemical molecular dynamical code 'Colors-Excite' was used to investigate the photolysis of alkyl nitrites series, RONO (R=CH 3 and C(CH 3 ) 3 ) on copper surfaces. Our calculations showed that the photo-dissociated processes are associated with the alkyl substituents of RONO when adsorbed on copper surfaces. For R=CH 3 , a two-step photolysis reaction occurred, yielding diverse intermediate products including RO radical, NO, and HNO, consistent with those reported in gas phase. While for R=C(CH 3 ) 3 , only one-step photolysis reaction occurred and gave intermediate products of RO radical and NO. Consequently, pure RO species were achieved to adsorb on metal surfaces by removing the NO species in photolysis reaction. The detailed photo-dissociated behaviors of RONO on copper surfaces with different alkyl substituents which are uncovered by the present simulation can be extended to explain the diverse dissociative mechanism experimentally observed. The quantum chemical molecular dynamical code 'Colors-Excite' is proved to be highly applicable to the photo-dissociations on metal surfaces

  2. An eigenvalue approach to quantum plasmonics based on a self-consistent hydrodynamics method.

    Science.gov (United States)

    Ding, Kun; Chan, C T

    2018-02-28

    Plasmonics has attracted much attention not only because it has useful properties such as strong field enhancement, but also because it reveals the quantum nature of matter. To handle quantum plasmonics effects, ab initio packages or empirical Feibelman d-parameters have been used to explore the quantum correction of plasmonic resonances. However, most of these methods are formulated within the quasi-static framework. The self-consistent hydrodynamics model offers a reliable approach to study quantum plasmonics because it can incorporate the quantum effect of the electron gas into classical electrodynamics in a consistent manner. Instead of the standard scattering method, we formulate the self-consistent hydrodynamics method as an eigenvalue problem to study quantum plasmonics with electrons and photons treated on the same footing. We find that the eigenvalue approach must involve a global operator, which originates from the energy functional of the electron gas. This manifests the intrinsic nonlocality of the response of quantum plasmonic resonances. Our model gives the analytical forms of quantum corrections to plasmonic modes, incorporating quantum electron spill-out effects and electrodynamical retardation. We apply our method to study the quantum surface plasmon polariton for a single flat interface.

  3. Numerical perturbative methods in the quantum theory of physical systems

    International Nuclear Information System (INIS)

    Adam, G.

    1980-01-01

    During the last two decades, development of digital electronic computers has led to the deployment of new, distinct methods in theoretical physics. These methods, based on the advances of modern numerical analysis as well as on specific equations describing physical processes, enabled to perform precise calculations of high complexity which have completed and sometimes changed our image of many physical phenomena. Our efforts have concentrated on the development of numerical methods with such intrinsic performances as to allow a successful approach of some Key issues in present theoretical physics on smaller computation systems. The basic principle of such methods is to translate, in numerical analysis language, the theory of perturbations which is suited to numerical rather than to analytical computation. This idea has been illustrated by working out two problems which arise from the time independent Schroedinger equation in the non-relativistic approximation, within both quantum systems with a small number of particles and systems with a large number of particles, respectively. In the first case, we are led to the numerical solution of some quadratic ordinary differential equations (first section of the thesis) and in the second case, to the solution of some secular equations in the Brillouin area (second section). (author)

  4. A quantum chemical analysis of Zn and Sb doping and co-doping in SnO2

    Directory of Open Access Journals (Sweden)

    Luis Villamagua

    2017-10-01

    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.

  5. Chemical decontamination method for radioactive metal waste

    International Nuclear Information System (INIS)

    Onuma, Tsutomu; Tanaka, Akio; Shibuya, Sadao.

    1991-01-01

    When contaminants mainly composed of copper remained on the surface of stainless steel wastes sent from an electrolytic reduction as a first step are chemically decontaminated, metal wastes are discriminated to carbon steel wastes and stainless steel wastes. Then, the carbon steel wastes are applied only with the first step of immersing in a sulfuric acid solution, and stainless steel wastes are applied with a first step of immersing into a sulfuric acid solution for electrolytic reduction for a predetermined period of time and a second step of immersing into a liquid in which an oxidative metal salt is added to sulfuric acid. The decontamination liquid which is used for immersing the stainless steel wastes in the second step and the oxidation force of which is lowered is used as the sulfuric acid solution in the first step for the carbon steel wastes. In view of the above, the decontamination liquid of the second step can be utilized most effectively, enabling to greatly decrease the secondary wastes and to improve decontamination efficiency. (T.M.)

  6. Improved performance of nanowire–quantum-dot–polymer solar cells by chemical treatment of the quantum dot with ligand and solvent materials

    International Nuclear Information System (INIS)

    Nadarajah, A; Smith, T; Könenkamp, R

    2012-01-01

    We report a nanowire–quantum-dot–polymer solar cell consisting of a chemically treated CdSe quantum dot film deposited on n-type ZnO nanowires. The electron and hole collecting contacts are a fluorine-doped tin-oxide/zinc oxide layer and a P3HT/Au layer. This device architecture allows for enhanced light absorption and an efficient collection of photogenerated carriers. A detailed analysis of the chemical treatment of the quantum dots, their deposition, and the necessary annealing processes are discussed. We find that the surface treatment of CdSe quantum dots with pyridine, and the use of 1,2-ethanedithiol (EDT) ligands, critically improves the device performance. Annealing at 380 °C for 2 h is found to cause a structural conversion of the CdSe from its initial isolated quantum dot arrangement into a polycrystalline film with excellent surface conformality, thereby resulting in a further enhancement of device performance. Moreover, long-term annealing of 24 h leads to additional increases in device efficiency. Our best conversion efficiency reached for this type of cell is 3.4% under 85 mW cm −2 illumination. (paper)

  7. 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

    2012-01-01

    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.

  8. A deterministic alternative to the full configuration interaction quantum Monte Carlo method

    Energy Technology Data Exchange (ETDEWEB)

    Tubman, Norm M.; Lee, Joonho; Takeshita, Tyler Y.; Head-Gordon, Martin; Whaley, K. Birgitta [University of California, Berkeley, Berkeley, California 94720 (United States)

    2016-07-28

    Development of exponentially scaling methods has seen great progress in tackling larger systems than previously thought possible. One such technique, full configuration interaction quantum Monte Carlo, is a useful algorithm that allows exact diagonalization through stochastically sampling determinants. The method derives its utility from the information in the matrix elements of the Hamiltonian, along with a stochastic projected wave function, to find the important parts of Hilbert space. However, the stochastic representation of the wave function is not required to search Hilbert space efficiently, and here we describe a highly efficient deterministic method that can achieve chemical accuracy for a wide range of systems, including the difficult Cr{sub 2} molecule. We demonstrate for systems like Cr{sub 2} that such calculations can be performed in just a few cpu hours which makes it one of the most efficient and accurate methods that can attain chemical accuracy for strongly correlated systems. In addition our method also allows efficient calculation of excited state energies, which we illustrate with benchmark results for the excited states of C{sub 2}.

  9. Quantum chemical studies on structural, vibrational, nonlinear optical properties and chemical reactivity of indigo carmine dye

    Science.gov (United States)

    El-Mansy, M. A. M.

    2017-08-01

    Structural and vibrational spectroscopic studies were performed on indigo carmine (IC) isomers using FT-IR spectral analysis along with DFT/B3LYP method utilizing Gaussian 09 software. GaussView 5 program has been employed to perform a detailed interpretation of vibrational spectra. Simulation of infrared spectra has led to an excellent overall agreement with the observed spectral patterns. Mulliken population analyses on atomic charges, MEP, HOMO-LUMO, NLO, first order hyperpolarizability and thermodynamic properties have been examined by (DFT/B3LYP) method with the SDD basis set level. Density of state spectra (DOS) were calculated using GaussSum 3 at the same level of theory. Molecular modeling approved that DOS Spectra are the most significant tools for differentiating between two IC isomers so far. Moreover, The IC isomers (cis-isomer) have shown an extended applicability for manufacturing both NLO and photovoltaic devices such as solar cells.

  10. Investigation of Evaluation method of chemical runaway reaction

    International Nuclear Information System (INIS)

    Sato, Yoshihiko; Sasaya, Shinji; Kurakata, Koichiro; Nojiri, Ichiro

    2002-02-01

    Safety study 'Study of evaluation of abnormal occurrence for chemical substances in the nuclear fuel facilities' will be carried out from 2001 to 2005. In this study, the prediction of thermal hazards of chemical substances will be investigated and prepared. The hazard prediction method of chemical substances will be constructed from these results. Therefore, the hazard prediction methods applied in the chemical engineering in which the chemical substances with the hazard of fire and explosion were often treated were investigated. CHETAH (The ASTM Computer Program for Chemical Thermodynamic and Energy Release Evaluation) developed by ASTM (American Society for Testing and Materials) and TSS (Thermal Safety Software) developed by CISP (ChemInform St. Petersburg) were introduced and the fire and explosion hazards of chemical substances and reactions in the reprocessing process were evaluated. From these evaluated results, CHETAH could almost estimate the heat of reaction at 10% accuracy. It was supposed that CHETAH was useful as a screening for the hazards of fire and explosion of the new chemical substances and so on. TSS could calculate the reaction rate and the reaction behavior from the data measured by the various calorimeters rapidly. It was supposed that TSS was useful as an evaluation method for the hazards of fire and explosion of the new chemical reactions and so on. (author)

  11. Chemical Compounds and Extraction Methods of ?Maollahm?

    OpenAIRE

    Sadeghpoor, Omid; Dayeni, Manijeh; Razi, Samane

    2016-01-01

    Background: Maollahm or meat juice, a by-product of meat, is a traditional remedy in Persian medicine. This product was used as a nourishment or treatment substance for sick people. According to the ancient Persian medicine, animal meat has more affinity with the human body and the body easily absorbs its nutrition. Therefore, one could resort to maollahm for patients requiring urgent nourishment to boost and strengthen their body. Methods: In this work, different ways of preparing maollahm f...

  12. Quantum

    CERN Document Server

    Al-Khalili, Jim

    2003-01-01

    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.

  13. Investigation of Chemical Equilibrium Kinetics by the Electromigration Method

    CERN Document Server

    Bozhikov, G A; Bontchev, G D; Maslov, O D; Milanov, M V; Dmitriev, S N

    2002-01-01

    Measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the complex formation of Hf(IV) and DTPA is determined.

  14. A Synthetic Approach to the Transfer Matrix Method in Classical and Quantum Physics

    Science.gov (United States)

    Pujol, O.; Perez, J. P.

    2007-01-01

    The aim of this paper is to propose a synthetic approach to the transfer matrix method in classical and quantum physics. This method is an efficient tool to deal with complicated physical systems of practical importance in geometrical light or charged particle optics, classical electronics, mechanics, electromagnetics and quantum physics. Teaching…

  15. Toward prethreshold gate-based quantum simulation of chemical dynamics: using potential energy surfaces to simulate few-channel molecular collisions

    Science.gov (United States)

    Sornborger, Andrew T.; Stancil, Phillip; Geller, Michael R.

    2018-05-01

    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. Proposal of Realization Restricted Quantum Game with Linear Optic Method

    International Nuclear Information System (INIS)

    Zhao Haijun; Fang Ximing

    2006-01-01

    We present a quantum game with the restricted strategic space and its realization with linear optical system, which can be played by two players who are separated remotely. This game can also be realized on any other quantum computers. We find that the constraint brings some interesting properties that are useful for making game models.

  17. High performance computing and quantum trajectory method in CPU and GPU systems

    International Nuclear Information System (INIS)

    Wiśniewska, Joanna; Sawerwain, Marek; Leoński, Wiesław

    2015-01-01

    Nowadays, a dynamic progress in computational techniques allows for development of various methods, which offer significant speed-up of computations, especially those related to the problems of quantum optics and quantum computing. In this work, we propose computational solutions which re-implement the quantum trajectory method (QTM) algorithm in modern parallel computation environments in which multi-core CPUs and modern many-core GPUs can be used. In consequence, new computational routines are developed in more effective way than those applied in other commonly used packages, such as Quantum Optics Toolbox (QOT) for Matlab or QuTIP for Python

  18. Method of cleaning oil slicks and chemical spills

    International Nuclear Information System (INIS)

    Billings, L.

    1992-01-01

    This patent describes a method of cleaning a floating chemical spill on a body of water. It comprises: providing a quantity of popular bark-based pelleted or granular product, flotation means and a flexible net having openings generally smaller than the smallest whole pellet dimension of the pelleted product, spreading the net over a chemical spill on the body of water, connecting the floatation means to the net thereby supporting the net adjacent the surface of the body of water, placing the poplar bark-based product on the net, absorbing the floating chemical spill into the product, and removing the chemical soaked product from the body of water

  19. Quantum chemical analysis of Со2+ aqua complexes electrochemical reduction

    Directory of Open Access Journals (Sweden)

    Viktor F. Vargalyuk

    2017-11-01

    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]+.

  20. Quantum-chemical analysis of formation reactions of Со2+ complexes

    Directory of Open Access Journals (Sweden)

    Viktor F. Vargalyuk

    2017-11-01

    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.

  1. Classical-processing and quantum-processing signal separation methods for qubit uncoupling

    Science.gov (United States)

    Deville, Yannick; Deville, Alain

    2012-12-01

    The Blind Source Separation problem consists in estimating a set of unknown source signals from their measured combinations. It was only investigated in a non-quantum framework up to now. We propose its first quantum extensions. We thus introduce the Quantum Source Separation field, investigating both its blind and non-blind configurations. More precisely, we show how to retrieve individual quantum bits (qubits) only from the global state resulting from their undesired coupling. We consider cylindrical-symmetry Heisenberg coupling, which e.g. occurs when two electron spins interact through exchange. We first propose several qubit uncoupling methods which typically measure repeatedly the coupled quantum states resulting from individual qubits preparations, and which then statistically process the classical data provided by these measurements. Numerical tests prove the effectiveness of these methods. We then derive a combination of quantum gates for performing qubit uncoupling, thus avoiding repeated qubit preparations and irreversible measurements.

  2. New chemical-DSMC method in numerical simulation of axisymmetric rarefied reactive flow

    Science.gov (United States)

    Zakeri, Ramin; Kamali Moghadam, Ramin; Mani, Mahmoud

    2017-04-01

    The modified quantum kinetic (MQK) chemical reaction model introduced by Zakeri et al. is developed for applicable cases in axisymmetric reactive rarefied gas flows using the direct simulation Monte Carlo (DSMC) method. Although, the MQK chemical model uses some modifications in the quantum kinetic (QK) method, it also employs the general soft sphere collision model and Stockmayer potential function to properly select the collision pairs in the DSMC algorithm and capture both the attraction and repulsion intermolecular forces in rarefied gas flows. For assessment of the presented model in the simulation of more complex and applicable reacting flows, first, the air dissociation is studied in a single cell for equilibrium and non-equilibrium conditions. The MQK results agree well with the analytical and experimental data and they accurately predict the characteristics of the rarefied flowfield with chemical reaction. To investigate accuracy of the MQK chemical model in the simulation of the axisymmetric flow, air dissociation is also assessed in an axial hypersonic flow around two geometries, the sphere as a benchmark case and the blunt body (STS-2) as an applicable test case. The computed results including the transient, rotational and vibrational temperatures, species concentration in the stagnation line, and also the heat flux and pressure coefficient on the surface are compared with those of the other chemical methods like the QK and total collision energy (TCE) models and available analytical and experimental data. Generally, the MQK chemical model properly simulates the chemical reactions and predicts flowfield characteristics more accurate rather than the typical QK model. Although in some cases, results of the MQK approaches match with those of the TCE method, the main point is that the MQK does not need any experimental data or unrealistic assumption of specular boundary condition as used in the TCE method. Another advantage of the MQK model is the

  3. Quantum dots assisted photocatalysis for the chemiluminometric determination of chemical oxygen demand using a single interface flow system

    Energy Technology Data Exchange (ETDEWEB)

    Silvestre, Cristina I.C.; Frigerio, Christian [Requimte, Department of Chemistry, Faculty of Pharmacy, Porto University, Rua Anibal Cunha 164, 4099-030, Porto (Portugal); Santos, Joao L.M., E-mail: joaolms@ff.up.pt [Requimte, Department of Chemistry, Faculty of Pharmacy, Porto University, Rua Anibal Cunha 164, 4099-030, Porto (Portugal); Lima, Jose L.F.C. [Requimte, Department of Chemistry, Faculty of Pharmacy, Porto University, Rua Anibal Cunha 164, 4099-030, Porto (Portugal)

    2011-08-12

    Highlights: {yields} A novel flow method for the determination of chemical oxygen demand is proposed. {yields} CdTe nanocrystals are irradiated with UV light to generate strong oxidizing species. {yields} Reactive species promote a fast catalytic degradation of organic matter. {yields} Luminol is used as a chemiluminescence probe for indirect COD assessment. {yields} A single interface flow system was implemented to automate the assays. - Abstract: A novel flow method for the determination of chemical oxygen demand (COD) is proposed in this work. It relies on the combination of a fully automated single interface flow system, an on-line UV photocatalytic unit and quantum dot (QD) nanotechnology. The developed approach takes advantage of CdTe nanocrystals capacity to generate strong oxidizing species upon irradiation with UV light, which fostered a fast catalytic degradation of the organic compounds. Luminol was used as a chemiluminescence (CL) probe for indirect COD assessment, since it is easily oxidized by the QD generated species yielding a strong CL emission that is quenched in the presence of the organic matter. The proposed methodology allowed the determination of COD concentrations between 1 and 35 mg L{sup -1}, with good precision (R.S.D. < 1.1%, n = 3) and a sampling frequency of about 33 h{sup -1}. The procedure was applied to the determination of COD in wastewater certified reference materials and the obtained results showed an excellent agreement with the certified values.

  4. Variational methods for chemical and nuclear reactions

    International Nuclear Information System (INIS)

    Crawford, O.H.

