Quantum chemical studies of estrogenic compounds

USDA-ARS?s Scientific Manuscript database

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 ...

Accurate quantum chemical calculations

NASA Technical Reports Server (NTRS)

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

1989-01-01

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

Quantum-chemical Calculations in the Study of Antitumour Compounds

NASA Astrophysics Data System (ADS)

Luzhkov, V. B.; Bogdanov, G. N.

1986-01-01

The results of quantum-chemical calculations on antitumour preparations concerning the mechanism of their action at the electronic and molecular levels and structure-activity correlations are discussed in this review. Preparations whose action involves alkylating and free-radial mechanisms, complex-forming agents, and antimetabolites are considered. Modern quantum-chemical methods for calculations on biologically active substances are described. The bibliography includes 106 references.

Rhorix: An interface between quantum chemical topology and the 3D graphics program blender

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mills, Matthew J. L.; Sale, Kenneth L.; Simmons, Blake A.

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

Rhorix: An interface between quantum chemical topology and the 3D graphics program blender

DOE PAGES

Mills, Matthew J. L.; Sale, Kenneth L.; Simmons, Blake A.; ...

2017-08-31

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

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

NASA Astrophysics Data System (ADS)

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.

Diabatic models with transferrable parameters for generalized chemical reactions

NASA Astrophysics Data System (ADS)

Reimers, Jeffrey R.; McKemmish, Laura K.; McKenzie, Ross H.; Hush, Noel S.

2017-05-01

parameter space, and (iv), demonstrating the types of chemical reactions that may be suitable for exploitation as a chemical qubit in some quantum information processor.

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

PubMed

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.

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

PubMed

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.

Polynomial-time quantum algorithm for the simulation of chemical dynamics

PubMed Central

Kassal, Ivan; Jordan, Stephen P.; Love, Peter J.; Mohseni, Masoud; Aspuru-Guzik, Alán

2008-01-01

The computational cost of exact methods for quantum simulation using classical computers grows exponentially with system size. As a consequence, these techniques can be applied only to small systems. By contrast, we demonstrate that quantum computers could exactly simulate chemical reactions in polynomial time. Our algorithm uses the split-operator approach and explicitly simulates all electron-nuclear and interelectronic interactions in quadratic time. Surprisingly, this treatment is not only more accurate than the Born–Oppenheimer approximation but faster and more efficient as well, for all reactions with more than about four atoms. This is the case even though the entire electronic wave function is propagated on a grid with appropriately short time steps. Although the preparation and measurement of arbitrary states on a quantum computer is inefficient, here we demonstrate how to prepare states of chemical interest efficiently. We also show how to efficiently obtain chemically relevant observables, such as state-to-state transition probabilities and thermal reaction rates. Quantum computers using these techniques could outperform current classical computers with 100 qubits. PMID:19033207

Quantum Walks on the Line with Phase Parameters

NASA Astrophysics Data System (ADS)

Villagra, Marcos; Nakanishi, Masaki; Yamashita, Shigeru; Nakashima, Yasuhiko

In this paper, a study on discrete-time coined quantum walks on the line is presented. Clear mathematical foundations are still lacking for this quantum walk model. As a step toward this objective, the following question is being addressed: Given a graph, what is the probability that a quantum walk arrives at a given vertex after some number of steps? This is a very natural question, and for random walks it can be answered by several different combinatorial arguments. For quantum walks this is a highly non-trivial task. Furthermore, this was only achieved before for one specific coin operator (Hadamard operator) for walks on the line. Even considering only walks on lines, generalizing these computations to a general SU(2) coin operator is a complex task. The main contribution is a closed-form formula for the amplitudes of the state of the walk (which includes the question above) for a general symmetric SU(2) operator for walks on the line. To this end, a coin operator with parameters that alters the phase of the state of the walk is defined. Then, closed-form solutions are computed by means of Fourier analysis and asymptotic approximation methods. We also present some basic properties of the walk which can be deducted using weak convergence theorems for quantum walks. In particular, the support of the induced probability distribution of the walk is calculated. Then, it is shown how changing the parameters in the coin operator affects the resulting probability distribution.

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

PubMed

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.

The molecular structure of 4-methylpyridine-N-oxide: Gas-phase electron diffraction and quantum chemical calculations

NASA Astrophysics Data System (ADS)

Belova, Natalya V.; Girichev, Georgiy V.; Kotova, Vitaliya E.; Korolkova, Kseniya A.; Trang, Nguyen Hoang

2018-03-01

The molecular structure of 4-methylpiridine-N-oxide, 4-MePyO, has been studied by gas-phase electron diffraction monitored by mass spectrometry (GED/MS) and quantum chemical (DFT) calculations. Both, quantum chemistry and GED analyses resulted in CS molecular symmetry with the planar pyridine ring. Obtained molecular parameters confirm the hyperconjugation in the pyridine ring and the sp2 hybridization concept of the nitrogen and carbon atoms in the ring. The experimental geometric parameters are in a good agreement with the parameters for non-substituted N-oxide and reproduced very closely by DFT calculations. The presence of the electron-donating CH3 substituent in 4-MePyO leads to a decrease of the ipso-angle and to an increase of r(N→O) in comparison with the non-substituted PyO. Electron density distribution analysis has been performed in terms of natural bond orbitals (NBO) scheme. The nature of the semipolar N→O bond is discussed.

Ab initio Quantum Chemical and Experimental Reaction Kinetics Studies in the Combustion of Bipropellants

DTIC Science & Technology

2017-03-24

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

Quantum chemical approach to estimating the thermodynamics of metabolic reactions.

PubMed

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.

Quantum Chemical Approach to Estimating the Thermodynamics of Metabolic Reactions

PubMed Central

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

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 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. PMID:25387603

Order parameter fluctuations at a buried quantum critical point

PubMed Central

Feng, Yejun; Wang, Jiyang; Jaramillo, R.; van Wezel, Jasper; Haravifard, S.; Srajer, G.; Liu, Y.; Xu, Z.-A.; Littlewood, P. B.; Rosenbaum, T. F.

2012-01-01

Quantum criticality is a central concept in condensed matter physics, but the direct observation of quantum critical fluctuations has remained elusive. Here we present an X-ray diffraction study of the charge density wave (CDW) in 2H-NbSe2 at high pressure and low temperature, where we observe a broad regime of order parameter fluctuations that are controlled by proximity to a quantum critical point. X-rays can track the CDW despite the fact that the quantum critical regime is shrouded inside a superconducting phase; and in contrast to transport probes, allow direct measurement of the critical fluctuations of the charge order. Concurrent measurements of the crystal lattice point to a critical transition that is continuous in nature. Our results confirm the long-standing expectations of enhanced quantum fluctuations in low-dimensional systems, and may help to constrain theories of the quantum critical Fermi surface. PMID:22529348

Quantum Parameter Estimation: From Experimental Design to Constructive Algorithm

NASA Astrophysics Data System (ADS)

Yang, Le; Chen, Xi; Zhang, Ming; Dai, Hong-Yi

2017-11-01

In this paper we design the following two-step scheme to estimate the model parameter ω 0 of the quantum system: first we utilize the Fisher information with respect to an intermediate variable v=\\cos ({ω }0t) to determine an optimal initial state and to seek optimal parameters of the POVM measurement operators; second we explore how to estimate ω 0 from v by choosing t when a priori information knowledge of ω 0 is available. Our optimal initial state can achieve the maximum quantum Fisher information. The formulation of the optimal time t is obtained and the complete algorithm for parameter estimation is presented. We further explore how the lower bound of the estimation deviation depends on the a priori information of the model. Supported by the National Natural Science Foundation of China under Grant Nos. 61273202, 61673389, and 61134008

Chemical application of diffusion quantum Monte Carlo

NASA Technical Reports Server (NTRS)

Reynolds, P. J.; Lester, W. A., Jr.

1984-01-01

The diffusion quantum Monte Carlo (QMC) method gives a stochastic solution to the Schroedinger equation. This approach is receiving increasing attention in chemical applications as a result of its high accuracy. However, reducing statistical uncertainty remains a priority because chemical effects are often obtained as small differences of large numbers. As an example, the single-triplet splitting of the energy of the methylene molecule CH sub 2 is given. The QMC algorithm was implemented on the CYBER 205, first as a direct transcription of the algorithm running on the VAX 11/780, and second by explicitly writing vector code for all loops longer than a crossover length C. The speed of the codes relative to one another as a function of C, and relative to the VAX, are discussed. The computational time dependence obtained versus the number of basis functions is discussed and this is compared with that obtained from traditional quantum chemistry codes and that obtained from traditional computer architectures.

Parameter regimes for a single sequential quantum repeater

NASA Astrophysics Data System (ADS)

Rozpędek, F.; Goodenough, K.; Ribeiro, J.; Kalb, N.; Caprara Vivoli, V.; Reiserer, A.; Hanson, R.; Wehner, S.; Elkouss, D.

2018-07-01

Quantum key distribution allows for the generation of a secret key between distant parties connected by a quantum channel such as optical fibre or free space. Unfortunately, the rate of generation of a secret key by direct transmission is fundamentally limited by the distance. This limit can be overcome by the implementation of so-called quantum repeaters. Here, we assess the performance of a specific but very natural setup called a single sequential repeater for quantum key distribution. We offer a fine-grained assessment of the repeater by introducing a series of benchmarks. The benchmarks, which should be surpassed to claim a working repeater, are based on finite-energy considerations, thermal noise and the losses in the setup. In order to boost the performance of the studied repeaters we introduce two methods. The first one corresponds to the concept of a cut-off, which reduces the effect of decoherence during the storage of a quantum state by introducing a maximum storage time. Secondly, we supplement the standard classical post-processing with an advantage distillation procedure. Using these methods, we find realistic parameters for which it is possible to achieve rates greater than each of the benchmarks, guiding the way towards implementing quantum repeaters.