    1977-01-01

    All the variational functionals are derived which satisfy certain criteria of suitability for molecular and nuclear scattering, below the threshold energy for three-body breakup. The existence and uniqueness of solutions are proven. The most general suitable functional is specialized, by particular values of its parameters, to Kohn's taneta, Kato's cot(eta-theta), the inverse Kohn coeta, Kohn's S matrix, our S matrix, Lane and Robson's functional, and several new functionals, an infinite number of which are contained in the general expression. Four general ways of deriving algebraic methods from a given functional are discussed, and illustrated with specific algebraic results. These include equations of Lane and Robson and of Kohn, the fundamental R matrix relation, and new equations. The relative configuration space is divided as in the Wigner R matrix theory, and trial wavefunctions are needed for only the region where all the particles are interacting. In addition, a version of the general functional is presented which does not require any division of space

  5. Odour detection methods: olfactometry and chemical sensors.

    Science.gov (United States)

    Brattoli, Magda; de Gennaro, Gianluigi; de Pinto, Valentina; Loiotile, Annamaria Demarinis; Lovascio, Sara; Penza, Michele

    2011-01-01

    The complexity of the odours issue arises from the sensory nature of smell. From the evolutionary point of view olfaction is one of the oldest senses, allowing for seeking food, recognizing danger or communication: human olfaction is a protective sense as it allows the detection of potential illnesses or infections by taking into account the odour pleasantness/unpleasantness. Odours are mixtures of light and small molecules that, coming in contact with various human sensory systems, also at very low concentrations in the inhaled air, are able to stimulate an anatomical response: the experienced perception is the odour. Odour assessment is a key point in some industrial production processes (i.e., food, beverages, etc.) and it is acquiring steady importance in unusual technological fields (i.e., indoor air quality); this issue mainly concerns the environmental impact of various industrial activities (i.e., tanneries, refineries, slaughterhouses, distilleries, civil and industrial wastewater treatment plants, landfills and composting plants) as sources of olfactory nuisances, the top air pollution complaint. Although the human olfactory system is still regarded as the most important and effective "analytical instrument" for odour evaluation, the demand for more objective analytical methods, along with the discovery of materials with chemo-electronic properties, has boosted the development of sensor-based machine olfaction potentially imitating the biological system. This review examines the state of the art of both human and instrumental sensing currently used for the detection of odours. The olfactometric techniques employing a panel of trained experts are discussed and the strong and weak points of odour assessment through human detection are highlighted. The main features and the working principles of modern electronic noses (E-Noses) are then described, focusing on their better performances for environmental analysis. Odour emission monitoring carried out through

  6. Odour Detection Methods: Olfactometry and Chemical Sensors

    Directory of Open Access Journals (Sweden)

    Sara Lovascio

    2011-05-01

    Full Text Available The complexity of the odours issue arises from the sensory nature of smell. From the evolutionary point of view olfaction is one of the oldest senses, allowing for seeking food, recognizing danger or communication: human olfaction is a protective sense as it allows the detection of potential illnesses or infections by taking into account the odour pleasantness/unpleasantness. Odours are mixtures of light and small molecules that, coming in contact with various human sensory systems, also at very low concentrations in the inhaled air, are able to stimulate an anatomical response: the experienced perception is the odour. Odour assessment is a key point in some industrial production processes (i.e., food, beverages, etc. and it is acquiring steady importance in unusual technological fields (i.e., indoor air quality; this issue mainly concerns the environmental impact of various industrial activities (i.e., tanneries, refineries, slaughterhouses, distilleries, civil and industrial wastewater treatment plants, landfills and composting plants as sources of olfactory nuisances, the top air pollution complaint. Although the human olfactory system is still regarded as the most important and effective “analytical instrument” for odour evaluation, the demand for more objective analytical methods, along with the discovery of materials with chemo-electronic properties, has boosted the development of sensor-based machine olfaction potentially imitating the biological system. This review examines the state of the art of both human and instrumental sensing currently used for the detection of odours. The olfactometric techniques employing a panel of trained experts are discussed and the strong and weak points of odour assessment through human detection are highlighted. The main features and the working principles of modern electronic noses (E-Noses are then described, focusing on their better performances for environmental analysis. Odour emission monitoring

  7. 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.)

    2012-02-01

    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

  8. Safety in the Chemical Laboratory--Chemical Management: A Method for Waste Reduction.

    Science.gov (United States)

    Pine, Stanley H.

    1984-01-01

    Discusses methods for reducing or eliminating waste disposal problems in the chemistry laboratory, considering both economic and environmental aspects of the problems. Proposes inventory control, shared use, solvent recycling, zero effluent, and various means of disposing of chemicals. (JM)

  9. Chemical nature and structure of organic coating of quantum dots is crucial for their application in imaging diagnostics

    Science.gov (United States)

    Bakalova, Rumiana; Zhelev, Zhivko; Kokuryo, Daisuke; Spasov, Lubomir; Aoki, Ichio; Saga, Tsuneo

    2011-01-01

    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

  10. 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

    2017-08-21

    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.

  11. Evidence for excited-state intramolecular proton transfer in 4-chlorosalicylic acid from combined experimental and computational studies: Quantum chemical treatment of the intramolecular hydrogen bonding interaction

    Energy Technology Data Exchange (ETDEWEB)

    Paul, Bijan Kumar [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India); Guchhait, Nikhil, E-mail: nikhil.guchhait@rediffmail.com [Department of Chemistry, University of Calcutta, 92 Acharya Prafulla Chandra Road, Calcutta 700009 (India)

    2012-07-25

    Highlights: Black-Right-Pointing-Pointer Experimental and computational studies on the photophysics of 4-chlorosalicylic acid. Black-Right-Pointing-Pointer Spectroscopically established ESIPT reaction substantiated by theoretical calculation. Black-Right-Pointing-Pointer Quantum chemical treatment of IMHB unveils strength, nature and directional nature. Black-Right-Pointing-Pointer Superiority of quantum chemical treatment of H-bond over geometric criteria. Black-Right-Pointing-Pointer Role of H-bond as a modulator of aromaticity. -- Abstract: The photophysical study of a pharmaceutically important chlorine substituted derivative of salicylic acid viz., 4-chlorosalicylic acid (4ClSA) has been carried out by steady-state absorption, emission and time-resolved emission spectroscopy. A large Stokes shifted emission band with negligible solvent polarity dependence marks the spectroscopic signature of excited-state intramolecular proton transfer (ESIPT) reaction in 4ClSA. Theoretical calculation by ab initio and Density Functional Theory methods yields results consistent with experimental findings. Theoretical potential energy surfaces predict the occurrence of proton transfer in S{sub 1}-state. Geometrical and energetic criteria, Atoms-In-Molecule topological parameters, Natural Bond Orbital population analysis have been exploited to evaluate the intramolecular hydrogen bond (IMHB) interaction and to explore its directional nature. The inter-correlation between aromaticity and resonance assisted H-bond is also discussed in this context. Our results unveil that the quantum chemical treatment is a more accurate tool to assess hydrogen bonding interaction in comparison to geometrical criteria.

  12. Mathematical methods in physics distributions, Hilbert space operators, variational methods, and applications in quantum physics

    CERN Document Server

    Blanchard, Philippe

    2015-01-01

    The second edition of this textbook presents the basic mathematical knowledge and skills that are needed for courses on modern theoretical physics, such as those on quantum mechanics, classical and quantum field theory, and related areas.  The authors stress that learning mathematical physics is not a passive process and include numerous detailed proofs, examples, and over 200 exercises, as well as hints linking mathematical concepts and results to the relevant physical concepts and theories.  All of the material from the first edition has been updated, and five new chapters have been added on such topics as distributions, Hilbert space operators, and variational methods.   The text is divided into three main parts. Part I is a brief introduction to distribution theory, in which elements from the theories of ultradistributions and hyperfunctions are considered in addition to some deeper results for Schwartz distributions, thus providing a comprehensive introduction to the theory of generalized functions. P...

  13. Quantum-Chemical Insights into the Self-Assembly of Carbon-Based Supramolecular Complexes

    Directory of Open Access Journals (Sweden)

    Joaquín Calbo

    2018-01-01

    Full Text Available Understanding how molecular systems self-assemble to form well-organized superstructures governed by noncovalent interactions is essential in the field of supramolecular chemistry. In the nanoscience context, the self-assembly of different carbon-based nanoforms (fullerenes, carbon nanotubes and graphene with, in general, electron-donor molecular systems, has received increasing attention as a means of generating potential candidates for technological applications. In these carbon-based systems, a deep characterization of the supramolecular organization is crucial to establish an intimate relation between supramolecular structure and functionality. Detailed structural information on the self-assembly of these carbon-based nanoforms is however not always accessible from experimental techniques. In this regard, quantum chemistry has demonstrated to be key to gain a deep insight into the supramolecular organization of molecular systems of high interest. In this review, we intend to highlight the fundamental role that quantum-chemical calculations can play to understand the supramolecular self-assembly of carbon-based nanoforms through a limited selection of supramolecular assemblies involving fullerene, fullerene fragments, nanotubes and graphene with several electron-rich π-conjugated systems.

  14. QSAR analysis of salicylamide isosteres with the use of quantum chemical molecular descriptors.

    Science.gov (United States)

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

    2009-02-01

    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.

  15. Low Temperature Synthesis of CdSe Quantum Dots with Amine Derivative and Their Chemical Kinetics

    Science.gov (United States)

    Seongmi Hwang,; Youngmin Choi,; Sunho Jeong,; Hakyun Jung,; Chang Gyoun Kim,; Teak-Mo Chung,; Beyong-Hwan Ryu,

    2010-05-01

    The chemical kinetics of growing CdSe nanocrystals was studied in order to investigate the effects of amine capping agents on the size of resulting quantum dots (QDs). CdSe QDs were prepared in phenyl ether, and the amine ligand dependence of QD size was determined. The results show that the size of CdSe nanocrystals can be regulated by controlling reaction rate, with smaller QDs being formed in slower processes. The results of photoluminescence (PL) studies show that the emission wavelengths of the QDs well correlate with particle size. This simple process for forming different-sized QDs, which uses a cheap solvent and various capping agents, has the potential for preparing CdSe nanocrystals more economically.

  16. A theoretical quantum chemical study of alanine formation in interstellar medium

    Science.gov (United States)

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

    2017-08-01

    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.

  17. Applications of the infinite momentum method to quantum electrodynamics and bound state problem

    International Nuclear Information System (INIS)

    Brodsky, S.J.

    1973-01-01

    It is shown that the infinite momentum method is a valid and useful calculational alternative to standard perturbation theory methods. The most exciting future applications may be in bound state problems in quantum electrodynamics

  18. Calculation of Multiphase Chemical Equilibrium by the Modified RAND Method

    DEFF Research Database (Denmark)

    Tsanas, Christos; Stenby, Erling Halfdan; Yan, Wei

    2017-01-01

    method. The modified RAND extends the classical RAND method from single-phase chemical reaction equilibrium of ideal systems to multiphase chemical equilibrium of nonideal systems. All components in all phases are treated in the same manner and the system Gibbs energy can be used to monitor convergence....... This is the first time that modified RAND was applied to multiphase chemical equilibrium systems. The combined algorithm was tested using nine examples covering vapor–liquid (VLE) and vapor–liquid–liquid equilibria (VLLE) of ideal and nonideal reaction systems. Successive substitution provided good initial......A robust and efficient algorithm for simultaneous chemical and phase equilibrium calculations is proposed. It combines two individual nonstoichiometric solving procedures: a nested-loop method with successive substitution for the first steps and final convergence with the second-order modified RAND...

  19. Chemical analysis of cyanide in cyanidation process: review of methods

    International Nuclear Information System (INIS)

    Nova-Alonso, F.; Elorza-Rodriguez, E.; Uribe-Salas, A.; Perez-Garibay, R.

    2007-01-01

    Cyanidation, the world wide method for precious metals recovery, the chemical analysis of cyanide, is a very important, but complex operation. Cyanide can be present forming different species, each of them with different stability, toxicity, analysis method and elimination technique. For cyanide analysis, there exists a wide selection of analytical methods but most of them present difficulties because of the interference of species present in the solution. This paper presents the different available methods for chemical analysis of cyanide: titration, specific electrode and distillation, giving special emphasis on the interferences problem, with the aim of helping in the interpretation of the results. (Author)

  20. Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions

    Science.gov (United States)

    Yang, Lei; Cheng, Zhe; Liu, Ze; Liu, Meilin

    2015-01-13

    Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.

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

    Directory of Open Access Journals (Sweden)

    Zhengde Tan

    2013-01-01

    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.

  2. New method for control over exciton states in quantum wells

    International Nuclear Information System (INIS)

    Maslov, A Yu; Proshina, O V

    2010-01-01

    The theoretical study of the exciton states in the quantum well is performed with regard to the distinctions of the dielectric properties of quantum well and barrier materials. The strong exciton-phonon interaction is shown to be possible in materials with high ionicity. This leads to the essential modification of the exciton states. The relationship between the exciton binding energy, along with oscillator strength and the barrier material dielectric properties is found. This suggests the feasibility of the exciton spectrum parameter control by the choice of the barrier material. It is shown that such exciton spectrum engineering also is possible in the quantum wells based on the materials with low ionicity. The reason is the dielectric confinement effect in the quantum wells.

  3. Quantum image pseudocolor coding based on the density-stratified method

    Science.gov (United States)

    Jiang, Nan; Wu, Wenya; Wang, Luo; Zhao, Na

    2015-05-01

    Pseudocolor processing is a branch of image enhancement. It dyes grayscale images to color images to make the images more beautiful or to highlight some parts on the images. This paper proposes a quantum image pseudocolor coding scheme based on the density-stratified method which defines a colormap and changes the density value from gray to color parallel according to the colormap. Firstly, two data structures: quantum image GQIR and quantum colormap QCR are reviewed or proposed. Then, the quantum density-stratified algorithm is presented. Based on them, the quantum realization in the form of circuits is given. The main advantages of the quantum version for pseudocolor processing over the classical approach are that it needs less memory and can speed up the computation. Two kinds of examples help us to describe the scheme further. Finally, the future work are analyzed.

  4. Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

    Science.gov (United States)

    Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

    2014-05-01

    The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

  5. Intra- und intermolecular hydrogen bonds. Spectroscopic, quantum chemical and molecular dynamics studies

    International Nuclear Information System (INIS)

    Simperler, A.

    1999-03-01

    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

  6. Analytic methods for field induced tunneling in quantum wells

    Indian Academy of Sciences (India)

    Analytic methods for field induced tunneling in quantum wells with arbitrary potential profiles ... Electric field induced tunneling is studied in three different types of quantum wells by solving time-independent effective mass ... Current Issue : Vol.

  7. Scholar-activating teaching materials for quantum physics. Pt. 2. Basic facts of quantum physics and heuristic methods

    International Nuclear Information System (INIS)

    Huebel, Horst

    2010-01-01

    Traditionally in the center of interest on quantum physics referring to schools the question lies, whether electrons and photons are now particles or waves, a question, which is often characterized by the phrase ''wave-particle dualism'', which notoriously not exists in its original meaning. Against that by the author - basing on important preparatory works of Kueblbeck and Mueller - a new concept for the treatment of quantum physics for the school was proposed, which puts ''basic facts'' in the foreground, comparable with the Kueblbeck-Mueller ''characteristic features''. The ''basic facts'' are similar to axioms of quantum physics, by means of which a large number of experiments and phenomena can be ''explained'' at least qualitatively - in a heuristic way -. Instead of the so-called ''wave-particle dualism'' here uncertainty and complementarity are put in the foreground. The new concept is in the Internet under http://www.forphys.de extensively presented with many further materials. In the partial volumes of this publication manifold and carefully elaborated teaching materials are presented, by means of which scholars can get themselves the partial set of quantum physics referring to schools by different methods like learn at stations, short referates, Internet research, group puzzle, the query-sheet or the card-index method etc. In the present 2. part materials for the ''basic facts'' of quantum physics are prepared, by which also modern experiments can be interpreted. Here deals it with the getting of knowledge and application of the ''basic Facts''. This pursues also by real scholar experiments, simulations and analogy tests. The scholars obtain so more simply than generally a deeper insight in quantum physics.

  8. Chemical Methods to Knock Down the Amyloid Proteins

    Directory of Open Access Journals (Sweden)

    Na Gao

    2017-06-01

    Full Text Available Amyloid proteins are closely related with amyloid diseases and do tremendous harm to human health. However, there is still a lack of effective strategies to treat these amyloid diseases, so it is important to develop novel methods. Accelerating the clearance of amyloid proteins is a favorable method for amyloid disease treatment. Recently, chemical methods for protein reduction have been developed and have attracted much attention. In this review, we focus on the latest progress of chemical methods that knock down amyloid proteins, including the proteolysis-targeting chimera (PROTAC strategy, the “recognition-cleavage” strategy, the chaperone-mediated autophagy (CMA strategy, the selectively light-activatable organic and inorganic molecules strategy and other chemical strategies.

  9. POSSIBLE NATURE OF THE RADIATION-INDUCED SIGNAL IN NAILS: HIGH-FIELD EPR, CONFIRMING CHEMICAL SYNTHESIS, AND QUANTUM CHEMICAL CALCULATIONS.

    Science.gov (United States)

    Tipikin, Dmitriy S; Swarts, Steven G; Sidabras, Jason W; Trompier, François; Swartz, Harold M

    2016-12-01

    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

  10. POSSIBLE NATURE OF THE RADIATION-INDUCED SIGNAL IN NAILS: HIGH-FIELD EPR, CONFIRMING CHEMICAL SYNTHESIS, AND QUANTUM CHEMICAL CALCULATIONS

    Science.gov (United States)

    Tipikin, Dmitriy S.; Swarts, Steven G.; Sidabras, Jason W.; Trompier, François; Swartz, Harold M.

    2016-01-01

    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

  11. Effect of drying methods on the chemical composition of three ...

    African Journals Online (AJOL)

    Three methods of drying (oven, sun and smoke) were used to dry Bonga spp., Sardinella spp. and Heterotis niloticus. The physico-chemical and minerals contents of the sample were determined using standard methods. Oven dried H. niloticus recorded the highest (16.42%) moisture content while the least moisture content ...

  12. A identification system for chemical warfare agents with PGNAA method

    International Nuclear Information System (INIS)

    Wang Bairong; Yin Guanghua; Yang Zhongping

    2006-01-01

    The principle and the experimental commanding of Chemical warfare Agents Identification with PGNAA method are discussed in this paper. The choosing of Detector, neutron source and the data processing method are detailed. Finally, a set of experimental instruments composed of Cf-232 and BGO detector is developed based on the theory discussed above. (authors)

  13. Identification system for chemical warfare agents with PGNAA method

    International Nuclear Information System (INIS)

    Wang Bairong; Yin Guanghua; Yang Zhongpin

    2007-01-01

    The principle and the experimental commanding of Chemical warfare Agents Identification with PGNAA method are discussed in this paper. The choosing of detector, neutron source and the data processing method are detailed. Finally, a set of experimental instruments composed of Cf-232 and BGO detector is developed based on this theory discussed above. (authors)

  14. Methods of uranium isotpic separation by chemical exchange chromatography

    International Nuclear Information System (INIS)

    Pena V, L.A.; Valle M, L.

    1985-01-01

    Chemical exchange chromatography as applied to isotope separation has undergone a constant development during the last few years. The results so far indicate that this method could eventually become commercially useful. This work presents a critical review of the experimental methods presently under study by principal research groups, and which have not get been compared. (Author)

  15. Insights: A New Method to Balance Chemical Equations.

    Science.gov (United States)

    Garcia, Arcesio

    1987-01-01

    Describes a method designed to balance oxidation-reduction chemical equations. Outlines a method which is based on changes in the oxidation number that can be applied to both molecular reactions and ionic reactions. Provides examples and delineates the steps to follow for each type of equation balancing. (TW)

  16. New methods of sup(111)In chemical separation

    International Nuclear Information System (INIS)

    Santos, D.F.; Osso Junior, J.A.; Bastos, M.A.V.; Britto, J.L.Q.; Silva, R.F.

    1986-01-01

    The cation exchange and thermochromatography methods for chemical separation of sup(111) In from silver targets are described. The cation exchange method is based on the difference between In and Ag distribution coefficients on cation exchange resin treated with HNO sub(3). The thermochromatography consists of indium diffusion on silver melted after sublimation and posterior condensation. (M.C.K.)

  17. Chemically modulated graphene quantum dot for tuning the photoluminescence as novel sensory probe

    Science.gov (United States)

    Hwang, Eunhee; Hwang, Hee Min; Shin, Yonghun; Yoon, Yeoheung; Lee, Hanleem; Yang, Junghee; Bak, Sora; Lee, Hyoyoung

    2016-12-01

    A band gap tuning of environmental-friendly graphene quantum dot (GQD) becomes a keen interest for novel applications such as photoluminescence (PL) sensor. Here, for tuning the band gap of GQD, a hexafluorohydroxypropanyl benzene (HFHPB) group acted as a receptor of a chemical warfare agent was chemically attached on the GQD via the diazonium coupling reaction of HFHPB diazonium salt, providing new HFHPB-GQD material. With a help of the electron withdrawing HFHPB group, the energy band gap of the HFHPB-GQD was widened and its PL decay life time decreased. As designed, after addition of dimethyl methyl phosphonate (DMMP), the PL intensity of HFHPB-GQD sensor sharply increased up to approximately 200% through a hydrogen bond with DMMP. The fast response and short recovery time was proven by quartz crystal microbalance (QCM) analysis. This HFHPB-GQD sensor shows highly sensitive to DMMP in comparison with GQD sensor without HFHPB and graphene. In addition, the HFHPB-GQD sensor showed high selectivity only to the phosphonate functional group among many other analytes and also stable enough for real device applications. Thus, the tuning of the band gap of the photoluminescent GQDs may open up new promising strategies for the molecular detection of target substrates.

  18. Quantum chemical and thermodynamic calculations of fulvic and humic copper complexes in reactions of malachite and azurite formation

    International Nuclear Information System (INIS)

    Fomin, Vitaliy N.; Gogol, Daniil B.; Rozhkovoy, Ivan E.; Ponomarev, Dmitriy L.

    2017-01-01

    This article provides a thermodynamic evaluation of the reactions of humic and fulvic acids in the process of malachite and azurite mineralogenesis. Semi-empirical methods AM/1, MNDO, PM3, PM5, PM6 and PM7 were used to compute the heat of formation, enthalpy and entropy for thermodynamic calculations of the reactions performed on the basis of Hess's law. It is shown that methods PM6 and PM7 in the MOPAC software package provide good compliance with experimental and calculated heats of formation for copper complexes and alkaline earth metal complexes with organic acids. It is found that the malachite and azurite formation processes involving humus complexing substances are thermodynamically possible. - Highlights: • Copper and alkali-earth metal complexes with humic and fulvic acids are considered. • Quantum chemical calculation of thermodynamics for the structures was performed. • Semi-empirical methods PM6 and PM7 provide best correlation for the properties. • Parameters of basic copper carbonate formation reactions were obtained by Hess's law. • Processes of malachite and azurite formation from humus complexes are possible.

  19. 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.

    1985-01-01

    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

  20. X-ray diffraction, vibrational and quantum chemical investigations of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid

    Science.gov (United States)

    Arjunan, V.; Marchewka, Mariusz K.; Pietraszko, A.; Kalaivani, M.

    2012-11-01

    The structural investigations of the molecular complex of 2-methyl-4-nitroaniline with trichloroacetic acid, namely 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid (C11H10Cl6N2O6) have been performed by means of single crystal and powder X-ray diffraction method. The complex was formed with accompanying proton transfer from trichloroacetic acid molecule to 2-methyl-4-nitroaniline. The studied crystal is built up of singly protonated 2-methyl-4-nitroanilinium cations, trichloroacetate anions and neutral trichloroacetic acid molecules. The crystals are monoclinic, space group P21/c, with a = 14.947 Å, b = 6.432 Å, c = 19.609 Å and Z = 4. The vibrational assignments and analysis of 2-methyl-4-nitroanilinium trichloroacetate trichloroacetic acid have also been performed by FTIR, FT-Raman and far-infrared spectral studies. More support on the experimental findings were added from the quantum chemical studies performed with DFT (B3LYP) method using 6-31G**, cc-pVDZ, 6-31G and 6-31++G basis sets. The structural parameters, energies, thermodynamic parameters and the NBO charges of 2M4NATCA were also determined by the DFT methods.

  1. Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

    International Nuclear Information System (INIS)

    Li, Guanchen; Al-Abbasi, Omar; Von Spakovsky, Michael R

    2014-01-01

    This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H 2 ↔ FH + H

  2. Functional methods underlying classical mechanics, relativity and quantum theory

    International Nuclear Information System (INIS)

    Kryukov, A

    2013-01-01

    The paper investigates the physical content of a recently proposed mathematical framework that unifies the standard formalisms of classical mechanics, relativity and quantum theory. In the framework states of a classical particle are identified with Dirac delta functions. The classical space is ''made'' of these functions and becomes a submanifold in a Hilbert space of states of the particle. The resulting embedding of the classical space into the space of states is highly non-trivial and accounts for numerous deep relations between classical and quantum physics and relativity. One of the most striking results is the proof that the normal probability distribution of position of a macroscopic particle (equivalently, position of the corresponding delta state within the classical space submanifold) yields the Born rule for transitions between arbitrary quantum states.

  3. Intramolecular tautomerisation and the conformational variability of some classical mutagens – cytosine derivatives: quantum chemical study

    Directory of Open Access Journals (Sweden)

    Hovorun D. M.

    2011-04-01

    Full Text Available Aim. To determine the lifetime of the mutagenic cytosine derivatives through the investigation of the physicochemical mechanisms of their intramolecular proton transfer. Methods. Non-empirical quantum chemistry, the analysis of the electron density by means of Bader’s atoms in molecules (AIM theory and physicochemical kinetics were used. Results. It is shown that the modification of all investigated compounds, except DCyt, prevents their pairing in both mutagenic and canonical tautomeric forms with a base which is an interacting partner. This effect can inhibit their mutagenic potential. It is also established that Watson-Crick tautomeric hypothesis can be formally expanded for the investigated molecules so far as a lifetime of the mutagenic tautomers much more exceeds characteristic time for the incorporation of one nucleotides pair by DNA biosynthesis machinery. It seems that just within the frame of this hypothesis it will be possible to give an adequate explanation of the mechanisms of mutagenic action of N4-aminocytosine, N4-methoxycytosine, N4-hydroxycytosine and N4dehydrocytosine, which have much more energy advantageous imino form in comparison with amino form. Conclusions. For the first time the comprehensive conformational analysis of a number of classical mutagens, namely cytosine derivatives, has been performed using the methods of non-empirical quantum chemistry at the MP2/6-311++G (2df,pd//B3LYP/6-311++G(d,p level of theory

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

    KAUST Repository

    Risko, Chad

    2011-03-15

    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.

  5. Mixed quantum-classical studies of energy partitioning in unimolecular chemical reactions

    Science.gov (United States)

    Bladow, Landon Lowell

    A mixed quantum-classical reaction path Hamiltonian method is utilized to study the dynamics of unimolecular reactions. The method treats motion along the reaction path classically and treats the transverse vibrations quantum mechanically. The theory leads to equations that predict the disposai of the exit-channel potential energy to product translation and vibration. In addition, vibrational state distributions are obtained for the product normal modes. Vibrational excitation results from the curvature of the minimum energy reaction path. The method is applied to six unimolecular reactions: HF elimination from fluoroethane, 1,1-difluoroethane, 1,1-difluoroethene, and trifluoromethane; and HCl elimination from chloroethane and acetyl chloride. The minimum energy paths were calculated at either the MP2 or B3LYP level of theory. In all cases, the majority of the vibrational excitation of the products occurs in the HX fragment. The results are compared to experimental data and other theoretical results, where available. The best agreement between the experimental and calculated HX vibrational distributions is found for the halogenated ethanes, and the experimental deduction that the majority of the HX vibrational excitation arises from the potential energy release is supported. It is believed that the excess energy provided in experiments contributes to the poorer agreement between experiment and theory observed for HF elimination from 1,1-difluoroethene and trifluoromethane. An attempt is described to incorporate a treatment of the excess energy into the present method. However, the sign of the curvature coupling elements is then found to affect the dynamics. Overall, the method appears to be an efficient dynamical tool for modeling the disposal of the exit-channel potential energy in unimolecular reactions.

  6. Molcas 8: New capabilities for multiconfigurational quantum chemical calculations across the periodic table.

    Science.gov (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

    2016-02-15

    In this report, we summarize and describe the recent unique updates and additions to the Molcas quantum chemistry program suite as contained in release version 8. These updates include natural and spin orbitals for studies of magnetic properties, local and linear scaling methods for the Douglas-Kroll-Hess transformation, the generalized active space concept in MCSCF methods, a combination of multiconfigurational wave functions with density functional theory in the MC-PDFT method, additional methods for computation of magnetic properties, methods for diabatization, analytical gradients of state average complete active space SCF in association with density fitting, methods for constrained fragment optimization, large-scale parallel multireference configuration interaction including analytic gradients via the interface to the Columbus package, and approximations of the CASPT2 method to be used for computations of large systems. In addition, the report includes the description of a computational machinery for nonlinear optical spectroscopy through an interface to the QM/MM package Cobramm. Further, a module to run molecular dynamics simulations is added, two surface hopping algorithms are included to enable nonadiabatic calculations, and the DQ method for diabatization is added. Finally, we report on the subject of improvements with respects to alternative file options and parallelization. © 2015 Wiley Periodicals, Inc.

  7. Molecular structure of tris(cyclopropylsilyl)amine as determined by gas electron diffraction and quantum-chemical calculations

    Science.gov (United States)

    Vishnevskiy, Yuri V.; Abaev, Maxim A.; Ivanov, Arkadii A.; Vilkov, Lev V.; Dakkouri, Marwan

    2008-10-01

    The molecular structure and conformation of tris(cyclopropylsilyl)amine (TCPSA) has been studied by means of gas-phase electron diffraction at 338 K and quantum-chemical calculations. A total of 12 relatively stable conformations of TCPSA molecule were considered. According to the experimental results and the DFT calculations the most stable conformer corresponds to a configuration (according to the Prelog-Klyne notation) of the type (-ac)(-ac)(+ac)-(-ac)(-ac)(+ac), where the first three parentheses describe the three different Si-N-Si-C torsional angles and the latter ones depict the rotation of the three cyclopropyl groups about the C ring-Si axes, respectively. The quantum-mechanical calculations were performed using various density functional (B3LYP, X3LYP and O3LYP) and perturbation MP2 methods in combination with double- and triple- ζ basis sets plus polarization and diffuse functions. The most important experimental geometrical parameters of TCPSA ( ra Å, ∠ h1 degrees) are: (Si-N) av = 1.741(3), (Si-C) av = 1.866(4), (C-C) av = 1.510(3), (C-C(Si)) av = 1.535(3), (N-Si-C) av = 115.1(18)°. For the purpose of comparison and searching for reasons leading to the planarity of the Si 3N moiety in trisilylated amines we carried out NBO analysis and optimized the geometries of numerous silylamines. Among these compounds was tris(allylsilyl)amine (TASA), which is isovalent and isoelectronic to TCPSA. Utilizing the structural results we obtained we could show that Si +⋯Si + electrostatic repulsive interaction is predominantly responsible for the planarity of the Si 3N skeleton in TCPSA and in all other trisilylamines we considered. We also found that regardless the size and partial charges of the substituents the Si-N-Si bond angle in various disilylamines amounts to 130 ± 2°.

  8. FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin

    Science.gov (United States)

    Arjunan, V.; Sakiladevi, S.; Marchewka, M. K.; Mohan, S.

    2013-05-01

    3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm-1, respectively. 1H and 13C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G**, high level 6-311++G** and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method.

  9. Introduction to functional and path integral methods in quantum field theory

    International Nuclear Information System (INIS)

    Strathdee, J.

    1991-11-01

    The following aspects concerning the use of functional and path integral methods in quantum field theory are discussed: generating functionals and the effective action, perturbation series, Yang-Mills theory and BRST symmetry. 10 refs, 3 figs

  10. Method of evaluation of structural (screen) and quantum graininess of X-ray pictures

    Energy Technology Data Exchange (ETDEWEB)

    Gurvich, A M; Shamanov, A A; Erofeeva, N D [Nauchno-Issledovatel' skij Inst. Rentgenologii i Radiologii, Moscow (USSR)

    1979-03-01

    Proposed is a method for quantitative determination of graininess of X-ray pictures (gamma-ray images), the graininess being conditioned by the structure of amplifying screens and quantum fluctuations. The method is based on the determination of threshold brightness at which the picture graininess becomes obvious. It is shown that at low effective quantum energy (Esub(eff.) <= 50 keV) the graininess observed is for the most part structural (screen). Its growth is connected with quantum fluctuations when increasing Esub(eff.) up to 150 keV and using screens with high output values of X-ray luminescence and the coefficient of spectral accordance to the film.

  11. Quantum mechanical simulation methods for studying biological systems

    International Nuclear Information System (INIS)

    Bicout, D.; Field, M.

    1996-01-01

    Most known biological mechanisms can be explained using fundamental laws of physics and chemistry and a full understanding of biological processes requires a multidisciplinary approach in which all the tools of biology, chemistry and physics are employed. An area of research becoming increasingly important is the theoretical study of biological macromolecules where numerical experimentation plays a double role of establishing a link between theoretical models and predictions and allowing a quantitative comparison between experiments and models. This workshop brought researchers working on different aspects of the development and application of quantum mechanical simulation together, assessed the state-of-the-art in the field and highlighted directions for future research. Fourteen lectures (theoretical courses and specialized seminars) deal with following themes: 1) quantum mechanical calculations of large systems, 2) ab initio molecular dynamics where the calculation of the wavefunction and hence the energy and forces on the atoms for a system at a single nuclear configuration are combined with classical molecular dynamics algorithms in order to perform simulations which use a quantum mechanical potential energy surface, 3) quantum dynamical simulations, electron and proton transfer processes in proteins and in solutions and finally, 4) free seminars that helped to enlarge the scope of the workshop. (N.T.)

  12. 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

    2015-03-01

    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.

  13. Quantum chemical study of the structure, spectroscopy and reactivity of NO+.(H2O) n=1-5 clusters.

    Science.gov (United States)

    Linton, Kirsty A; Wright, Timothy G; Besley, Nicholas A

    2018-03-13

    Quantum chemical methods including Møller-Plesset perturbation (MP2) theory and density functional theory (DFT) have been used to study the structure, spectroscopy and reactivity of NO + (H 2 O) n =1-5 clusters. MP2/6-311++G** calculations are shown to describe the structure and spectroscopy of the clusters well. DFT calculations with exchange-correlation functionals with a low fraction of Hartree-Fock exchange give a binding energy of NO + (H 2 O) that is too high and incorrectly predict the lowest energy structure of NO + (H 2 O) 2 , and this error may be associated with a delocalization of charge onto the water molecule directly binding to NO + Ab initio molecular dynamics (AIMD) simulations were performed to study the NO + (H 2 O) 5 [Formula: see text] H + (H 2 O) 4 + HONO reaction to investigate the formation of HONO from NO + (H 2 O) 5 Whether an intracluster reaction to form HONO is observed depends on the level of electronic structure theory used. Of note is that methods that accurately describe the relative energies of the product and reactant clusters did not show reactions on the timescales studied. This suggests that in the upper atmosphere the reaction may occur owing to the energy present in the NO + (H 2 O) 5 complex following its formation.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

  14. Fluorescent carbon quantum dots synthesized by chemical vapor deposition: An alternative candidate for electron acceptor in polymer solar cells

    Science.gov (United States)

    Cui, Bo; Yan, Lingpeng; Gu, Huimin; Yang, Yongzhen; Liu, Xuguang; Ma, Chang-Qi; Chen, Yongkang; Jia, Husheng

    2018-01-01

    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.

  15. A semiclassical method in the theory of light scattering by semiconductor quantum dots

    International Nuclear Information System (INIS)

    Lang, I. G.; Korovin, L. I.; Pavlov, S. T.

    2008-01-01

    A semiclassical method is proposed for the theoretical description of elastic light scattering by arbitrary semiconductor quantum dots under conditions of size quantization. This method involves retarded potentials and allows one to dispense with boundary conditions for electric and magnetic fields. Exact results for the Umov-Poynting vector at large distances from quantum dots in the case of monochromatic and pulsed irradiation and formulas for differential scattering cross sections are obtained

  16. Stochastic methods for the fermion determinant in lattice quantum chromodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Finkenrath, Jacob Friedrich

    2015-02-17

    In this thesis, algorithms in lattice quantum chromodynamics are presented by developing and using stochastic methods for fermion determinant ratios. For that an integral representation is proved which can be used also for non hermitian matrices. The stochastic estimation or the Monte Carlo integration of this integral representation introduces stochastic fluctuations which are controlled by using Domain Decomposition of the Dirac operator and introducing interpolation techniques. Determinant ratios of the lattice fermion operator, here the Wilson Dirac operator, are needed for corrections of the Boltzmann weight. These corrections have interesting applications e.g. in the mass by using mass reweighting. It will be shown that mass reweighting can be used e.g. to improve extrapolation in the light quark mass towards the chiral or physical point or to introduce an isospin breaking by splitting up the mass of the light quark. Furthermore the extraction of the light quark masses will be shown by using dynamical 2 flavor CLS ensembles. Stochastic estimation of determinant ratios can be used in Monte Carlo algorithms, e.g. in the Partial Stochastic Multi Step algorithm which can sample two mass-degenerate quarks. The idea is to propose a new configuration weighted by the pure gauge weight and including afterwards the fermion weight by using Metropolis accept-reject steps. It is shown by using an adequate interpolation with relative gauge fixing and a hierarchical filter structure that it is possible to simulate moderate lattices up to (2.1 fm){sup 4}. Furthermore the iteration of the pure gauge update can be increased which can decouple long autocorrelation times from the weighting with the fermions. Moreover a novel Hybrid Monte Carlo algorithm based on Domain Decomposition and combined with mass reweighting is presented. By using Domain Decomposition it is possible to split up the mass term in the Schur complement and the block operators. By introducing a higher mass

  17. Coupled quantum-classical method for long range charge transfer: relevance of the nuclear motion to the quantum electron dynamics

    International Nuclear Information System (INIS)

    Da Silva, Robson; Hoff, Diego A; Rego, Luis G C

    2015-01-01

    Charge and excitonic-energy transfer phenomena are fundamental for energy conversion in solar cells as well as artificial photosynthesis. Currently, much interest is being paid to light-harvesting and energy transduction processes in supramolecular structures, where nuclear dynamics has a major influence on electronic quantum dynamics. For this reason, the simulation of long range electron transfer in supramolecular structures, under environmental conditions described within an atomistic framework, has been a difficult problem to study. This work describes a coupled quantum mechanics/molecular mechanics method that aims at describing long range charge transfer processes in supramolecular systems, taking into account the atomistic details of large molecular structures, the underlying nuclear motion, and environmental effects. The method is applied to investigate the relevance of electron–nuclei interaction on the mechanisms for photo-induced electron–hole pair separation in dye-sensitized interfaces as well as electronic dynamics in molecular structures. (paper)

  18. APPLICATION OF CHEMICAL METHODS TO THE SOLID WASTE MANAGEMENT

    Directory of Open Access Journals (Sweden)

    C. P. Bulimaga

    2008-12-01

    Full Text Available The present article is a synthesis analysis of application of chemical methods for the development of technologies of hazardous waste management. Here are offered some technologies of neutralization of the waste containing hexacyanofferates, galvanic wastes and those with contain of vanadium, which are collected at Power Thermoelectric Plants.

  19. Comparison of traditional physico-chemical methods and molecular ...

    African Journals Online (AJOL)

    This study was aim to review the efficiency of molecular markers and traditional physico-chemical methods for the identification of basmati rice. The study involved 44 promising varieties of Indica rices collected from geographically distant places and adapted to irrigated and aerobic agro-ecosystems. Quality data for ...