Quantum sensing of the phase-space-displacement parameters using a single trapped ion

NASA Astrophysics Data System (ADS)

Ivanov, Peter A.; Vitanov, Nikolay V.

2018-03-01

We introduce a quantum sensing protocol for detecting the parameters characterizing the phase-space displacement by using a single trapped ion as a quantum probe. We show that, thanks to the laser-induced coupling between the ion's internal states and the motion mode, the estimation of the two conjugated parameters describing the displacement can be efficiently performed by a set of measurements of the atomic state populations. Furthermore, we introduce a three-parameter protocol capable of detecting the magnitude, the transverse direction, and the phase of the displacement. We characterize the uncertainty of the two- and three-parameter problems in terms of the Fisher information and show that state projective measurement saturates the fundamental quantum Cramér-Rao bound.

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

PubMed

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.

Chemical accuracy from quantum Monte Carlo for the benzene dimer.

PubMed

Azadi, Sam; Cohen, R E

2015-09-14

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

Quantum chemical calculations of Cr2O3/SnO2 using density functional theory method

NASA Astrophysics Data System (ADS)

Jawaher, K. Rackesh; Indirajith, R.; Krishnan, S.; Robert, R.; Das, S. Jerome

2018-03-01

Quantum chemical calculations have been employed to study the molecular effects produced by Cr2O3/SnO2 optimised structure. The theoretical parameters of the transparent conducting metal oxides were calculated using DFT / B3LYP / LANL2DZ method. The optimised bond parameters such as bond lengths, bond angles and dihedral angles were calculated using the same theory. The non-linear optical property of the title compound was calculated using first-order hyperpolarisability calculation. The calculated HOMO-LUMO analysis explains the charge transfer interaction between the molecule. In addition, MEP and Mulliken atomic charges were also calculated and analysed.

QSAR, DFT and quantum chemical studies on the inhibition potentials of some carbozones for the corrosion of mild steel in HCl.

PubMed

Eddy, Nnabuk O; Ita, Benedict I

2011-02-01

Experimental aspects of the inhibition of the corrosion of mild steel in HCl solutions by some carbozones were studied using gravimetric, thermometric and gasometric methods, while a theoretical study was carried out using density functional theory, a quantitative structure-activity relation, and quantum chemical principles. The results obtained indicated that the studied carbozones are good adsorption inhibitors for the corrosion of mild steel in HCl. The inhibition efficiencies of the studied carbozones were found to increase with increasing concentration of the respective inhibitor. A strong correlation was found between the average inhibition efficiency and some quantum chemical parameters, and also between the experimental and theoretical inhibition efficiencies (obtained from the quantitative structure-activity relation).

Exponential energy growth due to slow parameter oscillations in quantum mechanical systems.

PubMed

Turaev, Dmitry

2016-05-01

It is shown that a periodic emergence and destruction of an additional quantum number leads to an exponential growth of energy of a quantum mechanical system subjected to a slow periodic variation of parameters. The main example is given by systems (e.g., quantum billiards and quantum graphs) with periodically divided configuration space. In special cases, the process can also lead to a long period of cooling that precedes the acceleration, and to the desertion of the states with a particular value of the quantum number.

Quantum demultiplexer of quantum parameter-estimation information in quantum networks

NASA Astrophysics Data System (ADS)

Xie, Yanqing; Huang, Yumeng; Wu, Yinzhong; Hao, Xiang

2018-05-01

The quantum demultiplexer is constructed by a series of unitary operators and multipartite entangled states. It is used to realize information broadcasting from an input node to multiple output nodes in quantum networks. The scheme of quantum network communication with respect to phase estimation is put forward through the demultiplexer subjected to amplitude damping noises. The generalized partial measurements can be applied to protect the transferring efficiency from environmental noises in the protocol. It is found out that there are some optimal coherent states which can be prepared to enhance the transmission of phase estimation. The dynamics of state fidelity and quantum Fisher information are investigated to evaluate the feasibility of the network communication. While the state fidelity deteriorates rapidly, the quantum Fisher information can be enhanced to a maximum value and then decreases slowly. The memory effect of the environment induces the oscillations of fidelity and quantum Fisher information. The adjustment of the strength of partial measurements is helpful to increase quantum Fisher information.

Parameters for the RM1 Quantum Chemical Calculation of Complexes of the Trications of Thulium, Ytterbium and Lutetium

PubMed Central

Filho, Manoel A. M.; Dutra, José Diogo L.; Rocha, Gerd B.; Simas, Alfredo M.

2016-01-01

The RM1 quantum chemical model for the calculation of complexes of Tm(III), Yb(III) and Lu(III) is advanced. Subsequently, we tested the models by fully optimizing the geometries of 126 complexes. We then compared the optimized structures with known crystallographic ones from the Cambridge Structural Database. Results indicate that, for thulium complexes, the accuracy in terms of the distances between the lanthanide ion and its directly coordinated atoms is about 2%. Corresponding results for ytterbium and lutetium are both 3%, levels of accuracy useful for the design of lanthanide complexes, targeting their countless applications. PMID:27223475

Mutual information as an order parameter for quantum synchronization

NASA Astrophysics Data System (ADS)

Ameri, V.; Eghbali-Arani, M.; Mari, A.; Farace, A.; Kheirandish, F.; Giovannetti, V.; Fazio, R.

2015-01-01

Spontaneous synchronization is a fundamental phenomenon, important in many theoretical studies and applications. Recently, this effect has been analyzed and observed in a number of physical systems close to the quantum-mechanical regime. In this work we propose mutual information as a useful order parameter which can capture the emergence of synchronization in very different contexts, ranging from semiclassical to intrinsically quantum-mechanical systems. Specifically, we first study the synchronization of two coupled Van der Pol oscillators in both classical and quantum regimes and later we consider the synchronization of two qubits inside two coupled optical cavities. In all these contexts, we find that mutual information can be used as an appropriate figure of merit for determining the synchronization phases independently of the specific details of the system.

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

PubMed

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.

Parameter Estimation of Fractional-Order Chaotic Systems by Using Quantum Parallel Particle Swarm Optimization Algorithm

PubMed Central

Huang, Yu; Guo, Feng; Li, Yongling; Liu, Yufeng

2015-01-01

Parameter estimation for fractional-order chaotic systems is an important issue in fractional-order chaotic control and synchronization and could be essentially formulated as a multidimensional optimization problem. A novel algorithm called quantum parallel particle swarm optimization (QPPSO) is proposed to solve the parameter estimation for fractional-order chaotic systems. The parallel characteristic of quantum computing is used in QPPSO. This characteristic increases the calculation of each generation exponentially. The behavior of particles in quantum space is restrained by the quantum evolution equation, which consists of the current rotation angle, individual optimal quantum rotation angle, and global optimal quantum rotation angle. Numerical simulation based on several typical fractional-order systems and comparisons with some typical existing algorithms show the effectiveness and efficiency of the proposed algorithm. PMID:25603158

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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 190-800 nm 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.

Listening to Chemical Materials: Determination of the Photophysical Parameters by Photoacoustic Spectroscopy

NASA Astrophysics Data System (ADS)

Yang, Y. T.; Zhang, S. Y.; Liu, X. J.

2012-11-01

Recently, photoacoustic (PA) spectroscopy has emerged as a valuable tool for the study of various kinds of materials. Herein, we present the results of PA spectral studies of chemical materials. First, the PA study on luminescent materials in condensed states is reported. Combining with the luminescence technique, the energy transfer efficiency and the intrinsic luminescence quantum yield are determined for a europium (III) complex in the glassy state, smectic A phase, and the isotropic liquid. Second, neodymium (III) compounds with l-glycine, l-phenylalanine, and l-tryptophan are synthesized and their PA spectra are reported. The nephelauxetic ratio and Sinha parameter are calculated based on the PA spectra. The environmental effect on the f-f transitions of the neodymium(III) ion is also studied.

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.

PubMed

Dibetsoe, Masego; Olasunkanmi, Lukman O; Fayemi, Omolola E; Yesudass, Sasikumar; Ramaganthan, Baskar; Bahadur, Indra; Adekunle, Abolanle S; Kabanda, Mwadham M; Ebenso, Eno E

2015-08-28

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 analysis on the

Influence of Constraint in Parameter Space on Quantum Games

NASA Astrophysics Data System (ADS)

Zhao, Hai-Jun; Fang, Xi-Ming

2004-04-01

We study the influence of the constraint in the parameter space on quantum games. Decomposing SU(2) operator into product of three rotation operators and controlling one kind of them, we impose a constraint on the parameter space of the players' operator. We find that the constraint can provide a tuner to make the bilateral payoffs equal, so that the mismatch of the players' action at multi-equilibrium could be avoided. We also find that the game exhibits an intriguing structure as a function of the parameter of the controlled operators, which is useful for making game models.

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

PubMed

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.

GUP parameter from quantum corrections to the Newtonian potential

NASA Astrophysics Data System (ADS)

Scardigli, Fabio; Lambiase, Gaetano; Vagenas, Elias C.

2017-04-01

We propose a technique to compute the deformation parameter of the generalized uncertainty principle by using the leading quantum corrections to the Newtonian potential. We just assume General Relativity as theory of Gravitation, and the thermal nature of the GUP corrections to the Hawking spectrum. With these minimal assumptions our calculation gives, to first order, a specific numerical result. The physical meaning of this value is discussed, and compared with the previously obtained bounds on the generalized uncertainty principle deformation parameter.

A quantum informational approach for dissecting chemical reactions

NASA Astrophysics Data System (ADS)

Duperrouzel, Corinne; Tecmer, Paweł; Boguslawski, Katharina; Barcza, Gergely; Legeza, Örs; Ayers, Paul W.