  20. Effect of integration of cultural, botanical, and chemical methods of ...

    African Journals Online (AJOL)

    A field experiment was conducted from November 2011 to June 2013 to evaluate the effects of botanical, cultural, and chemical methods on termite colony survival, crop and wooden damage, and other biological activities in Ghimbi district of western Ethiopia. The termite mounds were dug and the following treatments were ...

  1. Electrochemical and chemical methods of metallizing plastic films

    OpenAIRE

    Chapples, J.

    1991-01-01

    This thesis describes two novel techniques for the metallization of non-electroactive polymer films and thicker sectioned polyethylene and nylon substrates. In the first approach, non-electroactive polymer substrates were impregnated with surface layers of polypyrrole and polyaniline, using electrochemical and chemical methods of polymerization. The relative merits of both these approaches are discussed and compared with other methods in the literature. The resultant composi...

  2. Synthesis, vibrational, NMR, quantum chemical and structure-activity relation studies of 2-hydroxy-4-methoxyacetophenone.

    Science.gov (United States)

    Arjunan, V; Devi, L; Subbalakshmi, R; Rani, T; Mohan, S

    2014-09-15

    The stable geometry of 2-hydroxy-4-methoxyacetophenone is optimised by DFT/B3LYP method with 6-311++G(∗∗) and cc-pVTZ basis sets. The structural parameters, thermodynamic properties and vibrational frequencies of the optimised geometry have been determined. The effects of substituents (hydroxyl, methoxy and acetyl groups) on the benzene ring vibrational frequencies are analysed. The vibrational frequencies of the fundamental modes of 2-hydroxy-4-methoxyacetophenone have been precisely assigned and analysed and the theoretical results are compared with the experimental vibrations. 1H and 13C NMR isotropic chemical shifts are calculated and assignments made are compared with the experimental values. The energies of important MO's, the total electron density and electrostatic potential of the compound are determined. Various reactivity and selectivity descriptors such as chemical hardness, chemical potential, softness, electrophilicity, nucleophilicity and the appropriate local quantities are calculated. Copyright © 2014 Elsevier B.V. All rights reserved.

  3. Soil chemical sensor and precision agricultural chemical delivery system and method

    Science.gov (United States)

    Colburn, Jr., John W.

    1991-01-01

    A real time soil chemical sensor and precision agricultural chemical delivery system includes a plurality of ground-engaging tools in association with individual soil sensors which measure soil chemical levels. The system includes the addition of a solvent which rapidly saturates the soil/tool interface to form a conductive solution of chemicals leached from the soil. A multivalent electrode, positioned within a multivalent frame of the ground-engaging tool, applies a voltage or impresses a current between the electrode and the tool frame. A real-time soil chemical sensor and controller senses the electrochemical reaction resulting from the application of the voltage or current to the leachate, measures it by resistivity methods, and compares it against pre-set resistivity levels for substances leached by the solvent. Still greater precision is obtained by calibrating for the secondary current impressed through solvent-less soil. The appropriate concentration is then found and the servo-controlled delivery system applies the appropriate amount of fertilizer or agricultural chemicals substantially in the location from which the soil measurement was taken.

  4. New methods for the measurement and alteration of quantum states

    International Nuclear Information System (INIS)

    Steuernagel, O.

    1996-01-01

    Themes of this thesis are the mathematical representation, measurement-technical reconstruction, and preparation of quantum states as well as their alteration by measurement. The main topics of the considerations are quantum-mechanical system states, the complet description of which pursues by means of density operators. The first chapter presents a general mathematical scheme for the representaion of density operators by means of projection operators. The second chapter explains a scheme for the syntehsis of Fock states by means of a linear mixer. The third chapter answers the question, whether spontaneous emitted light, which is emitted by an atom with large spatial extension, can show self-interferences and lets conclude on thee coherent structure of the c.m. wave function of the emitting atom. The last chapter reconstructs measurement results on the coherence loss of atoms in an atomic-beam experiment by spontaneous emission in the language of the density-operator formalism

  5. 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

    2013-01-01

    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)

  6. Molecular Structure of Phenytoin: NMR, UV-Vis and Quantum Chemical Calculations

    Directory of Open Access Journals (Sweden)

    Raluca Luchian

    2015-12-01

    Full Text Available Due to the presence of the carbonyl and imide groups in the structure of 5,5-diphenylhydantoin (DPH, the possibility for this compound to be involved in hydrogen bonding intermolecular interactions is obvious. Even though such interactions are presumably responsible for the mechanism of action of this drug, however, to the best of our knowledge, the self-hydrogen bonding interactions between the DPH monomers have not been addressed till now. Furthermore, studies reporting on the spectroscopic characteristics of this molecule are scarcely reported in the literature. Here we report on the possible dimers of DPH, investigated by quantum chemical calculations at B3LYP/6-31+G(2d,2p level of theory. Twelve unique DPH dimers were structurally optimized in gas-phase, as well as in ethanol and DMSO and then were used to compute the population-averaged UV-Vis and NMR spectra using Boltzmann statistics. UV-Vis and NMR techniques were employed to assess experimentally the spectroscopical response of this compound. DFT calculations are also used to investigate the structural transformations between the solid and liquid phase, as well as for describing the electronic transitions and for the assignment of NMR spectra of DPH.

  7. 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.

    2014-01-01

    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

  8. Thiobenzamide: Structure of a free molecule as studied by gas electron diffraction and quantum chemical calculations

    Science.gov (United States)

    Kolesnikova, Inna N.; Putkov, Andrei E.; Rykov, Anatolii N.; Shishkov, Igor F.

    2018-06-01

    The equilibrium (re) molecular structure of thiobenzamide along with rh1 structure has been determined in gas phase using gas electron-diffraction (GED) at about 127 °C and quantum-chemical calculations (QC). Rovibrational distance corrections to the thermal averaged GED structure have been computed with anharmonic force constants obtained at the MP2/cc-pVTZ level of theory. According to the results of GED and QC thiobenzamide exists as mixture of two non-planar enantiomers of C1 symmetry. The selected equilibrium geometrical parameters of thiobenzamide (re, Å and ∠e, deg) are the following: (Cdbnd S) = 1.641(4), (Csbnd N) = 1.352(2), (Csbnd C) = 1.478(9), (Cdbnd C)av = 1.395(2), CCN = 114.7(5), CCS = 123.4(5), C2C1C7S = 31(4), C6C1C7N = 29(4). The structure of thiobenzamide in the gas phase is markedly different to that in the literature for the single crystal. The differences between the gas and the solid structures are ascribed to the presence of intermolecular hydrogen bonding in the solid phase.

  9. Quantum chemical spectral characterization of CH2NH2+ for remote sensing of Titan's atmosphere

    Science.gov (United States)

    Thackston, Russell; Fortenberry, Ryan C.

    2018-01-01

    Cassini has shown that CH2NH2+ is likely present in relatively high abundance in Titan's upper atmosphere. Relatively little is known about this molecule even though it contains the same number of electrons as ethylene, a molecule of significance to Titan's chemistry. Any studies on CH2NH2+ with application to Titan or its atmospheric chemistry will have to be done remotely at this point with the end of the fruitful Cassini mission. Consequently, trusted quantum chemical techniques are utilized here to produce the rotational, vibrational, and rovibrational spectroscopic constants for CH2NH2+ for the first time. The methodology produces a tightly fit potential energy surface here that is well-behaved indicating a strong credence in the accuracy for the produced values. Most notably, the 884.1 cm-1 NH2 out-of-plane bend is the brightest of the vibrational frequencies reported here for CH2NH2+ , and an observed and unattributed feature in this spectral region has been documented but never assigned to a molecular carrier. Follow-up IR or radio observations making use of the 540 GHz to 660 GHz range with the 0.45 D molecular dipole moment will have to be undertaken in order to confirm this or any attribution, but the data provided in this work will greatly assist in any such studies related to CH2NH2+.

  10. The Nature of the Interactions in Triethanolammonium-Based Ionic Liquids. A Quantum Chemical Study.

    Science.gov (United States)

    Fedorova, Irina V; Safonova, Lyubov P

    2018-05-10

    Structural features and interionic interactions play a crucial role in determining the overall stability of ionic liquids and their physicochemical properties. Therefore, we performed high-level quantum-chemical study of different cation-anion pairs representing the building units of protic ionic liquids based on triethanolammonium cation and anions of sulfuric, nitric, phosphoric, and phosphorus acids to provide essential insight into these phenomena at the molecular level. It was shown that every structure is stabilized through multiple H bonds between the protons in the N-H and O-H groups of the cation and different oxygen atoms of the anion acid. Using atoms in molecules topological parameters and natural bond orbital analysis, we determined the nature and strength of these interactions. Our calculations suggest that the N-H group of the cation has more proton donor-like character than the O-H group that makes the N-H···O hydrogen bonds stronger. A close relation between the binding energies of these ion pairs and experimental melting points was established: the smaller the absolute value of the binding energy between ions, the lower is the melting point.

  11. Silicon Oxysulfide, OSiS: Rotational Spectrum, Quantum-Chemical Calculations, and Equilibrium Structure.

    Science.gov (United States)

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

    2011-06-02

    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.

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

    Directory of Open Access Journals (Sweden)

    Tibebe Lemma

    2017-12-01

    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.

  13. Method of making an improved superconducting quantum interference device

    International Nuclear Information System (INIS)

    Wu, C.T.; Falco, C.M.; Kampwirth, R.T.

    1977-01-01

    An improved superconducting quantum interference device is made by sputtering a thin film of an alloy of three parts niobium to one part tin in a pattern comprising a closed loop with a narrow region, depositing a thin film of a radiation shield such as copper over the niobium-tin, scribing a narrow line in the copper over the narrow region, exposing the structure at the scribed line to radiation and removing the deposited copper

  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

    2007-01-01

    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

    2009-01-01

    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. Kinetic-quantum chemical model for catalytic cycles: the Haber-Bosch process and the effect of reagent concentration.

    Science.gov (United States)

    Kozuch, Sebastian; Shaik, Sason

    2008-07-03

    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.

  17. Manual of selected physico-chemical analytical methods. IV

    International Nuclear Information System (INIS)

    Beran, M.; Klosova, E.; Krtil, J.; Sus, F.; Kuvik, V.; Vrbova, L.; Hamplova, M.; Lengyel, J.; Kelnar, L.; Zakouril, K.

    1990-11-01

    The Central Testing Laboratory of the Nuclear Research Institute at Rez has for a decade been participating in the development of analytical procedures and has been providing analyses of samples of different types and origin. The analytical procedures developed have been published in special journals and a number of them in the Manuals of analytical methods, in three parts. The 4th part of the Manual contains selected physico-chemical methods developed or modified by the Laboratory in the years 1986-1990 within the project ''Development of physico-chemical analytical methods''. In most cases, techniques are involved for non-nuclear applications. Some can find wider applications, especially in analyses of environmental samples. Others have been developed for specific cases of sample analyses or require special instrumentation (mass spectrometer), which partly restricts their applicability by other institutions. (author)

  18. Method for fractional solid-waste sampling and chemical analysis

    DEFF Research Database (Denmark)

    Riber, Christian; Rodushkin, I.; Spliid, Henrik

    2007-01-01

    four subsampling methods and five digestion methods, paying attention to the heterogeneity and the material characteristics of the waste fractions, it was possible to determine 61 substances with low detection limits, reasonable variance, and high accuracy. For most of the substances of environmental...... of variance (20-85% of the overall variation). Only by increasing the sample size significantly can this variance be reduced. The accuracy and short-term reproducibility of the chemical characterization were good, as determined by the analysis of several relevant certified reference materials. Typically, six...... to eight different certified reference materials representing a range of concentrations levels and matrix characteristics were included. Based on the documentation provided, the methods introduced were considered satisfactory for characterization of the chemical composition of waste-material fractions...

  19. Non-local currents in 2D QFT: an alternative To - the quantum inverse scattering method

    International Nuclear Information System (INIS)

    Bernard, D.; Leclair, A.; Cornell Univ., Ithaca, NY

    1990-01-01

    The formalism based on non-local charges that we propose provides an alternative to the quantum inverse scattering method for solving integrable quantum field theories in 2D. The content of the paper is: 1. Introduction: historical background. 2. The NLC approach to 2D QFT: a summary. 3 Exchange algebras and on-shell conservation laws: why non-local charges are useful. 4. The lattice construction: the geometrical origin of non-local conserved currents. 5. The continuum construction: how to deal with non-local conserved currents. 6. Examples: Yangian and quantum group currents. 7 Conclusions: open problems. 22 refs., 4 figs

  20. Method for innovative synthesis-design of chemical process flowsheets

    DEFF Research Database (Denmark)

    Kumar Tula, Anjan; Gani, Rafiqul

    Chemical process synthesis-design involve the identification of the processing route to reach a desired product from a specified set of raw materials, design of the operations involved in the processing route, the calculations of utility requirements, the calculations of waste and emission...... to the surrounding and many more. Different methods (knowledge-based [1], mathematical programming [2], hybrid, etc.) have been proposed and are also currently employed to solve these synthesis-design problems. D’ Anterroches [3] proposed a group contribution based approach to solve the synthesis-design problem...... of chemical processes, where, chemical process flowsheets could be synthesized in the same way as atoms or groups of atoms are synthesized to form molecules in computer aided molecular design (CAMD) techniques [4]. That, from a library of building blocks (functional process-groups) and a set of rules to join...

  1. 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.

    2006-01-01

    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

  2. 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: arvids@utpl.edu.ec; 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)

    2006-05-31

    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.

  3. A quantum-chemical study of oxygen-vacancy defects in PbTiO3 crystals

    International Nuclear Information System (INIS)

    Stashans, Arvids; Serrano, Sheyla; Medina, Paul

    2006-01-01

    Investigation of an oxygen vacancy and F center in the cubic and tetragonal lattices of PbTiO 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

  4. Comparison of Methods for Computing the Exchange Energy of quantum helium and hydrogen

    International Nuclear Information System (INIS)

    Cayao, J. L. C. D.

    2009-01-01

    I investigate approach methods to find the exchange energy for quantum helium and hydrogen. I focus on Heitler-London, Hund-Mullikan, Molecular Orbital and variational approach methods. I use Fock-Darwin states centered at the potential minima as the single electron wavefunctions. Using these we build Slater determinants as the basis for the two electron problem. I do a comparison of methods for two electron double dot (quantum hydrogen) and for two electron single dot (quantum helium) in zero and finite magnetic field. I show that the variational, Hund-Mullikan and Heitler-London methods are in agreement with the exact solutions. Also I show that the exchange energy calculation by Heitler-London (HL) method is an excellent approximation for large inter dot distances and for single dot in magnetic field is an excellent approximation the Variational method. (author)

  5. Quantum Chemical Calculations Using Accelerators: Migrating Matrix Operations to the NVIDIA Kepler GPU and the Intel Xeon Phi.

    Science.gov (United States)

    Leang, Sarom S; Rendell, Alistair P; Gordon, Mark S

    2014-03-11

    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.

  6. Molecular dynamic and quantum chemical calculations for phthalazine derivatives as corrosion inhibitors of mild steel in 1 M HCl

    Energy Technology Data Exchange (ETDEWEB)

    Musa, Ahmed Y., E-mail: AMUSA6@UWO.CA [Department of Chemistry, University of Western Ontario, 1151 Richmond Street, London, Ontario, N6A 5B7 (Canada); Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi, 43600 Selangor (Malaysia); Jalgham, Ramzi T.T.; Mohamad, Abu Bakar [Department of Chemical and Process Engineering, Universiti Kebangsaan Malaysia, Bangi, 43600 Selangor (Malaysia)

    2012-03-15

    Highlights: Black-Right-Pointing-Pointer The inhibition of three phthalazine derivatives was studied. Black-Right-Pointing-Pointer The inhibition efficiency increased in the following order: PTD < PT < PTO. Black-Right-Pointing-Pointer The adsorption energies were calculated using molecular dynamics simulations. Black-Right-Pointing-Pointer Quantum chemical parameters were calculated using the AM1, MNDO and PM3 methods. Black-Right-Pointing-Pointer The adsorption of phthalazine derivatives obeys the Langmuir adsorption isotherm. - Abstract: The abilities of phthalazine derivatives, including phthalazine (PT), phthalazone (PTO) and phthalhydrazide (PTD), to inhibit the corrosion of mild steel in 1 M HCl at 30 Degree-Sign C were studied using electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. Theoretical calculations were performed to investigate the electronic structures of the PT derivatives. Our results showed that the inhibition efficiencies of these derivatives improved with increases in concentration. The data also showed that PTD < PT < PTO in terms of the inhibiting efficiency. Theoretical calculations also revealed that PTO is expected to be the best inhibitor among the studied phthalazine derivatives.

  7. Electrochemical and quantum chemical studies of some indole derivatives as corrosion inhibitors for C38 steel in molar hydrochloric acid

    International Nuclear Information System (INIS)

    Lebrini, M.; Robert, F.; Vezin, H.; Roos, C.

    2010-01-01

    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 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 ΔG ads 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).

  8. Structure, vibrations and quantum chemical investigations of hydrogen bonded complex of bis(1-hydroxy-2-methylpropan-2-aminium)selenate

    Science.gov (United States)

    Thirunarayanan, S.; Arjunan, V.; Marchewka, M. K.; Mohan, S.

    2017-04-01

    The hydrogen bonded molecular complex bis(1-hydroxy-2-methylpropan-2-aminium)selenate (C8H24N2O6Se) has been prepared by the reaction of 2-amino-2-methyl propanol and selenic acid. The X-ray diffraction analysis revealed that the intermolecular proton transfer from selenic acid (SeO4H2) to 2-amino-2-methylpropanol results in the formation of bis(1-hydroxy-2-methylpropan-2-aminium)selenate (HMPAS) salt and the fragments are connected through H-bonding and ion pairing. The N-H⋯O and O-H⋯O interactions between 2-amino-2-methylpropanol and selenic acid determine the supramolecular arrangement in three-dimensional space. The salt crystallises in the space group P121/n1 of monoclinic system. The complete vibrational assignments of HMPAS have been performed by FTIR and FT-Raman spectroscopy. The experimental data are correlated with the structural properties namely the energy, thermodynamic parameters, atomic charges, hybridization concepts and vibrational frequencies determined by quantum chemical studies performed with B3LYP method using 6-311++G*, 6-31+G* and 6-31G** basis sets.

  9. Raman enhancement on ultra-clean graphene quantum dots produced by quasi-equilibrium plasma-enhanced chemical vapor deposition.

    Science.gov (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

    2018-01-15

    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. Method and apparatus for quantum information processing using entangled neutral-atom qubits

    Science.gov (United States)

    Jau, Yuan Yu; Biedermann, Grant; Deutsch, Ivan

    2018-04-03

    A method for preparing an entangled quantum state of an atomic ensemble is provided. The method includes loading each atom of the atomic ensemble into a respective optical trap; placing each atom of the atomic ensemble into a same first atomic quantum state by impingement of pump radiation; approaching the atoms of the atomic ensemble to within a dipole-dipole interaction length of each other; Rydberg-dressing the atomic ensemble; during the Rydberg-dressing operation, exciting the atomic ensemble with a Raman pulse tuned to stimulate a ground-state hyperfine transition from the first atomic quantum state to a second atomic quantum state; and separating the atoms of the atomic ensemble by more than a dipole-dipole interaction length.