2015-02-01

We present a conceptionally different approach to dissect bond-formation processes in metal-driven catalysis using concepts from quantum information theory. Our method uses the entanglement and correlation among molecular orbitals to analyze changes in electronic structure that accompany chemical processes. As a proof-of-principle example, the evolution of nickel-ethene bond-formation is dissected, which allows us to monitor the interplay of back-bonding and π-donation along the reaction coordinate. Furthermore, the reaction pathway of nickel-ethene complexation is analyzed using quantum chemistry methods, revealing the presence of a transition state. Our study supports the crucial role of metal-to-ligand back-donation in the bond-forming process of nickel-ethene.

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

NASA Astrophysics Data System (ADS)

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).

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

PubMed

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.

Adsorption, Thermodynamic and Quantum Chemical Studies of 1-hexyl-3-methylimidazolium Based Ionic Liquids as Corrosion Inhibitors for Mild Steel in HCl

PubMed Central

Mashuga, Motsie E.; Olasunkanmi, Lukman O.; Adekunle, Abolanle S.; Yesudass, Sasikumar; Kabanda, Mwadham M.; Ebenso, Eno E.

2015-01-01

The inhibition of mild steel corrosion in 1 M HCl solution by some ionic liquids (ILs) namely, 1-hexyl-3-methylimidazolium trifluoromethanesulfonate [HMIM][TfO], 1-hexyl-3-methylimidazolium tetrafluoroborate [HMIM][BF4], 1-hexyl-3-methylimidazolium hexafluorophosphate [HMIM][PF6], and 1-hexyl-3-methylimidazolium iodide [HMIM][I] was investigated using electrochemical measurements, spectroscopic analyses and quantum chemical calculations. All the ILs showed appreciably high inhibition efficiency. At 303 K, the results of electrochemical measurements indicated that the studied ILs are mixed-type inhibitors. The adsorption studies showed that all the four ILs adsorb spontaneously on steel surface with [HMIM][TfO], [HMIM][BF4] and [HMIM][I] obeying Langmuir adsorption isotherm, while [HMIM][PF6] conformed better with Temkin adsorption isotherm. Spectroscopic analyses suggested the formation of Fe/ILs complexes. Some quantum chemical parameters were calculated to corroborate experimental results.

Quantum Degeneracy in Atomic Point Contacts Revealed by Chemical Force and Conductance

NASA Astrophysics Data System (ADS)

Sugimoto, Yoshiaki; Ondráček, Martin; Abe, Masayuki; Pou, Pablo; Morita, Seizo; Perez, Ruben; Flores, Fernando; Jelínek, Pavel

2013-09-01

Quantum degeneracy is an important concept in quantum mechanics with large implications to many processes in condensed matter. Here, we show the consequences of electron energy level degeneracy on the conductance and the chemical force between two bodies at the atomic scale. We propose a novel way in which a scanning probe microscope can detect the presence of degenerate states in atomic-sized contacts even at room temperature. The tunneling conductance G and chemical binding force F between two bodies both tend to decay exponentially with distance in a certain distance range, usually maintaining direct proportionality G∝F. However, we show that a square relation G∝F2 arises as a consequence of quantum degeneracy between the interacting frontier states of the scanning tip and a surface atom. We demonstrate this phenomenon on the Si(111)-(7×7) surface reconstruction where the Si adatom possesses a strongly localized dangling-bond state at the Fermi level.

Triple coupling and parameter resonance in quantum optomechanics with a single atom

NASA Astrophysics Data System (ADS)

Chang, Yue; Ian, H.; Sun, C. P.

2009-11-01

We study the energy level structure and quantum dynamics for a cavity optomechanical system assisted by a single atom. It is found that a triple coupling involving a photon, a phonon and an atom cannot be described only by the quasi-orbital angular momentum at frequency resonance, there also exists the phenomenon of parameter resonance, namely, when the system parameters are matched in some way, the evolution of the end mirror of the cavity is conditioned by the dressed states of the photon-atom subsystem. The quantum decoherence due to this conditional dynamics is studied in detail. In the quasi-classical limit of very large angular momentum, this system will behave like a standard cavity-QED system described by the Jaynes-Cummings (J-C) model when the angular momentum operators are transformed to bosonic operators of a single mode. We test this observation with an experimentally accessible parameter.

Studies on the Conformational Landscape of Tert-Butyl Acetate Using Microwave Spectroscopy and Quantum Chemical Calculations

NASA Astrophysics Data System (ADS)

Zhao, YueYue; Mouhib, Halima; Li, Guohua; Stahl, Wolfgang; Kleiner, Isabelle

2014-06-01

The tert-Butyl acetate molecule was studied using a combination of quantum chemical calculations and molecular beam Fourier transform microwave spectroscopy in the 9 to 14 GHz range. Due to its rather rigid frame, the molecule possesses only two different conformers: one of Cs and one of C1 symmetry. According to ab initio calculations, the Cs conformer is 46 kJ/mol lower in energy and is the one observed in the supersonic jet. We report on the structure and dynamics of the most abundant conformer of tert-butyl acetate, with accurate rotational and centrifugal distortion constants. Additionally, the barrier to internal rotation of the acetyl methyl group was determined. Splittings due to the internal rotation of the methyl group of up to 1.3 GHz were observed in the spectrum. Using the programs XIAM and BELGI-Cs, we determine the barrier height to be about 113 cm-1 and compare the molecular parameters obtained from these two codes. Additionally, the experimental rotational constants were used to validate numerous quantum chemical calculations. This study is part of a larger project which aims at determining the lowest energy conformers of organic esters and ketones which are of interest for flavor or perfume synthetic applications Project partly supported by the PHC PROCOPE 25059YB.

Quantum chemical study of methane oxidation species

NASA Technical Reports Server (NTRS)

Jackels, Charles F.

1993-01-01

The research funded by this project has focused on quantum chemical investigations of molecular species thought to be important in the chemistry of the earth's upper and lower atmospheres. The body of this report contains brief discussions of the results of the several phases of this investigation. In many instances these results have been presented at scientific meetings and/or published in refereed journals. Those bibliographic references are given. In addition to the study of specific chemical systems, there were several phases during the course of this investigation where much of the effort went into the development and modification of computer codes necessary to carry out these calculations on the wide range of computer equipment used during this study. This type of code maintenance and development work did not generally result in publications and presentations, but a brief review is given.

Chemically Triggered Formation of Two-Dimensional Epitaxial Quantum Dot Superlattices.

PubMed

Walravens, Willem; De Roo, Jonathan; Drijvers, Emile; Ten Brinck, Stephanie; Solano, Eduardo; Dendooven, Jolien; Detavernier, Christophe; Infante, Ivan; Hens, Zeger

2016-07-26

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 restore nanocrystal stoichiometry can trigger the formation of epitaxial superlattices of PbSe and PbS quantum dots. More specifically, we show that both chalcogen-adding (sodium sulfide) and lead oleate displacing (amines) additives induce small area epitaxial superlattices of PbSe quantum dots. In the latter case, the amine basicity is a sensitive handle to tune the superlattice symmetry, with strong and weak bases yielding pseudohexagonal or quasi-square lattices, respectively. Through density functional theory calculations and in situ titrations monitored by nuclear magnetic resonance spectroscopy, we link this observation to the concomitantly different coordination enthalpy and ligand displacement potency of the amine. Next to that, an initial ∼10% reduction of the initial ligand density prior to monolayer formation and addition of a mild, lead oleate displacing chemical trigger such as aniline proved key to induce square superlattices with long-range, square micrometer order; an effect that is the more pronounced the larger the quantum dots. Because the approach applies to PbS quantum dots as well, we conclude that it offers a reproducible and rational method for the formation of highly ordered epitaxial quantum dot superlattices.

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

NASA Astrophysics Data System (ADS)

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.

The structure and photochemical transformation of cyclopropylacetylene radical cation as revealed by matrix EPR and quantum chemical study

NASA Astrophysics Data System (ADS)

Shiryaeva, Ekaterina S.; Tyurin, Daniil A.; Feldman, Vladimir I.

2012-05-01

The primary radical cation of cyclopropylacetylene was first characterized by EPR spectroscopy in low-temperature freon matrices. The assignment was confirmed by specific deuteration and quantum-chemical calculations at PBE0 and CCSD(T) levels. Photolysis with visible light led to irreversible transformation of the initial species to a ring-open structure. Detailed computational analysis of energy and magnetic resonance parameters of possible reaction products justified formation of pent-3-en-1-yne radical cation (presumably, a (Z)-isomer). This conclusion was also supported by the effect of specific deuteration.

Quantum Monte Carlo tunneling from quantum chemistry to quantum annealing

NASA Astrophysics Data System (ADS)

Mazzola, Guglielmo; Smelyanskiy, Vadim N.; Troyer, Matthias

2017-10-01

Quantum tunneling is ubiquitous across different fields, from quantum chemical reactions and magnetic materials to quantum simulators and quantum computers. While simulating the real-time quantum dynamics of tunneling is infeasible for high-dimensional systems, quantum tunneling also shows up in quantum Monte Carlo (QMC) simulations, which aim to simulate quantum statistics with resources growing only polynomially with the system size. Here we extend the recent results obtained for quantum spin models [Phys. Rev. Lett. 117, 180402 (2016), 10.1103/PhysRevLett.117.180402], and we study continuous-variable models for proton transfer reactions. We demonstrate that QMC simulations efficiently recover the scaling of ground-state tunneling rates due to the existence of an instanton path, which always connects the reactant state with the product. We discuss the implications of our results in the context of quantum chemical reactions and quantum annealing, where quantum tunneling is expected to be a valuable resource for solving combinatorial optimization problems.

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

NASA Astrophysics Data System (ADS)

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.

Effect of laser pulse shaping parameters on the fidelity of quantum logic gates.