  11. Some Phthalocyanine and Naphthalocyanine Derivatives as Corrosion Inhibitors for Aluminium in Acidic Medium: Experimental, Quantum Chemical Calculations, QSAR Studies and Synergistic Effect of Iodide Ions

    Directory of Open Access Journals (Sweden)

    Masego Dibetsoe

    2015-08-01

    Full Text Available The effects of seven macrocyclic compounds comprising four phthalocyanines (Pcs namely 1,4,8,11,15,18,22,25-octabutoxy-29H,31H-phthalocyanine (Pc1, 2,3,9,10,16,17,23,24-octakis(octyloxy-29H,31H-phthalocyanine (Pc2, 2,9,16,23-tetra-tert-butyl-29H,31H-phthalocyanine (Pc3 and 29H,31H-phthalocyanine (Pc4, and three naphthalocyanines namely 5,9,14,18,23,27,32,36-octabutoxy-2,3-naphthalocyanine (nPc1, 2,11,20,29-tetra-tert-butyl-2,3-naphthalocyanine (nPc2 and 2,3-naphthalocyanine (nP3 were investigated on the corrosion of aluminium (Al in 1 M HCl using a gravimetric method, potentiodynamic polarization technique, quantum chemical calculations and quantitative structure activity relationship (QSAR. Synergistic effects of KI on the corrosion inhibition properties of the compounds were also investigated. All the studied compounds showed appreciable inhibition efficiencies, which decrease with increasing temperature from 30 °C to 70 °C. At each concentration of the inhibitor, addition of 0.1% KI increased the inhibition efficiency compared to the absence of KI indicating the occurrence of synergistic interactions between the studied molecules and I− ions. From the potentiodynamic polarization studies, the studied Pcs and nPcs are mixed type corrosion inhibitors both without and with addition of KI. The adsorption of the studied molecules on Al surface obeys the Langmuir adsorption isotherm, while the thermodynamic and kinetic parameters revealed that the adsorption of the studied compounds on Al surface is spontaneous and involves competitive physisorption and chemisorption mechanisms. The experimental results revealed the aggregated interactions between the inhibitor molecules and the results further indicated that the peripheral groups on the compounds affect these interactions. The calculated quantum chemical parameters and the QSAR results revealed the possibility of strong interactions between the studied inhibitors and metal surface. QSAR

  12. The effects of a stress field and chemical diffusion on electronic behaviour in InAs/GaAs quantum dots

    International Nuclear Information System (INIS)

    Zhang Xu; Wang Chongyu

    2006-01-01

    The effects of a stress field and chemical diffusion on electronic behaviour in self-assembled InAs/GaAs quantum dots (QD) are investigated by using first-principle calculations. We find that a potential well appears in a QD without a lattice misfit and chemical diffusion, and both stress field and Ga chemical diffusion can induce the formation of a potential barrier, which strongly affects the electronic behaviour within the QD. The stress field can localize electrons to the base of the QD. And associated with Ga diffusion, the stress field will induce an inverted electronic alignment. The electronic behaviour in the QD without a stress field does not present the confined or localized characteristics caused by a lattice misfit, atomic size and Ga diffusion. This study provides useful information for modulating electronic behaviour by introducing a stress field and chemical diffusion

  13. Investigation by perturbative and analytical method of electronic properties of square quantum well under electric field

    Directory of Open Access Journals (Sweden)

    Mustafa Kemal BAHAR

    2010-06-01

    Full Text Available In this study, the effects of applied electric field on the isolated square quantum well was investigated by analytic and perturbative method. The energy eigen values and wave functions in quantum well were found by perturbative method. Later, the electric field effects were investigated by analytic method, the results of perturbative and analytic method were compared. As well as both of results fit with each other, it was observed that externally applied electric field changed importantly electronic properties of the system.

  14. Method for discovering relationships in data by dynamic quantum clustering

    Science.gov (United States)

    Weinstein, Marvin; Horn, David

    2014-10-28

    Data clustering is provided according to a dynamical framework based on quantum mechanical time evolution of states corresponding to data points. To expedite computations, we can approximate the time-dependent Hamiltonian formalism by a truncated calculation within a set of Gaussian wave-functions (coherent states) centered around the original points. This allows for analytic evaluation of the time evolution of all such states, opening up the possibility of exploration of relationships among data-points through observation of varying dynamical-distances among points and convergence of points into clusters. This formalism may be further supplemented by preprocessing, such as dimensional reduction through singular value decomposition and/or feature filtering.

  15. Determination of the transmission coefficients for quantum structures using FDTD method.

    Science.gov (United States)

    Peng, Yangyang; Wang, Xiaoying; Sui, Wenquan

    2011-12-01

    The purpose of this work is to develop a simple method to incorporate quantum effect in traditional finite-difference time-domain (FDTD) simulators. Witch could make it possible to co-simulate systems include quantum structures and traditional components. In this paper, tunneling transmission coefficient is calculated by solving time-domain Schrödinger equation with a developed FDTD technique, called FDTD-S method. To validate the feasibility of the method, a simple resonant tunneling diode (RTD) structure model has been simulated using the proposed method. The good agreement between the numerical and analytical results proves its accuracy. The effectness and accuracy of this approach makes it a potential method for analysis and design of hybrid systems includes quantum structures and traditional components.

  16. ZnS nanoflakes deposition by modified chemical method

    International Nuclear Information System (INIS)

    Desai, Mangesh A.; Sartale, S. D.

    2014-01-01

    We report deposition of zinc sulfide nanoflakes on glass substrates by modified chemical method. The modified chemical method involves adsorption of zinc–thiourea complex on the substrate and its dissociation in presence of hydroxide ions to release sulfur ions from thiourea which react with zinc ions present in the complex to form zinc sulfide nanoflakes at room temperature. Influence of zinc salt and thiourea concentrations ratios on the morphology of the films was investigated by scanning electron microscope (SEM). The ratio of zinc and thiourea in the zinc–thiourea complex significantly affect the size of the zinc sulfide nanoflakes, especially width and density of the nanoflakes. The X-ray diffraction analysis exhibits polycrystalline nature of the zinc sulfide nanoflakes with hexagonal phase

  17. Method and apparatus for controlling gas evolution from chemical reactions

    Science.gov (United States)

    Skorpik, James R.; Dodson, Michael G.

    1999-01-01

    The present invention is directed toward monitoring a thermally driven gas evolving chemical reaction with an acoustic apparatus. Signals from the acoustic apparatus are used to control a heater to prevent a run-away condition. A digestion module in combination with a robotic arm further automate physical handling of sample material reaction vessels. The invention is especially useful for carrying out sample procedures defined in EPA Methods SW-846.

  18. Structural studies of crystals of organic and organoelement compounds using modern quantum chemical calculations within the framework of the density functional theory

    International Nuclear Information System (INIS)

    Korlyukov, Alexander A; Antipin, Mikhail Yu

    2012-01-01

    The review generalizes the results of structural studies of crystals of organic and organometallic compounds by modern quantum chemical calculations within the framework of the density functional theory reported in the last decade. Features of the software for such calculations are discussed. Examples of the use of quantum chemical calculations for the studies of the electronic structure, spectroscopic and other physicochemical properties of molecular crystals are presented. The bibliography includes 223 references.

  19. An efficient quantum mechanical method for radical pair recombination reactions.

    Science.gov (United States)

    Lewis, Alan M; Fay, Thomas P; Manolopoulos, David E

    2016-12-28

    The standard quantum mechanical expressions for the singlet and triplet survival probabilities and product yields of a radical pair recombination reaction involve a trace over the states in a combined electronic and nuclear spin Hilbert space. If this trace is evaluated deterministically, by performing a separate time-dependent wavepacket calculation for each initial state in the Hilbert space, the computational effort scales as O(Z 2 log⁡Z), where Z is the total number of nuclear spin states. Here we show that the trace can also be evaluated stochastically, by exploiting the properties of spin coherent states. This results in a computational effort of O(MZlog⁡Z), where M is the number of Monte Carlo samples needed for convergence. Example calculations on a strongly coupled radical pair with Z>10 6 show that the singlet yield can be converged to graphical accuracy using just M=200 samples, resulting in a speed up by a factor of >5000 over a standard deterministic calculation. We expect that this factor will greatly facilitate future quantum mechanical simulations of a wide variety of radical pairs of interest in chemistry and biology.

  20. Towards spectral geometric methods for Euclidean quantum gravity

    Science.gov (United States)

    Panine, Mikhail; Kempf, Achim

    2016-04-01

    The unification of general relativity with quantum theory will also require a coming together of the two quite different mathematical languages of general relativity and quantum theory, i.e., of differential geometry and functional analysis, respectively. Of particular interest in this regard is the field of spectral geometry, which studies to which extent the shape of a Riemannian manifold is describable in terms of the spectra of differential operators defined on the manifold. Spectral geometry is hard because it is highly nonlinear, but linearized spectral geometry, i.e., the task to determine small shape changes from small spectral changes, is much more tractable and may be iterated to approximate the full problem. Here, we generalize this approach, allowing, in particular, nonequal finite numbers of shape and spectral degrees of freedom. This allows us to study how well the shape degrees of freedom are encoded in the eigenvalues. We apply this strategy numerically to a class of planar domains and find that the reconstruction of small shape changes from small spectral changes is possible if enough eigenvalues are used. While isospectral nonisometric shapes are known to exist, we find evidence that generically shaped isospectral nonisometric shapes, if existing, are exceedingly rare.

  1. Radical cations in radiation chemistry of aldehydes. ESR study and quantum chemical analysis

    International Nuclear Information System (INIS)

    Belevskii, V.N.; Tyurin, D.A.; Chuvilkin, N.D.

    1998-01-01

    Quantum-chemical (MNDO-UHF) calculations of electronic, spin and energy characteristics of radical cations (RC) of ethanal, propanal, butanal, and pentanal and their distonic isomers were performed. The calculations both with 'frozen' (vertical ionization) and completely optimize geometry (adiabatic approximation) were made. It was been shown that the most positive charge and spin population are localized at O atoms and adjacent C atom as well as at aldehyde protons. The C-H bonds corresponding to those protons as well as neighboring C-O and C-C bonds are considerable weaker (longer) in radical cations as compared to their neutral precursors. That is why such reaction centers are apt to deprotonation with the formation of acyl radical as well as to α- and β-splitting (scission) which are well-known from aldehydes mass-spectra. Our calculations shown that distonic RC (products of intramolecular H-atom transfer) are more stable as compare to their classical isomers: e.g. the difference in energy ΔE = -0.95 eV, -1.2 eV, and -1.5 eV for tree distonic isomers of butanal RC as compare to classical isomer, ΔE -1.2 eV for distonic RC of ethanal. The results of calculations are effectively correlated with ESR data obtained in freonic solutions, X- and gamma-irradiated at 77 K and in liquid aldehydes, X-irradiated by using 2,4,6-tri-tert-burylnitrosobenzene (BNB) and t-BuNO (NtB) as a spin traps. (author)

  2. Photophysics of α-furil at room temperature and 77 K: Spectroscopic and quantum chemical studies

    Energy Technology Data Exchange (ETDEWEB)

    Kundu, Pronab; Chattopadhyay, Nitin, E-mail: nitin.chattopadhyay@yahoo.com [Department of Chemistry, Jadavpur University, Kolkata 700 032 (India)

    2016-06-21

    Steady state and time resolved spectroscopic measurements have been exploited to assign the emissions from different conformations of α-furil (2, 2′-furil) in solution phase at room temperature as well as cryogen (liquid nitrogen, LN{sub 2}) frozen matrices of ethanol and methylcyclohexane. Room temperature studies reveal a single fluorescence from the trans-planar conformer of the fluorophore or two fluorescence bands coming from the trans-planar and the relaxed skew forms depending on excitation at the nπ{sup ∗} or the ππ{sup ∗} absorption band, respectively. Together with the fluorescence bands, the LN{sub 2} studies in both the solvents unambiguously ascertain two phosphorescence emissions with lifetimes 5 ± 0.3 ms (trans-planar triplet) and 81 ± 3 ms (relaxed skew triplet). Quantum chemical calculations have been performed using density functional theory at CAM-B3LYP/6-311++G{sup ∗∗} level to prop up the spectroscopic surveillance. The simulated potential energy curves (PECs) illustrate that α-furil is capable of giving two emissions from each of the S{sub 1} and the T{sub 1} states—one corresponding to the trans-planar and the other to the relaxed skew conformation. Contrary to the other 1,2-dicarbonyl molecular systems like benzil and α-naphthil, α-furil does not exhibit any fluorescence from its second excited singlet (S{sub 2}) state. This is ascribed to the proximity of the minimum of the PEC of the S{sub 2} state and the hill-top of the PEC of the S{sub 1} state.

  3. Quantum Chemical Benchmarking, Validation, and Prediction of Acidity Constants for Substituted Pyridinium Ions and Pyridinyl Radicals.

    Science.gov (United States)

    Keith, John A; Carter, Emily A

    2012-09-11

    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.

  4. Research on Quantum Authentication Methods for the Secure Access Control Among Three Elements of Cloud Computing

    Science.gov (United States)

    Dong, Yumin; Xiao, Shufen; Ma, Hongyang; Chen, Libo

    2016-12-01

    Cloud computing and big data have become the developing engine of current information technology (IT) as a result of the rapid development of IT. However, security protection has become increasingly important for cloud computing and big data, and has become a problem that must be solved to develop cloud computing. The theft of identity authentication information remains a serious threat to the security of cloud computing. In this process, attackers intrude into cloud computing services through identity authentication information, thereby threatening the security of data from multiple perspectives. Therefore, this study proposes a model for cloud computing protection and management based on quantum authentication, introduces the principle of quantum authentication, and deduces the quantum authentication process. In theory, quantum authentication technology can be applied in cloud computing for security protection. This technology cannot be cloned; thus, it is more secure and reliable than classical methods.

  5. Study on magnetite nanoparticles synthesized by chemical method

    International Nuclear Information System (INIS)

    Pei Wenli; Kumada, H.; Natusme, T.; Saito, H.; Ishio, S.

    2007-01-01

    Magnetite nanoparticles with controlled size were synthesized by chemical method. Higher deposition temperature and a rapid-raising temperature procedure are favorable to particle size distribution and fabrication of monodisperse nanoparticles. The larger nanoparticles can be synthesized by the two-step method. The large nanoparticle (up to 25 nm) without agglomeration was successfully produced. The saturation magnetization of 11 nm magnetite particles was 45 emu/g at room temperature, which is smaller than that of bulk magnetite due to surface effect. Hysteresis of the magnetite nanoparticle was very small, indicating superparamagnetic behavior. The magnetic domains of the 11 nm magnetite nanoparticles were successfully observed by MFM

  6. Approximate method for stochastic chemical kinetics with two-time scales by chemical Langevin equations

    International Nuclear Information System (INIS)

    Wu, Fuke; Tian, Tianhai; Rawlings, James B.; Yin, George

    2016-01-01

    The frequently used reduction technique is based on the chemical master equation for stochastic chemical kinetics with two-time scales, which yields the modified stochastic simulation algorithm (SSA). For the chemical reaction processes involving a large number of molecular species and reactions, the collection of slow reactions may still include a large number of molecular species and reactions. Consequently, the SSA is still computationally expensive. Because the chemical Langevin equations (CLEs) can effectively work for a large number of molecular species and reactions, this paper develops a reduction method based on the CLE by the stochastic averaging principle developed in the work of Khasminskii and Yin [SIAM J. Appl. Math. 56, 1766–1793 (1996); ibid. 56, 1794–1819 (1996)] to average out the fast-reacting variables. This reduction method leads to a limit averaging system, which is an approximation of the slow reactions. Because in the stochastic chemical kinetics, the CLE is seen as the approximation of the SSA, the limit averaging system can be treated as the approximation of the slow reactions. As an application, we examine the reduction of computation complexity for the gene regulatory networks with two-time scales driven by intrinsic noise. For linear and nonlinear protein production functions, the simulations show that the sample average (expectation) of the limit averaging system is close to that of the slow-reaction process based on the SSA. It demonstrates that the limit averaging system is an efficient approximation of the slow-reaction process in the sense of the weak convergence.

  7. FTIR, FT-Raman, FT-NMR and quantum chemical investigations of 3-acetylcoumarin.

    Science.gov (United States)

    Arjunan, V; Sakiladevi, S; Marchewka, M K; Mohan, S

    2013-05-15

    3-Acetylcoumarin (3AC) was synthesised by a Knoevenagel reaction. Conformational analysis using the B3LYP method was also carried out to determine the most stable conformation of the compound. FTIR and FT-Raman spectra of 3AC have been recorded in the range 4000-400 and 4000-100 cm(-1), respectively. (1)H and (13)C NMR spectra have also been recorded. The complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the experimental FTIR and FT-Raman data and quantum mechanical studies. The experimental vibrational frequencies were compared with the wavenumbers obtained theoretically from the DFT-B3LYP/B3PW91 gradient calculations employing the standard 6-31G(**), high level 6-311++G(**) and cc-pVTZ basis sets for optimised geometry of the compound. The frontier molecular orbital energies of the compound are determined by DFT method. Copyright © 2013 Elsevier B.V. All rights reserved.

  8. Quantum chemical analysis of binary and ternary ferromagnetic alloys; Quantenchemische Untersuchungen binaerer und ternaerer ferromagnetischer Legierungen

    Energy Technology Data Exchange (ETDEWEB)

    Jacobs, Yasemin Erika Charlotte

    2007-02-23

    In this work the electronic structures, densities of states, chemical bonding, magnetic exchange Parameters and Curie temperatures of binary and ternary ferromagnetic alloys are analyzed. The electronic structure of ferromagnetic MnAl has been calculated using density-functional techniques (TB-LMTO-ASA, FPLAPW) and quantum chemically analyzed by means of the crystal orbital Hamilton population analysis. The crystal structure of the ferromagnetic tetragonal MnAl may be understood to originate from the structure of nonmagnetic cubic MnAl with a CsCl motif through a two-step process. While the nonmagnetic cubic structure is stable against a structural deformation, antibonding Mn-Mn interactions at the Fermi level lead to spin polarization and the onset of magnetism, i.e., a symmetry reduction taking place solely in the electronic degrees of freedom, by that emptying antibonding Mn-Mn states. Residual antibonding Al--Al states can only be removed by a subsequent, energetically smaller structural deformation towards the tetragonal system. As a final result, homonuclear bonding is strengthened and heteronuclear bonding is weakened. Corresponding DFT calculations of the electronic structure as well as the calculation of the chemical bonding and the magnetic exchange interactions have been performed on the basis of LDA and GGA for a series of ferromagnetic full Heusler alloys of general formula Co2MnZ (Z=Ga,Si,Ge,Sn), Rh2MnZ (Z=Ge,Sn,Pb), Ni2MnZ (Z=Ga,In,Sn), Pd2MnZ (Z=Sn,Sb) and Cu2MnZ (Z=Al,In,Sn). The connection between the electronic spectra and the magnetic interactions have been studied. Correlations between the chemical bondings in Heusler alloys derived from COHP analysis and magnetic phenomena are obvious, and different mechanisms leading to spin polarization and ferromagnetism are derived. The band dependence of the exchange parameters, their dependence on volume and valence electron concentration have been thoroughly analyzed within the Green function technique

  9. Methods for accurate calculations in high-energy quantum electrodynamics

    Energy Technology Data Exchange (ETDEWEB)

    Ericsson, K. E. [Institute of Theoretical Physics, Uppsala (Sweden)

    1963-01-15

    In this paper ''quantum electrodynamics'' (QED) will be used in the sense of a closed theory of point-like photons and electrons. Muons could then easily be included. We make the usual assumption that the perturbation expansion of renormalized QED gives at least an asymptotic expression of the exact theory, i.e. that the sum over a few terms in the beginning of the perturbation series is a good approximation of the exact theory. We expect QED in this sense to break down at small distances, i. e. at large momentum transfers, because of structure effects resulting from other kinds of interaction, primarily the interactions of the electromagnetic field with the current of strongly interacting particles. This will first show up as vacuum polarization through mesons. On the other hand we have no reason to believe that the fundamental theory of electrodynamics, i.e. the theory of a massless vector field interacting with a.conserved current, will break down.