PubMed

Zaari, Ryan R; Brown, Alex

2012-09-14

The effect of varying parameters specific to laser pulse shaping instruments on resulting fidelities for the ACNOT(1), NOT(2), and Hadamard(2) quantum logic gates are studied for the diatomic molecule (12)C(16)O. These parameters include varying the frequency resolution, adjusting the number of frequency components and also varying the amplitude and phase at each frequency component. A time domain analytic form of the original discretized frequency domain laser pulse function is derived, providing a useful means to infer the resulting pulse shape through variations to the aforementioned parameters. We show that amplitude variation at each frequency component is a crucial requirement for optimal laser pulse shaping, whereas phase variation provides minimal contribution. We also show that high fidelity laser pulses are dependent upon the frequency resolution and increasing the number of frequency components provides only a small incremental improvement to quantum gate fidelity. Analysis through use of the pulse area theorem confirms the resulting population dynamics for one or two frequency high fidelity laser pulses and implies similar dynamics for more complex laser pulse shapes. The ability to produce high fidelity laser pulses that provide both population control and global phase alignment is attributed greatly to the natural evolution phase alignment of the qubits involved within the quantum logic gate operation.

Tunable Quantum Spin Liquidity in the 1 /6 th-Filled Breathing Kagome Lattice

NASA Astrophysics Data System (ADS)

Akbari-Sharbaf, A.; Sinclair, R.; Verrier, A.; Ziat, D.; Zhou, H. D.; Sun, X. F.; Quilliam, J. A.

2018-06-01

We present measurements on a series of materials, Li2 In1 -xScx Mo3 O8 , that can be described as a 1 /6 th-filled breathing kagome lattice. Substituting Sc for In generates chemical pressure which alters the breathing parameter nonmonotonically. Muon spin rotation experiments show that this chemical pressure tunes the system from antiferromagnetic long range order to a quantum spin liquid phase. A strong correlation with the breathing parameter implies that it is the dominant parameter controlling the level of magnetic frustration, with increased kagome symmetry generating the quantum spin liquid phase. Magnetic susceptibility measurements suggest that this is related to distinct types of charge order induced by changes in lattice symmetry, in line with the theory of Chen et al. [Phys. Rev. B 93, 245134 (2016), 10.1103/PhysRevB.93.245134]. The specific heat for samples at intermediate Sc concentration, which have the minimum breathing parameter, show consistency with the predicted U (1 ) quantum spin liquid.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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), 1H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong 1H-1H homonuclear dipolar couplings and narrow 1H 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) 1H 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 1H-1H 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 information for

Double quantum coherence ESR spectroscopy and quantum chemical calculations on a BDPA biradical.

PubMed

Haeri, Haleh Hashemi; Spindler, Philipp; Plackmeyer, Jörn; Prisner, Thomas

2016-10-26

Carbon-centered radicals are interesting alternatives to otherwise commonly used nitroxide spin labels for dipolar spectroscopy techniques because of their narrow ESR linewidth. Herein, we present a novel BDPA biradical, where two BDPA (α,α,γ,γ-bisdiphenylene-β-phenylallyl) radicals are covalently tethered by a saturated biphenyl acetylene linker. The inter-spin distance between the two spin carrier fragments was measured using double quantum coherence (DQC) ESR methodology. The DQC experiment revealed a mean distance of only 1.8 nm between the two unpaired electron spins. This distance is shorter than the predictions based on a simple modelling of the biradical geometry with the electron spins located at the central carbon atoms. Therefore, DFT (density functional theory) calculations were performed to obtain a picture of the spin delocalization, which may give rise to a modified dipolar interaction tensor, and to find those conformations that correspond best to the experimentally observed inter-spin distance. Quantum chemical calculations showed that the attachment of the biphenyl acetylene linker at the second position of the fluorenyl ring of BDPA did not affect the spin population or geometry of the BDPA radical. Therefore, spin delocalization and geometry optimization of each BDPA moiety could be performed on the monomeric unit alone. The allylic dihedral angle θ 1 between the fluorenyl rings in the monomer subunit was determined to be 30° or 150° using quantum chemical calculations. The proton hyperfine coupling constant calculated from both energy minima was in very good agreement with literature values. Based on the optimal monomer geometries and spin density distributions, the dipolar coupling interaction between both BDPA units could be calculated for several dimer geometries. It was shown that the rotation of the BDPA units around the linker axis (θ 2 ) does not significantly influence the dipolar coupling strength when compared to the allylic

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

PubMed

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

2014-12-10

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, (13)C and (1)H 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. Copyright © 2014 Elsevier B.V. All rights reserved.

Cluster Quantum Chemical Study of the Grignard Reagent Formation

NASA Astrophysics Data System (ADS)

Tulub, A. V.; Porsev, V. V.

The main stages of the Grignard reagent formation are described in a framework of quantum chemical cluster model. We have established two kinds of the adsorption of CH3Hal on Mgn clusters, one of which leads to radical formation and the second is responsible for radical free dissociate adsorption. The charge redistribution in cluster CH3MgnHal result to the strong electrostatic interaction with ether and Grignard reagent formation without any activation barrier.

Lighting up micromotors with quantum dots for smart chemical sensing.

PubMed

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.

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

PubMed

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.

A Parameter-Free Semilocal Exchange Energy Functional for Two-Dimensional Quantum Systems.

PubMed

Patra, Abhilash; Jana, Subrata; Samal, Prasanjit

2018-04-05

The method of constructing semilocal density functional for exchange in two dimensions using one of the premier approaches, i.e., density matrix expansion, is revisited, and an accurate functional is constructed. The form of the functional is quite simple and includes no adjustable semiempirical parameters. In it, the kinetic energy dependent momentum is used to compensate nonlocal effects of the system. The functional is then examined by considering the very well-known semiconductor quantum dot systems. And despite its very simple form, the results obtained for quantum dots containing a higher number of electrons agrees pretty well with that of the standard exact exchange theory. Some of the desired properties relevant for the two-dimensional exchange functional and the lower bound associated with it are also discussed. It is observed that the above parameter-free semilocal exchange functional satisfies most of the discussed conditions.

Universality in quantum chaos and the one-parameter scaling theory.

PubMed

García-García, Antonio M; Wang, Jiao

2008-02-22

The one-parameter scaling theory is adapted to the context of quantum chaos. We define a generalized dimensionless conductance, g, semiclassically and then study Anderson localization corrections by renormalization group techniques. This analysis permits a characterization of the universality classes associated to a metal (g-->infinity), an insulator (g-->0), and the metal-insulator transition (g-->g(c)) in quantum chaos provided that the classical phase space is not mixed. According to our results the universality class related to the metallic limit includes all the systems in which the Bohigas-Giannoni-Schmit conjecture holds but automatically excludes those in which dynamical localization effects are important. The universality class related to the metal-insulator transition is characterized by classical superdiffusion or a fractal spectrum in low dimensions (d < or = 2). Several examples are discussed in detail.

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

NASA Astrophysics Data System (ADS)

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.

Molecular mechanism of NDMA formation from N,N-dimethylsulfamide during ozonation: quantum chemical insights into a bromide-catalyzed pathway.

PubMed

Trogolo, Daniela; Mishra, Brijesh Kumar; Heeb, Michèle B; von Gunten, Urs; Arey, J Samuel

2015-04-07

During ozonation of drinking water, the fungicide metabolite N,N-dimethylsulfamide (DMS) can be transformed into a highly toxic product, N-nitrosodimethylamine (NDMA). We used quantum chemical computations and stopped-flow experiments to evaluate a chemical mechanism proposed previously to describe this transformation. Stopped-flow experiments indicate a pK(a) = 10.4 for DMS. Experiments show that hypobromous acid (HOBr), generated by ozone oxidation of naturally occurring bromide, brominates the deprotonated DMS(-) anion with a near-diffusion controlled rate constant (7.1 ± 0.6 × 10(8) M(-1) s(-1)), forming Br-DMS(-) anion. According to quantum chemical calculations, Br-DMS has a pK(a) ∼ 9.0 and thus remains partially deprotonated at neutral pH. The anionic Br-DMS(-) bromamine can react with ozone with a high rate constant (10(5 ± 2.5) M(-1) s(-1)), forming the reaction intermediate (BrNO)(SO2)N(CH3)2(-). This intermediate resembles a loosely bound complex between an electrophilic nitrosyl bromide (BrNO) molecule and an electron-rich dimethylaminosulfinate ((SO2)N(CH3)2(-)) fragment, based on inspection of computed natural charges and geometric parameters. This fragile complex undergoes immediate (10(10 ± 2.5) s(-1)) reaction by two branches: an exothermic channel that produces NDMA, and an entropy-driven channel giving non-NDMA products. Computational results bring new insights into the electronic nature, chemical equilibria, and kinetics of the elementary reactions of this pathway, enabled by computed energies of structures that are not possible to access experimentally.

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

[Application of quantum-chemical methods to prediction of the carcinogenicity of chemical substances].

PubMed

Zholdikova, Z I; Kharchevnikova, N V

2006-01-01

A version of logical-combinatorial JSM type intelligent system was used to predict the presence and the degree of a carcinogenic effect. This version was based on combined description of chemical substances including both structural and numeric parameters. The new version allows for the fact that the toxicity and danger caused by chemical substances often depend on their biological activation in the organism. The authors substantiate classifying chemicals according to their carcinogenic activity, and illustrate the use of the system to predict the carcinogenicity of polycyclic aromatic hydrocarbons using a model of bioactivation via the formation of diolepoxides, and the carcinogenicity of halogenated alkanes using a model of bioactivation via oxidative dehalogenation. The paper defined the boundary level of an energetic parameter, the exceeding of which correlated with the inhibition of halogenated alkanes's metabolism and the absence of carcinogenic activity.

Rhorix: An interface between quantum chemical topology and the 3D graphics program blender

PubMed Central

Sale, Kenneth L.; Simmons, Blake A.; Popelier, Paul L. A.