  10. Anharmonic effects in the quantum cluster equilibrium method

    Science.gov (United States)

    von Domaros, Michael; Perlt, Eva

    2017-03-01

    The well-established quantum cluster equilibrium (QCE) model provides a statistical thermodynamic framework to apply high-level ab initio calculations of finite cluster structures to macroscopic liquid phases using the partition function. So far, the harmonic approximation has been applied throughout the calculations. In this article, we apply an important correction in the evaluation of the one-particle partition function and account for anharmonicity. Therefore, we implemented an analytical approximation to the Morse partition function and the derivatives of its logarithm with respect to temperature, which are required for the evaluation of thermodynamic quantities. This anharmonic QCE approach has been applied to liquid hydrogen chloride and cluster distributions, and the molar volume, the volumetric thermal expansion coefficient, and the isobaric heat capacity have been calculated. An improved description for all properties is observed if anharmonic effects are considered.

  11. The determination of the chemical composition profile of the GaAs/AlGaAs heterostructures designed for quantum cascade lasers by means of synchrotron radiation

    International Nuclear Information System (INIS)

    Gaca, Jaroslaw; Wojcik, Marek; Bugajski, Maciej; Kosiel, Kamil

    2011-01-01

    The chemical composition profile of the GaAs/AlGaAs quantum cascade structures grown on (0 0 1) GaAs substrate by molecular beam epitaxy is studied by a synchrotron radiation high-resolution X-ray diffraction. The analysis is carried out for the whole structure as well for its parts. In order to determine some structural parameters, such as: the thickness and chemical composition of each layer making up the investigated structure, the profile of the interface between succeeding layers, and the preservation of the structure periodicity, the experimental X-ray diffraction profiles are compared with simulated ones calculated by means of Darwin dynamical theory of X-ray diffraction. It is shown that this method gives correct chemical composition profiles and allows for the evaluation of the deviations from the designed values of the structural parameters in most investigated cases. Limits of the method are discussed, especially by the determination of the chemical composition profile for thin heterostructures, such as those making active or injector regions.

  12. Determinantal and worldline quantum Monte Carlo methods for many-body systems

    International Nuclear Information System (INIS)

    Vekic, M.; White, S.R.

    1993-01-01

    We examine three different quantum Monte Carlo methods for studying systems of interacting particles. The determinantal quantum Monte Carlo method is compared to two different worldline simulations. The first worldline method consists of a simulation carried out in the real-space basis, while the second method is implemented using as basis the eigenstates of the Hamiltonian on blocks of the two-dimensional lattice. We look, in particular, at the Hubbard model on a 4x4 lattice with periodic boundary conditions. The block method is superior to the real-space method in terms of the computational cost of the simulation, but shows a much worse negative sign problem. For larger values of U and away from half-filling it is found that the real-space method can provide results at lower temperatures than the determinantal method. We show that the sign problem in the block method can be slightly improved by an appropriate choice of basis

  13. Investigation of chemical equilibrium kinetics by the electromigration method

    International Nuclear Information System (INIS)

    Bozhikov, G.A.; Ivanov, P.I.; Maslov, O.D.; Dmitriev, S.N.; Bontchev, G.D.; Milanov, M.V.

    2003-01-01

    The measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the formation a complex by Hf(IV) and diethylenetriaminepentaacetic acid (DTPA) is determined. The electrophoretic mobility, diffusion coefficient and stability constant of the [HfDTPA] - complex are calculated, taking into account experimental electrophoretic data obtained at 298.15±0.05 K and constant ionic strength. No-carrier-added 175 Hf radionuclide was used in electromigration experiments at concentrations of 10 -10 -10 -11 M. (orig.)

  14. A localized in vivo detection method for lactate using zero quantum coherence techniques

    NARCIS (Netherlands)

    van Dijk, J. E.; Bosman, D. K.; Chamuleau, R. A.; Bovee, W. M.

    1991-01-01

    A method is described to selectively measure lactate in vivo using proton zero quantum coherence techniques. The signal from lipids is eliminated. A surface coil and additionally slice selective localization are used. The resulting spectra demonstrate the good performance of the method

  15. 2D Quantum Simulation of MOSFET Using the Non Equilibrium Green's Function Method

    Science.gov (United States)

    Svizhenko, Alexel; Anantram, M. P.; Govindan, T. R.; Yan, Jerry (Technical Monitor)

    2000-01-01

    The objectives this viewgraph presentation summarizes include: (1) the development of a quantum mechanical simulator for ultra short channel MOSFET simulation, including theory, physical approximations, and computer code; (2) explore physics that is not accessible by semiclassical methods; (3) benchmarking of semiclassical and classical methods; and (4) study other two-dimensional devices and molecular structure, from discretized Hamiltonian to tight-binding Hamiltonian.

  16. A General Solid-State Synthesis of Chemically-Doped Fluorescent Graphene Quantum Dots for Bioimaging and Optoelectronic Applications

    KAUST Repository

    Ma, Chong-Bo

    2015-05-05

    Graphene quantum dots (GQDs) have attracted increasing interest because of their excellent properties such as strong photoluminescence, excellent biocompatibility and low cost. Herein, we develop a general method for the synthesis of doped and undoped GQDs, which relies on direct carbonization of organic precursors at solid state.

  17. A General Solid-State Synthesis of Chemically-Doped Fluorescent Graphene Quantum Dots for Bioimaging and Optoelectronic Applications

    KAUST Repository

    Ma, Chong-Bo; Zhu, Zhentong; Wang, Hang-Xing; Huang, Xiao; Zhang, Xiao; Qi, Xiaoying; Zhang, Haoli; Zhu, Yihan; Deng, Xia; Peng, Yong; Han, Yu; Zhang, Hua

    2015-01-01

    Graphene quantum dots (GQDs) have attracted increasing interest because of their excellent properties such as strong photoluminescence, excellent biocompatibility and low cost. Herein, we develop a general method for the synthesis of doped and undoped GQDs, which relies on direct carbonization of organic precursors at solid state.

  18. 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.

    2016-01-01

    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.

  19. An experimental design method leading to chemical Turing patterns.

    Science.gov (United States)

    Horváth, Judit; Szalai, István; De Kepper, Patrick

    2009-05-08

    Chemical reaction-diffusion patterns often serve as prototypes for pattern formation in living systems, but only two isothermal single-phase reaction systems have produced sustained stationary reaction-diffusion patterns so far. We designed an experimental method to search for additional systems on the basis of three steps: (i) generate spatial bistability by operating autoactivated reactions in open spatial reactors; (ii) use an independent negative-feedback species to produce spatiotemporal oscillations; and (iii) induce a space-scale separation of the activatory and inhibitory processes with a low-mobility complexing agent. We successfully applied this method to a hydrogen-ion autoactivated reaction, the thiourea-iodate-sulfite (TuIS) reaction, and noticeably produced stationary hexagonal arrays of spots and parallel stripes of pH patterns attributed to a Turing bifurcation. This method could be extended to biochemical reactions.

  20. A method of refining aromatic hydrocarbons from coal chemical production

    Energy Technology Data Exchange (ETDEWEB)

    Zieborak, K.; Koprowski, A.; Ratajczak, W.

    1979-10-01

    A method is disclosed for refining aromatic hydrocarbons of coal chemical production by contact of liquid aromatic hydrocarbons and their mixtures with a strongly acid macroporous sulfocationite in the H-form at atmospheric pressure and high temperature. The method is distinguished in that the aromatic hydrocarbons and their mixtures, from which alkali compounds have already been removed, are supplied for refinement with the sulfocationite with simultaneous addition of olefin derivatives of aromatic hydrocarbons, followed by separation of pure hydrocarbons by rectification. Styrene or alpha-methylstyrene is used as the olefin derivatives of the aromatic hydrocarbons. The method is performed in several stages with addition of olefin derivatives of aromatic hydrocarbons at each stage.

  1. Quantum Monte Carlo methods and strongly correlated electrons on honeycomb structures

    Energy Technology Data Exchange (ETDEWEB)

    Lang, Thomas C.

    2010-12-16

    In this thesis we apply recently developed, as well as sophisticated quantum Monte Carlo methods to numerically investigate models of strongly correlated electron systems on honeycomb structures. The latter are of particular interest owing to their unique properties when simulating electrons on them, like the relativistic dispersion, strong quantum fluctuations and their resistance against instabilities. This work covers several projects including the advancement of the weak-coupling continuous time quantum Monte Carlo and its application to zero temperature and phonons, quantum phase transitions of valence bond solids in spin-1/2 Heisenberg systems using projector quantum Monte Carlo in the valence bond basis, and the magnetic field induced transition to a canted antiferromagnet of the Hubbard model on the honeycomb lattice. The emphasis lies on two projects investigating the phase diagram of the SU(2) and the SU(N)-symmetric Hubbard model on the hexagonal lattice. At sufficiently low temperatures, condensed-matter systems tend to develop order. An exception are quantum spin-liquids, where fluctuations prevent a transition to an ordered state down to the lowest temperatures. Previously elusive in experimentally relevant microscopic two-dimensional models, we show by means of large-scale quantum Monte Carlo simulations of the SU(2) Hubbard model on the honeycomb lattice, that a quantum spin-liquid emerges between the state described by massless Dirac fermions and an antiferromagnetically ordered Mott insulator. This unexpected quantum-disordered state is found to be a short-range resonating valence bond liquid, akin to the one proposed for high temperature superconductors. Inspired by the rich phase diagrams of SU(N) models we study the SU(N)-symmetric Hubbard Heisenberg quantum antiferromagnet on the honeycomb lattice to investigate the reliability of 1/N corrections to large-N results by means of numerically exact QMC simulations. We study the melting of phases

  2. Classical Wigner method with an effective quantum force: application to reaction rates.

    Science.gov (United States)

    Poulsen, Jens Aage; Li, Huaqing; Nyman, Gunnar

    2009-07-14

    We construct an effective "quantum force" to be used in the classical molecular dynamics part of the classical Wigner method when determining correlation functions. The quantum force is obtained by estimating the most important short time separation of the Feynman paths that enter into the expression for the correlation function. The evaluation of the force is then as easy as classical potential energy evaluations. The ideas are tested on three reaction rate problems. The resulting transmission coefficients are in much better agreement with accurate results than transmission coefficients from the ordinary classical Wigner method.

  3. Methods of chemical and phase composition analysis of gallstones

    Science.gov (United States)

    Suvorova, E. I.; Pantushev, V. V.; Voloshin, A. E.

    2017-11-01

    This review presents the instrumental methods used for chemical and phase composition investigation of gallstones. A great body of data has been collected in the literature on the presence of elements and their concentrations, obtained by fluorescence microscopy, X-ray fluorescence spectroscopy, neutron activation analysis, proton (particle) induced X-ray emission, atomic absorption spectroscopy, high-resolution gamma-ray spectrometry, electron paramagnetic resonance. Structural methods—powder X-ray diffraction, infrared spectroscopy, Raman spectroscopy—provide information about organic and inorganic phases in gallstones. Stone morphology was studied at the macrolevel with optical microscopy. Results obtained by analytical scanning and transmission electron microscopy with X-ray energy dispersive spectrometry are discussed. The chemical composition and structure of gallstones determine the strategy of removing stone from the body and treatment of patients: surgery or dissolution in the body. Therefore one chapter of the review describes the potential of dissolution methods. Early diagnosis and appropriate treatment of the disease depend on the development of clinical methods for in vivo investigation, which gave grounds to present the main characteristics and potential of ultrasonography (ultrasound scanning), magnetic resonance imaging, and X-ray computed tomography.

  4. AN ANALYTICAL METHOD FOR CHEMICAL SPECIATION OF SELENIUM IN SOIL

    Directory of Open Access Journals (Sweden)

    Constantin Luca

    2010-10-01

    Full Text Available Selenium is an essential microelement, sometimes redoubtable, through its beneficial role - risk depending on its concentration in the food chain, at low dose is an important nutrient in the life of humans and animals, contrary at high doses, it becomes toxic. Selenium may be find itself in the environment (soil, sediment, water in many forms (oxidized, reduced, organometallic which determine their mobility and toxicity. Determination of chemical speciation (identification of different chemical forms provides much more complete information for a better understanding of the behavior and the potential impact on the environment. In this work we present the results of methodological research on the extraction of sequential forms of selenium in the soil and the coupling of analytical methods capable of identifying very small amounts of selenium in soils An efficient scheme of sequential extractions forms of selenium (SES consisting in atomic absorption spectrometry coupled with hydride generation (HGAAS has been developed into five experimental steps, detailed in the paper. This operational scheme has been applied to the analysis of chemical speciation in the following areas: the Bărăgan Plain and Central Dobrogea of Romania.

  5. An adaptive quantum mechanics/molecular mechanics method for the infrared spectrum of water: incorporation of the quantum effect between solute and solvent.

    Science.gov (United States)

    Watanabe, Hiroshi C; Banno, Misa; Sakurai, Minoru

    2016-03-14

    Quantum effects in solute-solvent interactions, such as the many-body effect and the dipole-induced dipole, are known to be critical factors influencing the infrared spectra of species in the liquid phase. For accurate spectrum evaluation, the surrounding solvent molecules, in addition to the solute of interest, should be treated using a quantum mechanical method. However, conventional quantum mechanics/molecular mechanics (QM/MM) methods cannot handle free QM solvent molecules during molecular dynamics (MD) simulation because of the diffusion problem. To deal with this problem, we have previously proposed an adaptive QM/MM "size-consistent multipartitioning (SCMP) method". In the present study, as the first application of the SCMP method, we demonstrate the reproduction of the infrared spectrum of liquid-phase water, and evaluate the quantum effect in comparison with conventional QM/MM simulations.

  6. Synthesis of Lead Sulfide Nanoparticles by Chemical Precipitation Method

    International Nuclear Information System (INIS)

    Chongad, L S; Sharma, A; Banerjee, M; Jain, A

    2016-01-01

    Lead sulfide (PbS) nanoparticles were prepared by chemical precipitation method (CPM) with the assistance of H 2 S gas. The microstructure and morphology of the synthesized nanoparticles have been investigated using X-ray diffraction (XRD) and transmission electron microscopy (TEM). The XRD patterns of the PbS nanoparticles reveal formation of cubic phase. To investigate the quality of prepared nanoparticles, the particles size, lattice constant, strain, dislocation density etc. have been determined using XRD. TEM images reveal formation of cubic nanoparticles and the particle size determined from TEM images agree well with those from XRD. (paper)

  7. Conformational, structural, vibrational, electronic and quantum chemical investigations of cis-2-methoxycinnamic acid

    Science.gov (United States)

    Arjunan, V.; Anitha, R.; Marchewka, M. K.; Mohan, S.; Yang, Haifeng

    2015-01-01

    The Fourier transform infrared (FTIR) and FT-Raman spectra of cis-2-methoxycinnamic acid have been measured in the range 4000-400 and 4000-100 cm-1, respectively. Complete vibrational assignment and analysis of the fundamental modes of the compound were carried out using the observed FTIR and FT-Raman data. The geometry was optimised without any symmetry constrains using the DFT/B3LYP method utilising 6-311++G∗∗ and cc-pVTZ basis sets. The thermodynamic stability and chemical reactivity descriptors of the molecule have been determined. The exact environment of C and H of the molecule has been analysed by NMR spectroscopies through 1H and 13C NMR chemical shifts of the molecule. The energies of the frontier molecular orbitals have also been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. The vibrational frequencies which were determined experimentally are compared with those obtained theoretically from density functional theory (DFT) gradient calculations employing the B3LYP/6-311++G∗∗ and cc-pVTZ methods.

  8. Method of trial distribution function for quantum turbulence

    International Nuclear Information System (INIS)

    Nemirovskii, Sergey K.

    2012-01-01

    Studying quantum turbulence the necessity of calculation the various characteristics of the vortex tangle (VT) appears. Some of 'crude' quantities can be expressed directly via the total length of vortex lines (per unit of volume) or the vortex line density L(t) and the structure parameters of the VT. Other more 'subtle' quantities require knowledge of the vortex line configurations {s(xi,t) }. Usually, the corresponding calculations are carried out with the use of more or less truthful speculations concerning arrangement of the VT. In this paper we review other way to solution of this problem. It is based on the trial distribution functional (TDF) in space of vortex loop configurations. The TDF is constructed on the basis of well established properties of the vortex tangle. It is designed to calculate various averages taken over stochastic vortex loop configurations. In this paper we also review several applications of the use this model to calculate some important characteristics of the vortex tangle. In particular we discussed the average superfluid mass current J induced by vortices and its dynamics. We also describe the diffusion-like processes in the nonuniform vortex tangle and propagation of turbulent fronts.

  9. Alternative Chemical Amplification Methods for Peroxy Radical Detection

    Science.gov (United States)

    Wood, E. C. D.

    2014-12-01

    Peroxy radicals (HO2, CH3O2, etc.) are commonly detected by the chemical amplification technique, in which ambient air is mixed with high concentrations of CO and NO, initiating a chain reaction that produces 30 - 200 NO2 molecules per sampled peroxy radical. The NO2 is then measured by one of several techniques. With the exception of CIMS-based techniques, the chemical amplification method has undergone only incremental improvements since it was first introduced in 1982. The disadvantages of the technique include the need to use high concentrations of CO and the greatly reduced sensitivity of the amplification chain length in the presence of water vapor. We present a new chemical amplification scheme in which either ethane or acetaldehyde is used in place of CO, with the NO2 product detected using Cavity Attenuated Phase Shift spectroscopy (CAPS). Under dry conditions, the amplification factor of the alternative amplifiers are approximately six times lower than the CO-based amplifier. The relative humidity "penalty" is not as severe, however, such that at typical ambient relative humidity (RH) values the amplification factor is within a factor of three of the CO-based amplifier. Combined with the NO2 sensitivity of CAPS and a dual-channel design, the detection limit of the ethane amplifier is less than 2 ppt (1 minute average, signal-to-noise ratio 2). The advantages of these alternative chemical amplification schemes are improved safety, a reduced RH correction, and increased sensitivity to organic peroxy radicals relative to HO2.

  10. Projection and nested force-gradient methods for quantum field theories

    Energy Technology Data Exchange (ETDEWEB)

    Shcherbakov, Dmitry

    2017-07-26

    For the Hybrid Monte Carlo algorithm (HMC), often used to study the fundamental quantum field theory of quarks and gluons, quantum chromodynamics (QCD), on the lattice, one is interested in efficient numerical time integration schemes which preserve geometric properties of the flow and are optimal in terms of computational costs per trajectory for a given acceptance rate. High order numerical methods allow the use of larger step sizes, but demand a larger computational effort per step; low order schemes do not require such large computational costs per step, but need more steps per trajectory. So there is a need to balance these opposing effects. In this work we introduce novel geometric numerical time integrators, namely, projection and nested force-gradient methods in order to improve the efficiency of the HMC algorithm in application to the problems of quantum field theories.