2017-01-01

Chemical research is assisted by the creation of visual representations that map concepts (such as atoms and bonds) to 3D objects. These concepts are rooted in chemical theory that predates routine solution of the Schrödinger equation for systems of interesting size. The method of Quantum Chemical Topology (QCT) provides an alternative, parameter‐free means to understand chemical phenomena directly from quantum mechanical principles. Representation of the topological elements of QCT has lagged behind the best tools available. Here, we describe a general abstraction (and corresponding file format) that permits the definition of mappings between topological objects and their 3D representations. Possible mappings are discussed and a canonical example is suggested, which has been implemented as a Python “Add‐On” named Rhorix for the state‐of‐the‐art 3D modeling program Blender. This allows chemists to use modern drawing tools and artists to access QCT data in a familiar context. A number of examples are discussed. © 2017 The Authors. Journal of Computational Chemistry Published by Wiley Periodicals, Inc. PMID:28857244

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Rongchun; Mroue, Kamal H.; Ramamoorthy, Ayyalusamy, E-mail: ramamoor@umich.edu

2015-10-14

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), {sup 1}H MAS NMR spectra of rigid solids still suffer from poor resolution and severe peak overlap caused by the strong {sup 1}H–{sup 1}H homonuclear dipolar couplings and narrow {sup 1}H chemical shift (CS) ranges, which rendermore » 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) {sup 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 {sup 1}H–{sup 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

Hydrogenic molecular transitions in double concentric quantum donuts by changing geometrical parameters

NASA Astrophysics Data System (ADS)

Ospina-Londoño, D. A.; Fulla, M. R.; Marín, J. H.

2013-03-01

In this work it is considered a versatile model to study two different ionization processes starting from a D20 homonuclear hydrogenic molecule confined in double concentric quantum donuts. Very narrow quantum donut circular cross sections are considered to separate the radial and angular variables in the D20 Hamiltonian by using the well-known adiabatic approximation D20 total energy as a function of the inter donor spacing and the outer donut center line radius is calculated. The salient features of an artificial D20 hydrogenic molecule such as the dissociation energy and the equilibrium length are strongly dependent on the quantum donut geometrical parameters. By increasing systematically the quantum donut outer center line radius, it is possible to understand a first ionization process: D20→D2++e-. A second ionization process D20→D-+D+ can be carried out by fixing the first donor position and gradually moving away the second one. The results obtained in this study are in good agreement with those previously obtained in the limiting cases of very large inter donor separation. The model proposed here is computationally economical and provides a realistic description of both ionization processes and the few-particle system confined in double concentric quantum donuts.

Recent Trends in Quantum Chemical Modeling of Enzymatic Reactions.

PubMed

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Yiteng; Kais, Sabre; Berman, Gennady Petrovich

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 ofmore » 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.« less

Quantum space and quantum completeness

NASA Astrophysics Data System (ADS)

Jurić, Tajron

2018-05-01

Motivated by the question whether quantum gravity can "smear out" the classical singularity we analyze a certain quantum space and its quantum-mechanical completeness. Classical singularity is understood as a geodesic incompleteness, while quantum completeness requires a unique unitary time evolution for test fields propagating on an underlying background. Here the crucial point is that quantum completeness renders the Hamiltonian (or spatial part of the wave operator) to be essentially self-adjoint in order to generate a unique time evolution. We examine a model of quantum space which consists of a noncommutative BTZ black hole probed by a test scalar field. We show that the quantum gravity (noncommutative) effect is to enlarge the domain of BTZ parameters for which the relevant wave operator is essentially self-adjoint. This means that the corresponding quantum space is quantum complete for a larger range of BTZ parameters rendering the conclusion that in the quantum space one observes the effect of "smearing out" the singularity.

Quantum-chemical investigations of spectroscopic properties of a fluorescence probe

NASA Astrophysics Data System (ADS)

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

2012-09-01

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

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

NASA Astrophysics Data System (ADS)

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.

Quantum Chemical Mass Spectrometry: Verification and Extension of the Mobile Proton Model for Histidine

NASA Astrophysics Data System (ADS)

Cautereels, Julie; Blockhuys, Frank

2017-06-01

The quantum chemical mass spectrometry for materials science (QCMS2) method is used to verify the proposed mechanism for proton transfer - the Mobile Proton Model (MPM) - by histidine for ten XHS tripeptides, based on quantum chemical calculations at the DFT/B3LYP/6-311+G* level of theory. The fragmentations of the different intermediate structures in the MPM mechanism are studied within the QCMS2 framework, and the energetics of the proposed mechanism itself and those of the fragmentations of the intermediate structures are compared, leading to the computational confirmation of the MPM. In addition, the calculations suggest that the mechanism should be extended from considering only the formation of five-membered ring intermediates to include larger-ring intermediates. [Figure not available: see fulltext.

Radiation and quantum chemical studies of chalcone derivatives.

PubMed

Gaikwad, P; Priyadarsini, K I; Naumov, S; Rao, B S M

2010-08-05

The reactions of oxidizing radicals ((*)OH, Br(2)(*-), and SO(4)(*-)) with -OH-, -CH(3)-, or -NH(2)-substituted indole chalcones and hydroxy benzenoid chalcones were studied by radiation and quantum chemical methods. The (*)OH radical was found to react by addition at diffusion-controlled rates (k = 1.1-1.7 x 10(10) dm(3) mol(-1) s(-1)), but Br(2)(*-) radical reacted by 2 orders of magnitude lower. Quantum chemical calculations at the B3LYP/6-31+G(d,p) level of theory have shown that the (C2-OH)(*), (C11-OH)(*), and (C10-OH)(*) adducts of the indole chalcones and the (C7-OH)(*) and (C8-OH)(*) adducts of the hydroxy benzenoid chalcones are more stable with DeltaH = -39 to -28 kcal mol(-1) and DeltaG = -32 to -19 kcal mol(-1). This suggests that (*)OH addition to the alpha,beta-unsaturated bond is a major reaction channel in both types of chalcones and is barrierless. The stability and lack of dehydration of the (*)OH adducts arise from two factors: strong frontier orbital interaction due to the low energy gap between interacting orbitals and the negligible Coulombic repulsion due to small absolute values of Mulliken charges. The transient absorption spectrum measured in the (*)OH radical reaction with all the indole chalcone derivatives exhibited a maximum at 390 nm, which is in excellent agreement with the computed value (394 nm). The formation of three phenolic products under steady-state radiolysis is in line with the three stable (*)OH adducts predicted by theory. Independent of the substituent, identical spectra (lambda(max) = 330-360 and approximately 580 nm) were obtained on one-electron oxidation of the three indole chalcones. MO calculations predict the deprotonation from the -NH group is more efficient than from the substituent due to the larger electron density on the N1 atom forming the chalcone indolyl radical. Its reduction potential was determined to be 0.56 V from the ABTS(*-)/ABTS(2-) couple. In benzenoid chalcones, the (*)OH adduct spectrum is

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

PubMed

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

Representations of the quantum doubles of finite group algebras and spectral parameter dependent solutions of the Yang-Baxter equation

DOE Office of Scientific and Technical Information (OSTI.GOV)

Dancer, K. A.; Isac, P. S.; Links, J.

2006-10-15

Quantum doubles of finite group algebras form a class of quasitriangular Hopf algebras that algebraically solve the Yang-Baxter equation. Each representation of the quantum double then gives a matrix solution of the Yang-Baxter equation. Such solutions do not depend on a spectral parameter, and to date there has been little investigation into extending these solutions such that they do depend on a spectral parameter. Here we first explicitly construct the matrix elements of the generators for all irreducible representations of quantum doubles of the dihedral groups D{sub n}. These results may be used to determine constant solutions of the Yang-Baxtermore » equation. We then discuss Baxterization ansaetze to obtain solutions of the Yang-Baxter equation with a spectral parameter and give several examples, including a new 21-vertex model. We also describe this approach in terms of minimal-dimensional representations of the quantum doubles of the alternating group A{sub 4} and the symmetric group S{sub 4}.« less

Quantum chemical methods for the investigation of photoinitiated processes in biological systems: theory and applications.

PubMed

Dreuw, Andreas

2006-11-13

With the advent of modern computers and advances in the development of efficient quantum chemical computer codes, the meaningful computation of large molecular systems at a quantum mechanical level became feasible. Recent experimental effort to understand photoinitiated processes in biological systems, for instance photosynthesis or vision, at a molecular level also triggered theoretical investigations in this field. In this Minireview, standard quantum chemical methods are presented that are applicable and recently used for the calculation of excited states of photoinitiated processes in biological molecular systems. These methods comprise configuration interaction singles, the complete active space self-consistent field method, and time-dependent density functional theory and its variants. Semiempirical approaches are also covered. Their basic theoretical concepts and mathematical equations are briefly outlined, and their properties and limitations are discussed. Recent successful applications of the methods to photoinitiated processes in biological systems are described and theoretical tools for the analysis of excited states are presented.

Quantum deformations of conformal algebras with mass-like deformation parameters

DOE Office of Scientific and Technical Information (OSTI.GOV)

Frydryszak, Andrzej; Lukierski, Jerzy; Mozrzymas, Marek

1998-12-15

We recall the mathematical apparatus necessary for the quantum deformation of Lie algebras, namely the notions of coboundary Lie algebras, classical r-matrices, classical Yang-Baxter equations (CYBE), Froebenius algebras and parabolic subalgebras. Then we construct the quantum deformation of D=1, D=2 and D=3 conformal algebras, showing that this quantization introduce fundamental mass parameters. Finally we consider with more details the quantization of D=4 conformal algebra. We build three classes of sl(4,C) classical r-matrices, satisfying CYBE and depending respectively on 8, 10 and 12 generators of parabolic subalgebras. We show that only the 8-dimensional r-matrices allow to impose the D=4 conformal o(4,2){approx_equal}su(2,2)more » reality conditions. Weyl reflections and Dynkin diagram automorphisms for o(4,2) define the class of admissible bases for given classical r-matrices.« less

Topology-preserving quantum deformation with non-numerical parameter

NASA Astrophysics Data System (ADS)

Aukhadiev, Marat; Grigoryan, Suren; Lipacheva, Ekaterina

2013-11-01

We introduce a class of compact quantum semigroups, that we call semigroup deformations of compact Abelian qroups. These objects arise from reduced semigroup -algebras, the generalization of the Toeplitz algebra. We study quantum subgroups, quantum projective spaces and quantum quotient groups for such objects, and show that the group is contained as a compact quantum subgroup in the deformation of itself. The connection with the weak Hopf algebra notion is described. We give a grading on the -algebra of the compact quantum semigroups constructed.