  11. Perturbative method for the derivation of quantum kinetic theory based on closed-time-path formalism

    International Nuclear Information System (INIS)

    Koide, Jun

    2002-01-01

    Within the closed-time-path formalism, a perturbative method is presented, which reduces the microscopic field theory to the quantum kinetic theory. In order to make this reduction, the expectation value of a physical quantity must be calculated under the condition that the Wigner distribution function is fixed, because it is the independent dynamical variable in the quantum kinetic theory. It is shown that when a nonequilibrium Green function in the form of the generalized Kadanoff-Baym ansatz is utilized, this condition appears as a cancellation of a certain part of contributions in the diagrammatic expression of the expectation value. Together with the quantum kinetic equation, which can be derived in the closed-time-path formalism, this method provides a basis for the kinetic-theoretical description

  12. A quantum chemical study of the N2H+ + e- → N2 + H reaction I: The linear dissociation path

    International Nuclear Information System (INIS)

    Talbi, D.

    2007-01-01

    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

  13. Full Quantum Dynamics Simulation of a Realistic Molecular System Using the Adaptive Time-Dependent Density Matrix Renormalization Group Method.

    Science.gov (United States)

    Yao, Yao; Sun, Ke-Wei; Luo, Zhen; Ma, Haibo

    2018-01-18

    The accurate theoretical interpretation of ultrafast time-resolved spectroscopy experiments relies on full quantum dynamics simulations for the investigated system, which is nevertheless computationally prohibitive for realistic molecular systems with a large number of electronic and/or vibrational degrees of freedom. In this work, we propose a unitary transformation approach for realistic vibronic Hamiltonians, which can be coped with using the adaptive time-dependent density matrix renormalization group (t-DMRG) method to efficiently evolve the nonadiabatic dynamics of a large molecular system. We demonstrate the accuracy and efficiency of this approach with an example of simulating the exciton dissociation process within an oligothiophene/fullerene heterojunction, indicating that t-DMRG can be a promising method for full quantum dynamics simulation in large chemical systems. Moreover, it is also shown that the proper vibronic features in the ultrafast electronic process can be obtained by simulating the two-dimensional (2D) electronic spectrum by virtue of the high computational efficiency of the t-DMRG method.

  14. Quantum Monte Carlo diagonalization method as a variational calculation

    International Nuclear Information System (INIS)

    Mizusaki, Takahiro; Otsuka, Takaharu; Honma, Michio.

    1997-01-01

    A stochastic method for performing large-scale shell model calculations is presented, which utilizes the auxiliary field Monte Carlo technique and diagonalization method. This method overcomes the limitation of the conventional shell model diagonalization and can extremely widen the feasibility of shell model calculations with realistic interactions for spectroscopic study of nuclear structure. (author)

  15. Green's functions in quantum chemistry - I. The Σ perturbation method

    International Nuclear Information System (INIS)

    Sebastian, K.L.

    1978-01-01

    As an improvement over the Hartree-Fock approximation, a Green's Function method - the Σ perturbation method - is investigated for molecular calculations. The method is applied to the hydrogen molecule and to the π-electron system of ethylene under PPP approximation. It is found that when the algebraic approximation is used, the energy obtained is better than that of the HF approach, but is not as good as that of the configuration-interaction method. The main advantage of this procedure is that it is devoid of the most serious defect of HF method, viz. incorrect dissociation limits. (K.B.)

  16. Quantum Dot Photovoltaics in the Extreme Quantum Confinement Regime: The Surface-Chemical Origins of Exceptional Air- and Light-Stability

    KAUST Repository

    Tang, Jiang

    2010-02-23

    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.

  17. Chemical methods for the determination of composition of cryolite

    International Nuclear Information System (INIS)

    Shivarudrappa, V.; Patil, B.N.; Marathe, S.G.; Jain, H.C.

    1989-01-01

    Preparation of uranium and plutonium alloys containing aluminium involves the use of cryolite and many times, cryolite which may be contaminated with alpha activity has to be analysed for its purity. In view of this, chemical methods for the determination of composition of commercial cryolite samples have been developed. Methods are standardised for the determination of individual constituents of cryolite viz., aluminium, sodium, fluoride and major impurities, calcium and magnesium. Studies on the dissolution of the sample, effect of one or more components on the determination of the other and their elimination are carried out. Aluminium and sodium are determined gravimetrically as oxinate and triple acetate respectively. Fluoride is determined by a volumetric procedure after cation exchange separtion of soluble fluoride. Calcium and magnesium are determined by a sequential pH-metri titration. This report describes the details of the procedures and the results of these studies for two commercial cryolite samples. (author). 7 tabs

  18. 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: Florian.Herzog@ph.tum.de; Wilde, Marc A., E-mail: mwilde@ph.tum.de [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)

    2015-08-31

    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.

  19. Quantum chemical analysis of the electronic structure and Moessbauer spectra parameters for low spin cyanide- and pyridine-hemichromes

    International Nuclear Information System (INIS)

    Khleskov, V.I.; Kolpakov, E.V.; Smirnov, A.B.

    1992-01-01

    The work contains results of quantum-chemical calculations of electronic structure and Moessbauer spectra parameters for low spin S=1/2 hexa-coordinated ferri-porphyrin complexes with cyanide (CN) and pyridine (Py) as axial ligands. Theoretical results made it possible to explain experimentally observed regularity of anomalous quadrupole splitting decrease after substitution of Py-ligands by CN. Comparison of theoretical and experimental data indicated that 2 E g must be the ground state of investigated hemichromes. In this state unpaired electron symmetrically occupies d π -orbitals of Fe-ion. (orig.)

  20. Combined friction force microscopy and quantum chemical investigation of the tribotronic response at the propylammonium nitrate-graphite interface.

    Science.gov (United States)

    Li, H; Atkin, R; Page, A J

    2015-06-28

    The energetic origins of the variation in friction with potential at the propylammonium nitrate-graphite interface are revealed using friction force microscopy (FFM) in combination with quantum chemical simulations. For boundary layer lubrication, as the FFM tip slides energy is dissipated via (1) boundary layer ions and (2) expulsion of near-surface ion layers from the space between the surface and advancing tip. Simulations reveal how changing the surface potential changes the ion composition of the boundary and near surface layer, which controls energy dissipation through both pathways, and thus the friction.

  1. Role of the chemical bonding for the time-dependent electron transport through an interacting quantum dot

    KAUST Repository

    Goker, Ali

    2011-06-01

    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.

  2. Role of the chemical bonding for the time-dependent electron transport through an interacting quantum dot

    KAUST Repository

    Goker, Ali; Zhu, Zhiyong; Manchon, Aurelien; Schwingenschlö gl, Udo

    2011-01-01

    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.

  3. Nonlinear Hamiltonian mechanics applied to molecular dynamics theory and computational methods for understanding molecular spectroscopy and chemical reactions

    CERN Document Server

    Farantos, Stavros C

    2014-01-01

    This brief presents numerical methods for describing and calculating invariant phase space structures, as well as solving the classical and quantum equations of motion for polyatomic molecules. Examples covered include simple model systems to realistic cases of molecules spectroscopically studied. Vibrationally excited and reacting molecules are nonlinear dynamical systems, and thus, nonlinear mechanics is the proper theory to elucidate molecular dynamics by investigating invariant structures in phase space. Intramolecular energy transfer, and the breaking and forming of a chemical bond have now found a rigorous explanation by studying phase space structures.

  4. Assessment of proposed electromagnetic quantum vacuum energy extraction methods

    OpenAIRE

    Moddel, Garret

    2009-01-01

    In research articles and patents several methods have been proposed for the extraction of zero-point energy from the vacuum. None has been reliably demonstrated, but the proposals remain largely unchallenged. In this paper the feasibility of these methods is assessed in terms of underlying thermodynamics principles of equilibrium, detailed balance, and conservation laws. The methods are separated into three classes: nonlinear processing of the zero-point field, mechanical extraction using Cas...

  5. Molecular Structure and Electronic Properties of Porphyrin-Thiophene-Perylene Using Quantum Chemical Calculation

    Directory of Open Access Journals (Sweden)

    Tatiya Chokbunpiam

    2010-01-01

    Full Text Available This study aimed to design a new series of compounds consisting of a porphyrin macrocycle linked to a perylene unit via a thiophenic bridge. The structural and electronic properties of the molecules, and the effects of mono- and di-substituents R on C3 and R′ on C4 of the thiophene ring were investigated using a quantum calculation approach. The results from the method validation revealed that using the density functional theory approach at B3LYP/6–31G(d data set was the optimal one, considering the accuracy attained and maintaining the computer time required within tractable limits. The results from the B3LYP/6–31G(d approach indicated that significant changes of the torsion angle between the molecular planes of the porphyrin and perylene rings, compared to that of the unsubstituted derivatives, were found in the di-substituted systems bearing R = R′ = −OCH3 and −NH2, and in a mono-substituted system having R = −H and R′=−NH2. The symmetric di-substitution does not provide a significantly lower HOMO-LUMO energy gap (ΔEg. Noticeable decreases in ΔEg were found only with the substitution patterns of: R, R′ = −OCH3, −H; −OH, −H; −N(CH32, −H; −H, −NH2. UV-visible spectra of all derivatives exhibited characteristic absorption maxima of the free bases of porphyrin and perylene.

  6. Structural, vibrational, electronic investigations and quantum chemical studies of 2-amino-4-methoxybenzothiazole

    Science.gov (United States)

    Arjunan, V.; Raj, Arushma; Santhanam, R.; Marchewka, M. K.; Mohan, S.

    2013-02-01

    Extensive vibrational investigations of 2-amino-4-methoxybenzothiazole have been carried out with FTIR and FT-Raman spectral techniques. The electronic structure of the molecule has been analysed by UV-Visible and NMR spectroscopies. The DFT studies were carried out with B3LYP and HF methods utilising 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets to determine the structural, thermodynamical, vibrational, electronic characteristics of the compound and also to understand the electronic and steric influence of the methoxy amino groups on the skeletal frequencies. The mixing of the fundamental modes was determined with the help of total energy distribution (TED). The energies of the frontier molecular orbitals have also been determined. The kinetic and thermodynamic stability and chemical hardness of the molecule have been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. 1H and 13C NMR chemical shifts and the electronic transitions of the molecule are also discussed.

  7. Structural, vibrational, electronic investigations and quantum chemical studies of 2-amino-4-methoxybenzothiazole.

    Science.gov (United States)

    Arjunan, V; Raj, Arushma; Santhanam, R; Marchewka, M K; Mohan, S

    2013-02-01

    Extensive vibrational investigations of 2-amino-4-methoxybenzothiazole have been carried out with FTIR and FT-Raman spectral techniques. The electronic structure of the molecule has been analysed by UV-Visible and NMR spectroscopies. The DFT studies were carried out with B3LYP and HF methods utilising 6-31G(d,p), 6-311++G(d,p) and cc-pVDZ basis sets to determine the structural, thermodynamical, vibrational, electronic characteristics of the compound and also to understand the electronic and steric influence of the methoxy amino groups on the skeletal frequencies. The mixing of the fundamental modes was determined with the help of total energy distribution (TED). The energies of the frontier molecular orbitals have also been determined. The kinetic and thermodynamic stability and chemical hardness of the molecule have been determined. Complete NBO analysis was also carried out to find out the intramolecular electronic interactions and their stabilisation energy. (1)H and (13)C NMR chemical shifts and the electronic transitions of the molecule are also discussed. Copyright © 2012 Elsevier B.V. All rights reserved.

  8. Teaching Basic Quantum Mechanics in Secondary School Using Concepts of Feynman Path Integrals Method

    Science.gov (United States)

    Fanaro, Maria de los Angeles; Otero, Maria Rita; Arlego, Marcelo

    2012-01-01

    This paper discusses the teaching of basic quantum mechanics in high school. Rather than following the usual formalism, our approach is based on Feynman's path integral method. Our presentation makes use of simulation software and avoids sophisticated mathematical formalism. (Contains 3 figures.)

  9. A novel method of including Landau level mixing in numerical studies of the quantum Hall effect

    International Nuclear Information System (INIS)

    Wooten, Rachel; Quinn, John; Macek, Joseph

    2013-01-01

    Landau level mixing should influence the quantum Hall effect for all except the strongest applied magnetic fields. We propose a simple method for examining the effects of Landau level mixing by incorporating multiple Landau levels into the Haldane pseudopotentials through exact numerical diagonalization. Some of the resulting pseudopotentials for the lowest and first excited Landau levels will be presented

  10. Application of the perturbation series expansion quantum Monte Carlo method to multiorbital systems having Hund's coupling

    International Nuclear Information System (INIS)

    Sakai, Shiro; Arita, Ryotaro; Aoki, Hideo

    2006-01-01

    We propose a new quantum Monte Carlo method especially intended to couple with the dynamical mean-field theory. The algorithm is not only much more efficient than the conventional Hirsch-Fye algorithm, but is applicable to multiorbital systems having an SU(2)-symmetric Hund's coupling as well

  11. Improved numerical methods for quantum field theory (Outstanding junior investigator award)

    International Nuclear Information System (INIS)

    Sokal, A.D.

    1992-01-01

    We are developing new and more efficient numerical methods for problems in quantum field theory. Our principal goal is to achieve radical reductions in critical slowing-down. We are concentrating at present on three new families of algorithms: multi-grid Monte Carlo, Swendsen-Wang and generalized Wolff-type embedding algorithms. In addition, we are making a high-precision numerical study of the hyperscaling conjecture for the self-avoiding walk, which is closely related to the triviality problem for var-phi 4 quantum field theory

  12. Improved numerical methods for quantum field theory (Outstanding junior investigator award)

    International Nuclear Information System (INIS)

    Sokal, A.D.

    1993-01-01

    We are developing new and more efficient numerical methods for problems in quantum field theory. Our principal goal is to achieve radical reductions in critical slowing-down. We are concentrating at present on three new families of algorithms: multi-grid Monte Carlo (MGMC), Swendsen-Wang (SW) and generalized Wolff-type embedding algorithms. In addition, we are making a high-precision numerical study of the hyperscaling conjecture for the self-avoiding walk, which is closely related to the triviality problem for var-phi 4 quantum field theory

  13. Electron-phonon thermalization in a scalable method for real-time quantum dynamics

    Science.gov (United States)

    Rizzi, Valerio; Todorov, Tchavdar N.; Kohanoff, Jorge J.; Correa, Alfredo A.

    2016-01-01

    We present a quantum simulation method that follows the dynamics of out-of-equilibrium many-body systems of electrons and oscillators in real time. Its cost is linear in the number of oscillators and it can probe time scales from attoseconds to hundreds of picoseconds. Contrary to Ehrenfest dynamics, it can thermalize starting from a variety of initial conditions, including electronic population inversion. While an electronic temperature can be defined in terms of a nonequilibrium entropy, a Fermi-Dirac distribution in general emerges only after thermalization. These results can be used to construct a kinetic model of electron-phonon equilibration based on the explicit quantum dynamics.

  14. Nonequilibrium chemical potential in a two-dimensional electron gas in the quantum-Hall-effect regime

    Energy Technology Data Exchange (ETDEWEB)

    Pokhabov, D. A., E-mail: pokhabov@isp.nsc.ru; Pogosov, A. G.; Budantsev, M. V.; Zhdanov, E. Yu.; Bakarov, A. K. [Russian Academy of Sciences, Rzhanov Institute of Semiconductor Physics, Siberian Branch (Russian Federation)

    2016-08-15

    The nonequilibrium state of a two-dimensional electron gas in the quantum-Hall-effect regime is studied in Hall bars equipped with additional inner contacts situated within the bar. The magnetic-field dependence of the voltage drop between different contact pairs are studied at various temperatures. It was found that the voltage between the inner and outer contacts exhibits peaks of significant amplitude in narrow magnetic-field intervals near integer filling factors. Furthermore, the magnetic-field dependence of the voltage in these intervals exhibits a hysteresis, whereas the voltage between the outer contacts remains zero in the entire magnetic-field range. The appearance of the observed voltage peaks and their hysteretic behavior can be explained by an imbalance between the chemical potentials of edge and bulk states, resulting from nonequilibrium charge redistribution between the edge and bulk states when the magnetic field sweeps under conditions of the quantum Hall effect. The results of the study significantly complement the conventional picture of the quantum Hall effect, explicitly indicating the existence of a significant imbalance at the edge of the two-dimensional electron gas: the experimentally observed difference between the electrochemical potentials of the edge and bulk exceeds the distance between Landau levels by tens of times.

  15. Schwinger's quantum action principle from Dirac’s formulation through Feynman’s path integrals, the Schwinger-Keldysh method, quantum field theory, to source theory

    CERN Document Server

    Milton, Kimball A

    2015-01-01

    Starting from the earlier notions of stationary action principles, these tutorial notes shows how Schwinger’s Quantum Action Principle descended from Dirac’s formulation, which independently led Feynman to his path-integral formulation of quantum mechanics. Part I brings out in more detail the connection between the two formulations, and applications are discussed. Then, the Keldysh-Schwinger time-cycle method of extracting matrix elements is described. Part II will discuss the variational formulation of quantum electrodynamics and the development of source theory.

  16. Comparison of continuum and atomistic methods for the analysis of InAs/GaAs quantum dots

    DEFF Research Database (Denmark)

    Barettin, D.; Pecchia, A.; Penazzi, G.

    2011-01-01

    We present a comparison of continuum k · p and atomistic empirical Tight Binding methods for the analysis of the optoelectronic properties of InAs/GaAs quantum dots.......We present a comparison of continuum k · p and atomistic empirical Tight Binding methods for the analysis of the optoelectronic properties of InAs/GaAs quantum dots....

  17. Method of waste stabilization with dewatered chemically bonded phosphate ceramics

    Science.gov (United States)

    Wagh, Arun; Maloney, Martin D.

    2010-06-29

    A method of stabilizing a waste in a chemically bonded phosphate ceramic (CBPC). The method consists of preparing a slurry including the waste, water, an oxide binder, and a phosphate binder. The slurry is then allowed to cure to a solid, hydrated CBPC matrix. Next, bound water within the solid, hydrated CBPC matrix is removed. Typically, the bound water is removed by applying heat to the cured CBPC matrix. Preferably, the quantity of heat applied to the cured CBPC matrix is sufficient to drive off water bound within the hydrated CBPC matrix, but not to volatalize other non-water components of the matrix, such as metals and radioactive components. Typically, a temperature range of between 100.degree. C.-200.degree. C. will be sufficient. In another embodiment of the invention wherein the waste and water have been mixed prior to the preparation of the slurry, a select amount of water may be evaporated from the waste and water mixture prior to preparation of the slurry. Another aspect of the invention is a direct anyhydrous CBPC fabrication method wherein water is removed from the slurry by heating and mixing the slurry while allowing the slurry to cure. Additional aspects of the invention are ceramic matrix waste forms prepared by the methods disclosed above.

  18. Molecular structure and spectroscopic characterization of Carbamazepine with experimental techniques and DFT quantum chemical calculations

    Science.gov (United States)

    Suhasini, M.; Sailatha, E.; Gunasekaran, S.; Ramkumaar, G. R.