Degenerate quantum codes and the quantum Hamming bound

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarvepalli, Pradeep; Klappenecker, Andreas

2010-03-15

The parameters of a nondegenerate quantum code must obey the Hamming bound. An important open problem in quantum coding theory is whether the parameters of a degenerate quantum code can violate this bound for nondegenerate quantum codes. In this article we show that Calderbank-Shor-Steane (CSS) codes, over a prime power alphabet q{>=}5, cannot beat the quantum Hamming bound. We prove a quantum version of the Griesmer bound for the CSS codes, which allows us to strengthen the Rains' bound that an [[n,k,d

SP_Ace: Stellar Parameters And Chemical abundances Estimator

NASA Astrophysics Data System (ADS)

Boeche, C.; Grebel, E. K.

2018-05-01

SP_Ace (Stellar Parameters And Chemical abundances Estimator) estimates the stellar parameters Teff, log g, [M/H], and elemental abundances. It employs 1D stellar atmosphere models in Local Thermodynamic Equilibrium (LTE). The code is highly automated and suitable for analyzing the spectra of large spectroscopic surveys with low or medium spectral resolution (R = 2000-20 000). A web service for calculating these values with the software is also available.

Quantum chemical study of a derivative of 3-substituted dithiocarbamic flavanone

NASA Astrophysics Data System (ADS)

Gosav, Steluta; Paduraru, Nicoleta; Maftei, Dan; Birsa, Mihail Lucian; Praisler, Mirela

2017-02-01

The aim of this work is to characterize a quite novel 3-dithiocarbamic flavonoid by vibrational spectroscopy in conjunction with Density Functional Theory (DFT) calculations. Quantum mechanics calculations of energies, geometries and vibrational wavenumbers in the ground state were carried out by using hybrid functional B3LYP with 6-311G(d,p) as basis set. The results indicate a remarkable agreement between the calculated molecular geometries, as well as vibrational frequencies, and the corresponding experimental data. In addition, a complete assignment of all the absorption bands present in the vibrational spectrum has been performed. In order to assess its chemical potential, quantum molecular descriptors characterizing the interactions between the 3-dithiocarbamic flavonoid and its biological receptors have been computed. The frontier molecular orbitals and the HOMO-LUMO energy gap have been used in order to explain the way in which the new molecule can interact with other species and to characterize its molecular chemical stability/reactivity. The molecular electrostatic potential (MEP) map, computed in order to identify the sites of the studied flavonoid that are most likely to interact with electrophilic and nucleophilic species, is discussed.

Investigations of the polarization behavior of quantum cascade lasers by Stokes parameters.

PubMed

Janassek, Patrick; Hartmann, Sébastien; Molitor, Andreas; Michel, Florian; Elsäßer, Wolfgang

2016-01-15

We experimentally investigate the full polarization behavior of mid-infrared emitting quantum cascade lasers (QCLs) in terms of measuring the complete Stokes parameters, instead of only projecting them on a linear polarization basis. We demonstrate that besides the pre-dominant linear TM polarization of the emitted light as governed by the selection rules of the intersubband transition, small non-TM contributions, e.g., circularly polarized light, are present reflecting the birefringent behavior of the semiconductor quantum well waveguide. Surprisingly unique is the persistence of these polarization properties well below laser threshold. These investigations give further insight into understanding, manipulating, and exploiting the polarization properties of QCLs, both from a laser point of view and with respect toward applications.

Nonlinear absorption properties of AlGaAs/GaAs multiple quantum wells grown by metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Lee, Hsing-Chung; Kost, A.; Kawase, M.; Hariz, A.; Dapkus, P. Daniel

1988-01-01

The nonlinear absorption properties of the excitonic resonances associated with multiple quantum wells (MQWs) in AlGaAs/GaAs grown by metalorganic chemical vapor deposition are reported. The dependence of the saturation properties on growth parameters, especially growth temperature, and the well width are described. The minimum measured saturation intensity for these materials is 250 W/sq cm, the lowest reported value to date. The low saturation intensities are the result of excellent minority carrier properties. A systematic study of minority carrier lifetimes in quantum wells are reported. Lifetimes range from 50-350 ns depending on growth temperature and well width. When corrected for lateral diffusion effects and the measured minority carrier lifetime, the saturation data suggest that saturation intensities as low as 2.3 W/sq cm can be achieved in this system. The first measurements of the dependence of the exciton area and the magnitude of the excitonic absorption on well width are prsented. The growth of MQW structures on transparent GaP substrates is demonstrated and the electroabsorption properties of these structures are reviewed.

Chlorination pattern effect on thermodynamic parameters and environmental degradability for C₁₀-SCCPs: Quantum chemical calculation based on virtual combinational library.

PubMed

Sun, Yuzhen; Pan, Wenxiao; Lin, Yuan; Fu, Jianjie; Zhang, Aiqian

2016-01-01

Short-chain chlorinated paraffins (SCCPs) are still controversial candidates for inclusion in the Stockholm Convention. The inherent mixture nature of SCCPs makes it rather difficult to explore their environmental behaviors. A virtual molecule library of 42,720 C10-SCCP congeners covering the full structure spectrum was constructed. We explored the structural effects on the thermodynamic parameters and environmental degradability of C10-SCCPs through semi-empirical quantum chemical calculations. The thermodynamic properties were acquired using the AM1 method, and frontier molecular orbital analysis was carried out to obtain the E(HOMO), E(LUMO) and E(LUMO)-E(HOMO) for degradability exploration at the same level. The influence of the chlorination degree (N(Cl)) on the relative stability and environmental degradation was elucidated. A novel structural descriptor, μ, was proposed to measure the dispersion of the chlorine atoms within a molecule. There were significant correlations between thermodynamic values and N(Cl), while the reported N(Cl)-dependent pollution profile of C10-SCCPs in environmental samples was basically consistent with the predicted order of formation stability of C10-SCCP congeners. In addition, isomers with large μ showed higher relative stability than those with small μ. This could be further verified by the relationship between μ and the reactivity of nucleophilic substitution and OH attack respectively. The C10-SCCP congeners with less Cl substitution and lower dispersion degree are susceptible to environmental degradation via nucleophilic substitution and hydroxyl radical attack, while direct photolysis of C10-SCCP congeners cannot readily occur due to the large E(LUMO)-E(HOMO) values. The chlorination effect and the conclusions were further checked with appropriate density functional theory (DFT) calculations. Copyright © 2015. Published by Elsevier B.V.

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

NASA Astrophysics Data System (ADS)

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.

Parameter Estimates in Differential Equation Models for Chemical Kinetics

ERIC Educational Resources Information Center

Winkel, Brian

2011-01-01

We discuss the need for devoting time in differential equations courses to modelling and the completion of the modelling process with efforts to estimate the parameters in the models using data. We estimate the parameters present in several differential equation models of chemical reactions of order n, where n = 0, 1, 2, and apply more general…

Macroscopicity of quantum superpositions on a one-parameter unitary path in Hilbert space

NASA Astrophysics Data System (ADS)

Volkoff, T. J.; Whaley, K. B.

2014-12-01

We analyze quantum states formed as superpositions of an initial pure product state and its image under local unitary evolution, using two measurement-based measures of superposition size: one based on the optimal quantum binary distinguishability of the branches of the superposition and another based on the ratio of the maximal quantum Fisher information of the superposition to that of its branches, i.e., the relative metrological usefulness of the superposition. A general formula for the effective sizes of these states according to the branch-distinguishability measure is obtained and applied to superposition states of N quantum harmonic oscillators composed of Gaussian branches. Considering optimal distinguishability of pure states on a time-evolution path leads naturally to a notion of distinguishability time that generalizes the well-known orthogonalization times of Mandelstam and Tamm and Margolus and Levitin. We further show that the distinguishability time provides a compact operational expression for the superposition size measure based on the relative quantum Fisher information. By restricting the maximization procedure in the definition of this measure to an appropriate algebra of observables, we show that the superposition size of, e.g., NOON states and hierarchical cat states, can scale linearly with the number of elementary particles comprising the superposition state, implying precision scaling inversely with the total number of photons when these states are employed as probes in quantum parameter estimation of a 1-local Hamiltonian in this algebra.

Machine learning action parameters in lattice quantum chromodynamics

NASA Astrophysics Data System (ADS)

Shanahan, Phiala E.; Trewartha, Daniel; Detmold, William

2018-05-01

Numerical lattice quantum chromodynamics studies of the strong interaction are important in many aspects of particle and nuclear physics. Such studies require significant computing resources to undertake. A number of proposed methods promise improved efficiency of lattice calculations, and access to regions of parameter space that are currently computationally intractable, via multi-scale action-matching approaches that necessitate parametric regression of generated lattice datasets. The applicability of machine learning to this regression task is investigated, with deep neural networks found to provide an efficient solution even in cases where approaches such as principal component analysis fail. The high information content and complex symmetries inherent in lattice QCD datasets require custom neural network layers to be introduced and present opportunities for further development.

Absolute parameters and chemical composition of the binary star OU Gem

NASA Astrophysics Data System (ADS)

Glazunova, L. V.; Mishenina, T. V.; Soubiran, C.; Kovtyukh, V. V.

2014-10-01

The absolute parameters and chemical composition of the BY Dra-type spectroscopic binary OU Gem (HD 45088) were determined on the basis of 10 high-resolution spectra. A new orbital solution of the binary system was determined, the binary ephemerides were specified, and the main physical and atmospheric parameters of the binary components were obtained. The chemical composition of both components was estimated for the first time for the stars of such type.

Surface emitting ring quantum cascade lasers for chemical sensing

NASA Astrophysics Data System (ADS)

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.

Simulating chemistry using quantum computers.

PubMed

Kassal, Ivan; Whitfield, James D; Perdomo-Ortiz, Alejandro; Yung, Man-Hong; Aspuru-Guzik, Alán

2011-01-01

The difficulty of simulating quantum systems, well known to quantum chemists, prompted the idea of quantum computation. One can avoid the steep scaling associated with the exact simulation of increasingly large quantum systems on conventional computers, by mapping the quantum system to another, more controllable one. In this review, we discuss to what extent the ideas in quantum computation, now a well-established field, have been applied to chemical problems. We describe algorithms that achieve significant advantages for the electronic-structure problem, the simulation of chemical dynamics, protein folding, and other tasks. Although theory is still ahead of experiment, we outline recent advances that have led to the first chemical calculations on small quantum information processors.

Quantum action for time-dependent Ginzburg-Landau equations

NASA Astrophysics Data System (ADS)

Thompson, R. S.

1994-02-01

A gauge-invariant formula is derived for the quantum action of a dirty superconductor with strong pair breaking. The major complication is the coupling between the order parameter and the electro-chemical potential, which is most simply expressed as an imaginary time integral. The perturbative modes of excitation are identified.

Quantum chemical approaches to [NiFe] hydrogenase.

PubMed

Vaissier, Valerie; Van Voorhis, Troy

2017-05-09

The mechanism by which [NiFe] hydrogenase catalyses the oxidation of molecular hydrogen is a significant yet challenging topic in bioinorganic chemistry. With far-reaching applications in renewable energy and carbon mitigation, significant effort has been invested in the study of these complexes. In particular, computational approaches offer a unique perspective on how this enzyme functions at an electronic and atomistic level. In this article, we discuss state-of-the art quantum chemical methods and how they have helped deepen our comprehension of [NiFe] hydrogenase. We outline the key strategies that can be used to compute the (i) geometry, (ii) electronic structure, (iii) thermodynamics and (iv) kinetic properties associated with the enzymatic activity of [NiFe] hydrogenase and other bioinorganic complexes. © 2017 The Author(s). Published by Portland Press Limited on behalf of the Biochemical Society.

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

ERIC Educational Resources Information Center

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…

Spectroscopic, quantum chemical calculation and molecular docking of dipfluzine

NASA Astrophysics Data System (ADS)

Srivastava, Karnica; Srivastava, Anubha; Tandon, Poonam; Sinha, Kirti; Wang, Jing

2016-12-01

Molecular structure and vibrational analysis of dipfluzine (C27H29FN2O) were presented using FT-IR and FT-Raman spectroscopy and quantum chemical calculations. The theoretical ground state geometry and electronic structure of dipfluzine are optimized by the DFT/B3LYP/6-311++G (d,p) method and compared with those of the crystal data. The 1D potential energy scan was performed by varying the dihedral angle using B3LYP functional at 6-31G(d,p) level of theory and thus the most stable conformer of the compound were determined. Molecular electrostatic potential surface (MEPS), frontier orbital analysis and electronic reactivity descriptor were used to predict the chemical reactivity of molecule. Energies of intra- and inter-molecular hydrogen bonds in molecule and their electronic aspects were investigated by natural bond orbital (NBO). To find out the anti-apoptotic activity of the title compound molecular docking studies have been performed against protein Fas.

A triple quantum dot based nano-electromechanical memory device

DOE Office of Scientific and Technical Information (OSTI.GOV)

Pozner, R.; Lifshitz, E.; Solid State Institute, Technion-Israel Institute of Technology, Haifa 32000

Colloidal quantum dots (CQDs) are free-standing nano-structures with chemically tunable electronic properties. This tunability offers intriguing possibilities for nano-electromechanical devices. In this work, we consider a nano-electromechanical nonvolatile memory (NVM) device incorporating a triple quantum dot (TQD) cluster. The device operation is based on a bias induced motion of a floating quantum dot (FQD) located between two bound quantum dots (BQDs). The mechanical motion is used for switching between two stable states, “ON” and “OFF” states, where ligand-mediated effective interdot forces between the BQDs and the FQD serve to hold the FQD in each stable position under zero bias. Consideringmore » realistic microscopic parameters, our quantum-classical theoretical treatment of the TQD reveals the characteristics of the NVM.« less

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

PubMed

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.

Machine learning action parameters in lattice quantum chromodynamics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shanahan, Phiala; Trewartha, Daneil; Detmold, William

Numerical lattice quantum chromodynamics studies of the strong interaction underpin theoretical understanding of many aspects of particle and nuclear physics. Such studies require significant computing resources to undertake. A number of proposed methods promise improved efficiency of lattice calculations, and access to regions of parameter space that are currently computationally intractable, via multi-scale action-matching approaches that necessitate parametric regression of generated lattice datasets. The applicability of machine learning to this regression task is investigated, with deep neural networks found to provide an efficient solution even in cases where approaches such as principal component analysis fail. Finally, the high information contentmore » and complex symmetries inherent in lattice QCD datasets require custom neural network layers to be introduced and present opportunities for further development.« less

Machine learning action parameters in lattice quantum chromodynamics

DOE PAGES

Shanahan, Phiala; Trewartha, Daneil; Detmold, William

2018-05-16

Numerical lattice quantum chromodynamics studies of the strong interaction underpin theoretical understanding of many aspects of particle and nuclear physics. Such studies require significant computing resources to undertake. A number of proposed methods promise improved efficiency of lattice calculations, and access to regions of parameter space that are currently computationally intractable, via multi-scale action-matching approaches that necessitate parametric regression of generated lattice datasets. The applicability of machine learning to this regression task is investigated, with deep neural networks found to provide an efficient solution even in cases where approaches such as principal component analysis fail. Finally, the high information contentmore » and complex symmetries inherent in lattice QCD datasets require custom neural network layers to be introduced and present opportunities for further development.« less

ASPCAP: THE APOGEE STELLAR PARAMETER AND CHEMICAL ABUNDANCES PIPELINE

DOE Office of Scientific and Technical Information (OSTI.GOV)

García Pérez, Ana E.; Majewski, Steven R.; Shane, Neville

2016-06-01

The Apache Point Observatory Galactic Evolution Experiment (APOGEE) has built the largest moderately high-resolution ( R  ≈ 22,500) spectroscopic map of the stars across the Milky Way, and including dust-obscured areas. The APOGEE Stellar Parameter and Chemical Abundances Pipeline (ASPCAP) is the software developed for the automated analysis of these spectra. ASPCAP determines atmospheric parameters and chemical abundances from observed spectra by comparing observed spectra to libraries of theoretical spectra, using χ {sup 2} minimization in a multidimensional parameter space. The package consists of a fortran90 code that does the actual minimization and a wrapper IDL code for book-keeping and datamore » handling. This paper explains in detail the ASPCAP components and functionality, and presents results from a number of tests designed to check its performance. ASPCAP provides stellar effective temperatures, surface gravities, and metallicities precise to 2%, 0.1 dex, and 0.05 dex, respectively, for most APOGEE stars, which are predominantly giants. It also provides abundances for up to 15 chemical elements with various levels of precision, typically under 0.1 dex. The final data release (DR12) of the Sloan Digital Sky Survey III contains an APOGEE database of more than 150,000 stars. ASPCAP development continues in the SDSS-IV APOGEE-2 survey.« less

Quantum transport under ac drive from the leads: A Redfield quantum master equation approach

NASA Astrophysics Data System (ADS)

Purkayastha, Archak; Dubi, Yonatan

2017-08-01

Evaluating the time-dependent dynamics of driven open quantum systems is relevant for a theoretical description of many systems, including molecular junctions, quantum dots, cavity-QED experiments, cold atoms experiments, and more. Here, we formulate a rigorous microscopic theory of an out-of-equilibrium open quantum system of noninteracting particles on a lattice weakly coupled bilinearly to multiple baths and driven by periodically varying thermodynamic parameters like temperature and chemical potential of the bath. The particles can be either bosonic or fermionic and the lattice can be of any dimension and geometry. Based on the Redfield quantum master equation under Born-Markov approximation, we derive a linear differential equation for an equal time two point correlation matrix, sometimes also called a single-particle density matrix, from which various physical observables, for example, current, can be calculated. Various interesting physical effects, such as resonance, can be directly read off from the equations. Thus, our theory is quite general and gives quite transparent and easy-to-calculate results. We validate our theory by comparing with exact numerical simulations. We apply our method to a generic open quantum system, namely, a double quantum dot coupled to leads with modulating chemical potentials. The two most important experimentally relevant insights from this are as follows: (i) Time-dependent measurements of current for symmetric oscillating voltages (with zero instantaneous voltage bias) can point to the degree of asymmetry in the system-bath coupling and (ii) under certain conditions time-dependent currents can exceed time-averaged currents by several orders of magnitude, and can therefore be detected even when the average current is below the measurement threshold.

Statistics of the work done on a quantum critical system by quenching a control parameter.

PubMed

Silva, Alessandro

2008-09-19

We study the statistics of the work done on a quantum critical system by quenching a control parameter in the Hamiltonian. We elucidate the relation between the probability distribution of the work and the Loschmidt echo, a quantity emerging usually in the context of dephasing. Using this connection we characterize the statistics of the work done on a quantum Ising chain by quenching locally or globally the transverse field. We show that for local quenches starting at criticality the probability distribution of the work displays an interesting edge singularity.