    2015-04-01

    A systematic vibrational spectroscopic assignment and analysis of Carbamazepine has been carried out by using FT-IR, FT-Raman and UV spectral data. The vibrational analysis were aided by electronic structure calculations - ab initio (RHF) and hybrid density functional methods (B3LYP) performed with standard basis set 6-31G(d,p). Molecular equilibrium geometries, electronic energies, natural bond order analysis, harmonic vibrational frequencies and IR intensities have been computed. A detailed interpretation of the vibrational spectra of the molecule has been made on the basis of the calculated Potential Energy Distribution (PED) by VEDA program. UV-visible spectrum of the compound was also recorded and the electronic properties, such as HOMO and LUMO energies and λmax were determined by HF/6-311++G(d,p) Time-Dependent method. The thermodynamic functions of the title molecule were also performed using the RHF and DFT methods. The restricted Hartree-Fock and density functional theory-based nuclear magnetic resonance (NMR) calculation procedure was also performed, and it was used for assigning the 13C and 1H NMR chemical shifts of Carbamazepine.

  19. Canonical methods in classical and quantum gravity: An invitation to canonical LQG

    Science.gov (United States)

    Reyes, Juan D.

    2018-04-01

    Loop Quantum Gravity (LQG) is a candidate quantum theory of gravity still under construction. LQG was originally conceived as a background independent canonical quantization of Einstein’s general relativity theory. This contribution provides some physical motivations and an overview of some mathematical tools employed in canonical Loop Quantum Gravity. First, Hamiltonian classical methods are reviewed from a geometric perspective. Canonical Dirac quantization of general gauge systems is sketched next. The Hamiltonian formultation of gravity in geometric ADM and connection-triad variables is then presented to finally lay down the canonical loop quantization program. The presentation is geared toward advanced undergradute or graduate students in physics and/or non-specialists curious about LQG.

  20. Microscopic origin of the fast blue-green luminescence of chemically synthesized non-oxidized silicon quantum dots.

    Science.gov (United States)

    Dohnalová, Kateřina; Fučíková, Anna; Umesh, Chinnaswamy P; Humpolíčková, Jana; Paulusse, Jos M J; Valenta, Jan; Zuilhof, Han; Hof, Martin; Gregorkiewicz, Tom

    2012-10-22

    The microscopic origin of the bright nanosecond blue-green photoluminescence (PL), frequently reported for synthesized organically terminated Si quantum dots (Si-QDs), has not been fully resolved, hampering potential applications of this interesting material. Here a comprehensive study of the PL from alkyl-terminated Si-QDs of 2-3 nm size, prepared by wet chemical synthesis is reported. Results obtained on the ensemble and those from the single nano-object level are compared, and they provide conclusive evidence that efficient and tunable emission arises due to radiative recombination of electron-hole pairs confined in the Si-QDs. This understanding paves the way towards applications of chemical synthesis for the development of Si-QDs with tunable sizes and bandgaps. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Wet chemical synthesis of quantum confined nanostructured tin oxide thin films by successive ionic layer adsorption and reaction technique

    Energy Technology Data Exchange (ETDEWEB)

    Murali, K.V., E-mail: kvmuralikv@gmail.com [School of Pure and Applied Physics, Department of Physics, Kannur University, Kerala 670327 (India); Department of Physics, Nehru Arts and Science College, Kanhangad, Kerala 671314 (India); Ragina, A.J. [School of Pure and Applied Physics, Department of Physics, Kannur University, Kerala 670327 (India); Department of Physics, Nehru Arts and Science College, Kanhangad, Kerala 671314 (India); Preetha, K.C. [School of Pure and Applied Physics, Department of Physics, Kannur University, Kerala 670327 (India); Department of Physics, Sree Narayana College, Kannur, Kerala 670007 (India); Deepa, K.; Remadevi, T.L. [School of Pure and Applied Physics, Department of Physics, Kannur University, Kerala 670327 (India); Department of Physics, Pazhassi Raja N.S.S. College, Mattannur, Kerala 670702 (India)

    2013-09-01

    Graphical abstract: - Highlights: • Quantum confined SnO{sub 2} thin films were synthesized at 80 °C by SILAR technique. • Film formation mechanism is discussed. • Films with snow like crystallite morphology offer high specific surface area. • The blue-shifted value of band gap confirmed the quantum confinement effect. • Present synthesis has advantages – low cost, low temperature and green friendly. - Abstract: Quantum confined nanostructured SnO{sub 2} thin films were synthesized at 353 K using ammonium chloride (NH{sub 4}Cl) and other chemicals by successive ionic layer adsorption and reaction technique. Film formation mechanism is discussed. Structural, morphological, optical and electrical properties were investigated and compared with the as-grown and annealed films fabricated without NH{sub 4}Cl solution. SnO{sub 2} films were polycrystalline with crystallites of tetragonal structure with grain sizes lie in the 5–8 nm range. Films with snow like crystallite morphology offer high specific surface area. The blue-shifted value of band gap of as-grown films confirmed the quantum confinement effect of grains. Refractive index of the films lies in the 2.1–2.3 range. Films prepared with NH{sub 4}Cl exhibit relatively lower resistivity of the order of 10{sup 0}–10{sup −1} Ω cm. The present synthesis has advantages such as low cost, low temperature and green friendly, which yields small particle size, large surface–volume ratio, and high crystallinity SnO{sub 2} films.

  2. Development of a benchtop baking method for chemically leavened crackers. II. Validation of the method

    Science.gov (United States)

    A benchtop baking method has been developed to predict the contribution of gluten functionality to overall flour performance for chemically leavened crackers. Using a diagnostic formula and procedure, dough rheology was analyzed to evaluate the extent of gluten development during mixing and machinin...

  3. ZnSe thin films by chemical bath deposition method

    Energy Technology Data Exchange (ETDEWEB)

    Lokhande, C.D.; Patil, P.S.; Tributsch, H. [Hahn-Meitner-Institute, Bereich Physikalische Chemie, Abt. CS, Glienicker Strasse-100, D-14109 Berlin (Germany); Ennaoui, A. [Hahn-Meitner-Institute, Bereich Physikalische Chemie, Abt. CG, Glienicker Strasse-100, D-14109 Berlin (Germany)

    1998-09-04

    The ZnSe thin films have been deposited onto glass substrates by the simple chemical bath deposition method using selenourea as a selenide ion source from an aqueous alkaline medium. The effect of Zn ion concentration, bath temperature and deposition time period on the quality and thickness of ZnSe films has been studied. The ZnSe films have been characterized by XRD, TEM, EDAX, TRMC (time-resolved microwave conductivity), optical absorbance and RBS techniques for their structural, compositional, electronic and optical properties. The as-deposited ZnSe films are found to be amorphous, Zn rich with optical band gap, Eg, equal to 2.9 eV

  4. Trace impurities in coal by wet chemical methods

    International Nuclear Information System (INIS)

    Pollock, E.N.

    1975-01-01

    In determining trace elements in coal by wet chemical methods, conventional atomic absorption spectroscopy (AAS) was used to determine Li, Be, V, Cr, Mn, Co, Ni, Cu, Zn, Ag, Cd, and Pb after dry ashing and acid dissolutions. A graphite furnace accessory was used for the flameless AAS determination of Bi, Se, Sn, Te, Be, Pb, As, Cd, Cr, Sb, and Ge. Mercury can be determined by flameless AAS after oxygen bomb combustion. Arsenic and antimony can be determined as their hydrides by AAS after low temperature ashing. Germanium, tin, bismuth, and tellurium can be determined as their hydrides by AAS after high temperature ashing. Selenium can be determined as its hydride by AAS after a special combustion procedure or after oxygen bomb combustion. Fluorine can be determined by specific ion analysis after oxygen bomb combustion. Boron can be determined colorimetrically. (U.S.)

  5. Studies of coupled chemical and catalytic coal conversion methods

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1990-01-01

    This report concerns our research on base-catalyzed coal solubilization and a new approach for hydrogen addition. The work on base-catalyzed, chemical solubilization is continuing. this report is focused on the hydrogenation research. Specifically it deals with the use of arene chromium carbonyl complexes as reagents for the addition of dideuterium to coal molecules. In one phase of the work, he has established that the aromatic hydrocarbons in a representative coal liquid can be converted in very good yield to arene chromium carbonyl compounds. In a second phase of the work directly related to our objective of improved methods for catalytic hydrogenation, he has established that the aromatic constituents of the same coal liquid add dideuterium in the presence of added napththalene chromium carbonyl.

  6. 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

    2016-01-01

    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

  7. Time-Resolved Quantum Cascade Laser Absorption Spectroscopy of Pulsed Plasma Assisted Chemical Vapor Deposition Processes Containing BCl3

    Science.gov (United States)

    Lang, Norbert; Hempel, Frank; Strämke, Siegfried; Röpcke, Jürgen

    2011-08-01

    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.

  8. Method of a covering space in quantum field theory

    International Nuclear Information System (INIS)

    Serebryanyj, E.M.

    1982-01-01

    To construct the Green function of the Laplace operator in the domain M bounded by conducting surfaces the generalized method of images is used. It is based on replacement of the domain M by its discrete bundle and that is why the term ''method of covering space'' is used. Continuing one of the coordinates to imaginary values the euclidean Green function is transformed into the causal one. This allows one to compute vacuum stress-energy tensor of the scalar massless field if the vacuum is stable [ru

  9. Combined use of computational chemistry and chemoinformatics methods for chemical discovery

    Energy Technology Data Exchange (ETDEWEB)

    Sugimoto, Manabu, E-mail: sugimoto@kumamoto-u.ac.jp [Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555 (Japan); Institute for Molecular Science, 38 Nishigo-Naka, Myodaiji, Okazaki 444-8585 (Japan); CREST, Japan Science and Technology Agency, 4-1-8 Honcho, Kawaguchi, Saitama 332-0012 (Japan); Ideo, Toshihiro; Iwane, Ryo [Graduate School of Science and Technology, Kumamoto University, 2-39-1, Kurokami, Chuo-ku, Kumamoto 860-8555 (Japan)

    2015-12-31

    Data analysis on numerical data by the computational chemistry calculations is carried out to obtain knowledge information of molecules. A molecular database is developed to systematically store chemical, electronic-structure, and knowledge-based information. The database is used to find molecules related to a keyword of “cancer”. Then the electronic-structure calculations are performed to quantitatively evaluate quantum chemical similarity of the molecules. Among the 377 compounds registered in the database, 24 molecules are found to be “cancer”-related. This set of molecules includes both carcinogens and anticancer drugs. The quantum chemical similarity analysis, which is carried out by using numerical results of the density-functional theory calculations, shows that, when some energy spectra are referred to, carcinogens are reasonably distinguished from the anticancer drugs. Therefore these spectral properties are considered of as important measures for classification.

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

    Science.gov (United States)

    Kamachi, Takashi; Yoshizawa, Kazunari

    2016-02-22

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

  11. Valence band structures of InAs/GaAs quantum rings using the Fourier transform method

    International Nuclear Information System (INIS)

    Jia Boyong; Yu Zhongyuan; Liu Yumin

    2009-01-01

    The valence band structures of strained InAs/GaAs quantum rings are calculated, with the four-band k · p model, in the framework of effective-mass envelope function theory. When determining the Hamiltonian matrix elements, we develop the Fourier transform method instead of the widely used analytical integral method. Using Fourier transform, we have investigated the energy levels as functions of the geometrical parameters of the rings and compared our results with those obtained by the analytical integral method. The results show that the energy levels in the quantum rings change dramatically with the inner radius, outer radius, average radius, width, height of the ring and the distance between two adjacent rings. Our method can be adopted in low-dimensional structures with arbitrary shape. Our results are consistent with those in the literature and should be helpful for studying and fabricating optoelectronic devices

  12. Quantum mechanical methods for calculation of force constants

    International Nuclear Information System (INIS)

    Mullally, D.J.

    1985-01-01

    The focus of this thesis is upon the calculation of force constants; i.e., the second derivatives of the potential energy with respect to nuclear displacements. This information is useful for the calculation of molecular vibrational modes and frequencies. In addition, it may be used for the location and characterization of equilibrium and transition state geometries. The methods presented may also be applied to the calculation of electric polarizabilities and infrared and Raman vibrational intensities. Two approaches to this problem are studied and evaluated: finite difference methods and analytical techniques. The most suitable method depends on the type and level of theory used to calculate the electronic wave function. Double point displacement finite differencing is often required for accurate calculation of the force constant matrix. These calculations require energy and gradient calculations on both sides of the geometry of interest. In order to speed up these calculations, a novel method is presented that uses geometry dependent information about the wavefunction. A detailed derivation for the analytical evaluation of force constants with a complete active space multiconfiguration self consistent field wave function is presented

  13. A method of constructive quantum mechanics of remarkable hidden beauty

    Czech Academy of Sciences Publication Activity Database

    Znojil, Miloslav

    2016-01-01

    Roč. 49, č. 45 (2016), č. článku 451003. ISSN 1751-8113 R&D Projects: GA ČR GA16-22945S Institutional support: RVO:61389005 Keywords : eigenvalue problems * iteration method Subject RIV: BE - Theoretical Physics Impact factor: 1.857, year: 2016

  14. Perspective: Ab initio force field methods derived from quantum mechanics

    Science.gov (United States)

    Xu, Peng; Guidez, Emilie B.; Bertoni, Colleen; Gordon, Mark S.

    2018-03-01

    It is often desirable to accurately and efficiently model the behavior of large molecular systems in the condensed phase (thousands to tens of thousands of atoms) over long time scales (from nanoseconds to milliseconds). In these cases, ab initio methods are difficult due to the increasing computational cost with the number of electrons. A more computationally attractive alternative is to perform the simulations at the atomic level using a parameterized function to model the electronic energy. Many empirical force fields have been developed for this purpose. However, the functions that are used to model interatomic and intermolecular interactions contain many fitted parameters obtained from selected model systems, and such classical force fields cannot properly simulate important electronic effects. Furthermore, while such force fields are computationally affordable, they are not reliable when applied to systems that differ significantly from those used in their parameterization. They also cannot provide the information necessary to analyze the interactions that occur in the system, making the systematic improvement of the functional forms that are used difficult. Ab initio force field methods aim to combine the merits of both types of methods. The ideal ab initio force fields are built on first principles and require no fitted parameters. Ab initio force field methods surveyed in this perspective are based on fragmentation approaches and intermolecular perturbation theory. This perspective summarizes their theoretical foundation, key components in their formulation, and discusses key aspects of these methods such as accuracy and formal computational cost. The ab initio force fields considered here were developed for different targets, and this perspective also aims to provide a balanced presentation of their strengths and shortcomings. Finally, this perspective suggests some future directions for this actively developing area.

  15. Controllable synthesis and characterization of CdS quantum dots by a microemulsion-mediated hydrothermal method

    Energy Technology Data Exchange (ETDEWEB)

    Chen, Rongrong; Han, Boning; Yang, Lin, E-mail: yanglin@hbu.edu.cn; Yang, Yanmin; Xu, Ying; Mai, Yaohua, E-mail: yaohuamai@hbu.edu.cn

    2016-04-15

    CdS QDs were successfully synthesized through a chemical reaction between cadmium acetate dehydrate and thioacetamide by using a microemulsion-mediated hydrothermal method. The properties of as-prepared CdS QDs can be controlled by using Emulsifier OP and CTAB surfactant, which produce a universal cubic phase and an unusual hexagonal phase, respectively. As a comparison, CdS QDs prepared by CTAB exhibit a better crystallinity and dispersibility. A possible mechanism involving the critical role of surfactant in the formation of crystal structure has also been explored in this paper. It is also found that the crystal size gradually increase with the increase of temperature, and the observation of red-shift in the absorption and emission peaks gives a clear evidence of the quantum confinement effect. All the desired properties of CdS QDs synthesized in this study imply the possibility of the preparation of high quality QDs under the appropriate reaction conditions.

  16. Impact of physical and chemical parameters on the hydroxyapatite nanopowder synthesized by chemical precipitation method

    Science.gov (United States)

    Thu Trang Pham, Thi; Phuong Nguyen, Thu; Pham, Thi Nam; Phuong Vu, Thi; Tran, Dai Lam; Thai, Hoang; Thanh Dinh, Thi Mai

    2013-09-01

    In this paper, the synthesis of hydroxyapatite (HAp) nanopowder was studied by chemical precipitation method at different values of reaction temperature, settling time, Ca/P ratio, calcination temperature, (NH4)2HPO4 addition rate, initial concentration of Ca(NO3)2 and (NH4)2HPO4. Analysis results of properties, morphology, structure of HAp powder from infrared (IR) spectra, x-ray diffraction (XRD), energy dispersive x-ray (EDX) spectra and scanning electron microscopy (SEM) indicated that the synthesized HAp powder had cylinder crystal shape with size less than 100 nm, single-phase structure. The variation of the synthesis conditions did not affect the morphology but affected the size of HAp crystals.

  17. Quantum Chemical Study of Supercritical Carbon Dioxide Effects on Combustion Kinetics.

    Science.gov (United States)

    Masunov, Artëm E; Wait, Elizabeth E; Atlanov, Arseniy A; Vasu, Subith S

    2017-05-18

    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 .

  18. A FPGA-based identity authority method in quantum key distribution system

    International Nuclear Information System (INIS)

    Cui Ke; Luo Chunli; Zhang Hongfei; Lin Shengzhao; Jin Ge; Wang Jian

    2012-01-01

    In this article, an identity authority method realized in hardware is developed which is used in quantum key distribution (QKD) systems. This method is based on LFSR-Teoplitz hashing matrix. Its benefits relay on its easy implementation in hardware and high secure coefficient. It can gain very high security by means of splitting part of the final key generated from QKD systems as the seed where it is required in the identity authority method. We propose an specific flow of the identity authority method according to the problems and features of the hardware. The proposed method can satisfy many kinds of QKD systems. (authors)

  19. Proceedings of quantum field theory, quantum mechanics, and quantum optics

    International Nuclear Information System (INIS)

    Dodonov, V.V.; Man; ko, V.I.

    1991-01-01

    This book contains papers presented at the XVIII International Colloquium on Group Theoretical Methods in Physics held in Moscow on June 4-9, 1990. Topics covered include; applications of algebraic methods in quantum field theory, quantum mechanics, quantum optics, spectrum generating groups, quantum algebras, symmetries of equations, quantum physics, coherent states, group representations and space groups

  20. Nonequilibrium Green's function method for quantum thermal transport

    Science.gov (United States)

    Wang, Jian-Sheng; Agarwalla, Bijay Kumar; Li, Huanan; Thingna, Juzar

    2014-12-01

    This review deals with the nonequilibrium Green's function (NEGF) method applied to the problems of energy transport due to atomic vibrations (phonons), primarily for small junction systems. We present a pedagogical introduction to the subject, deriving some of the well-known results such as the Laudauer-like formula for heat current in ballistic systems. The main aim of the review is to build the machinery of the method so that it can be applied to other situations, which are not directly treated here. In addition to the above, we consider a number of applications of NEGF, not in routine model system calculations, but in a few new aspects showing the power and usefulness of the formalism. In particular, we discuss the problems of multiple leads, coupled left-right-lead system, and system without a center. We also apply the method to the problem of full counting statistics. In the case of nonlinear systems, we make general comments on the thermal expansion effect, phonon relaxation time, and a certain class of mean-field approximations. Lastly, we examine the relationship between NEGF, reduced density matrix, and master equation approaches to thermal transport.