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

NASA Astrophysics Data System (ADS)

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.

Quantum Discord Preservation for Two Quantum-Correlated Qubits in Two Independent Reserviors

NASA Astrophysics Data System (ADS)

Xu, Lan

2018-03-01

We investigate the dynamics of quantum discord using an exactly solvable model where two qubits coupled to independent thermal environments. The quantum discord is employed as a non-classical correlation quantifier. By studying the quantum discord of a class of initial states, we find discord remains preserve for a finite time. The effects of the temperature, initial-state parameter, system-reservoir coupling constant and temperature difference parameter of the two independent reserviors are also investigated. We discover that the quantum nature loses faster in high temperature, however, one can extend the time of quantum nature by choosing smaller system-reservoir coupling constant, larger certain initial-state parameter and larger temperature difference parameter.

Noise-resistant spectral features for retrieving foliar chemical parameters

USDA-ARS?s Scientific Manuscript database

Foliar chemical constituents are important indicators for understanding vegetation growing status and ecosystem functionality. Provided the noncontact and nondestructive traits, the hyperspectral analysis is a superior and efficient method for deriving these parameters. In practical implementation o...

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

NASA Astrophysics Data System (ADS)

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.

High Color-Purity Green, Orange, and Red Light-Emitting Didoes Based on Chemically Functionalized Graphene Quantum Dots

NASA Astrophysics Data System (ADS)

Kwon, Woosung; Kim, Young-Hoon; Kim, Ji-Hee; Lee, Taehyung; Do, Sungan; Park, Yoonsang; Jeong, Mun Seok; Lee, Tae-Woo; Rhee, Shi-Woo

2016-04-01

Chemically derived graphene quantum dots (GQDs) to date have showed very broad emission linewidth due to many kinds of chemical bondings with different energy levels, which significantly degrades the color purity and color tunability. Here, we show that use of aniline derivatives to chemically functionalize GQDs generates new extrinsic energy levels that lead to photoluminescence of very narrow linewidths. We use transient absorption and time-resolved photoluminescence spectroscopies to study the electronic structures and related electronic transitions of our GQDs, which reveals that their underlying carrier dynamics is strongly related to the chemical properties of aniline derivatives. Using these functionalized GQDs as lumophores, we fabricate light-emitting didoes (LEDs) that exhibit green, orange, and red electroluminescence that has high color purity. The maximum current efficiency of 3.47 cd A-1 and external quantum efficiency of 1.28% are recorded with our LEDs; these are the highest values ever reported for LEDs based on carbon-nanoparticle phosphors. This functionalization of GQDs with aniline derivatives represents a new method to fabricate LEDs that produce natural color.

Characterization of heterocyclic rings through quantum chemical topology.

PubMed

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.

Quantum chemical calculations in the structural analysis of phloretin

NASA Astrophysics Data System (ADS)

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.

Towards quantum chemistry on a quantum computer.

PubMed

Lanyon, B P; Whitfield, J D; Gillett, G G; Goggin, M E; Almeida, M P; Kassal, I; Biamonte, J D; Mohseni, M; Powell, B J; Barbieri, M; Aspuru-Guzik, A; White, A G

2010-02-01

Exact first-principles calculations of molecular properties are currently intractable because their computational cost grows exponentially with both the number of atoms and basis set size. A solution is to move to a radically different model of computing by building a quantum computer, which is a device that uses quantum systems themselves to store and process data. Here we report the application of the latest photonic quantum computer technology to calculate properties of the smallest molecular system: the hydrogen molecule in a minimal basis. We calculate the complete energy spectrum to 20 bits of precision and discuss how the technique can be expanded to solve large-scale chemical problems that lie beyond the reach of modern supercomputers. These results represent an early practical step toward a powerful tool with a broad range of quantum-chemical applications.

Chemical and explosive detections using photo-acoustic effect and quantum cascade lasers

NASA Astrophysics Data System (ADS)

Choa, Fow-Sen

2013-12-01

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

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

NASA Astrophysics Data System (ADS)

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.

Prediction of contaminant persistence in aqueous phase: a quantum chemical approach.

PubMed

Blotevogel, Jens; Mayeno, Arthur N; Sale, Tom C; Borch, Thomas

2011-03-15

At contaminated field sites where active remediation measures are not feasible, monitored natural attenuation is sometimes the only alternative for surface water or groundwater decontamination. However, due to slow degradation rates of some contaminants under natural conditions, attenuation processes and their performance assessment can take several years to decades to complete. Here, we apply quantum chemical calculations to predict contaminant persistence in the aqueous phase. For the test compound hexamethylphosphoramide (HMPA), P-N bond hydrolysis is the only thermodynamically favorable reaction that may lead to its degradation under reducing conditions. Through calculation of aqueous Gibbs free energies of activation for all potential reaction mechanisms, it is predicted that HMPA hydrolyzes via an acid-catalyzed mechanism at pH < 8.2, and an uncatalyzed mechanism at pH 8.2-8.5. The estimated half-lives of thousands to hundreds of thousands of years over the groundwater-typical pH range of 6.0 to 8.5 indicate that HMPA will be persistent in the absence of suitable oxidants. At pH 0, where the hydrolysis reaction is rapid enough to enable measurement, the experimentally determined rate constant and half-life are in excellent agreement with the predicted values. Since the quantum chemical methodology described herein can be applied to virtually any contaminant or reaction of interest, it is especially valuable for the prediction of persistence when slow reaction rates impede experimental investigations and appropriate QSARs are unavailable.

Biomimetic, Mild Chemical Synthesis of CdTe-GSH Quantum Dots with Improved Biocompatibility

PubMed Central

Pérez-Donoso, José M.; Monrás, Juan P.; Bravo, Denisse; Aguirre, Adam; Quest, Andrew F.; Osorio-Román, Igor O.; Aroca, Ricardo F.; Chasteen, Thomas G.; Vásquez, Claudio C.

2012-01-01

Multiple applications of nanotechnology, especially those involving highly fluorescent nanoparticles (NPs) or quantum dots (QDs) have stimulated the research to develop simple, rapid and environmentally friendly protocols for synthesizing NPs exhibiting novel properties and increased biocompatibility. In this study, a simple protocol for the chemical synthesis of glutathione (GSH)-capped CdTe QDs (CdTe-GSH) resembling conditions found in biological systems is described. Using only CdCl2, K2TeO3 and GSH, highly fluorescent QDs were obtained under pH, temperature, buffer and oxygen conditions that allow microorganisms growth. These CdTe-GSH NPs displayed similar size, chemical composition, absorbance and fluorescence spectra and quantum yields as QDs synthesized using more complicated and expensive methods. CdTe QDs were not freely incorporated into eukaryotic cells thus favoring their biocompatibility and potential applications in biomedicine. In addition, NPs entry was facilitated by lipofectamine, resulting in intracellular fluorescence and a slight increase in cell death by necrosis. Toxicity of the as prepared CdTe QDs was lower than that observed with QDs produced by other chemical methods, probably as consequence of decreased levels of Cd+2 and higher amounts of GSH. We present here the simplest, fast and economical method for CdTe QDs synthesis described to date. Also, this biomimetic protocol favors NPs biocompatibility and helps to establish the basis for the development of new, “greener” methods to synthesize cadmium-containing QDs. PMID:22292028

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

PubMed

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.

Exploiting Locality in Quantum Computation for Quantum Chemistry.

PubMed

McClean, Jarrod R; Babbush, Ryan; Love, Peter J; Aspuru-Guzik, Alán

2014-12-18

Accurate prediction of chemical and material properties from first-principles quantum chemistry is a challenging task on traditional computers. Recent developments in quantum computation offer a route toward highly accurate solutions with polynomial cost; however, this solution still carries a large overhead. In this Perspective, we aim to bring together known results about the locality of physical interactions from quantum chemistry with ideas from quantum computation. We show that the utilization of spatial locality combined with the Bravyi-Kitaev transformation offers an improvement in the scaling of known quantum algorithms for quantum chemistry and provides numerical examples to help illustrate this point. We combine these developments to improve the outlook for the future of quantum chemistry on quantum computers.

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

NASA Astrophysics Data System (ADS)

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 TiO2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn2+ 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 Mn2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn2+ 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.

Parameter Estimation with Almost No Public Communication for Continuous-Variable Quantum Key Distribution

NASA Astrophysics Data System (ADS)

Lupo, Cosmo; Ottaviani, Carlo; Papanastasiou, Panagiotis; Pirandola, Stefano

2018-06-01

One crucial step in any quantum key distribution (QKD) scheme is parameter estimation. In a typical QKD protocol the users have to sacrifice part of their raw data to estimate the parameters of the communication channel as, for example, the error rate. This introduces a trade-off between the secret key rate and the accuracy of parameter estimation in the finite-size regime. Here we show that continuous-variable QKD is not subject to this constraint as the whole raw keys can be used for both parameter estimation and secret key generation, without compromising the security. First, we show that this property holds for measurement-device-independent (MDI) protocols, as a consequence of the fact that in a MDI protocol the correlations between Alice and Bob are postselected by the measurement performed by an untrusted relay. This result is then extended beyond the MDI framework by exploiting the fact that MDI protocols can simulate device-dependent one-way QKD with arbitrarily high precision.

Quantum Dot and Polymer Composite Cross-Reactive Array for Chemical Vapor Detection.

PubMed

Bright, Collin J; Nallon, Eric C; Polcha, Michael P; Schnee, Vincent P

2015-12-15

A cross-reactive chemical sensing array was made from CdSe Quantum Dots (QDs) and five different organic polymers by inkjet printing to create segmented fluorescent composite regions on quartz substrates. The sensor array was challenged with exposures from two sets of analytes, including one set of 14 different functionalized benzenes and one set of 14 compounds related to security concerns, including the explosives trinitrotoluene (TNT) and ammonium nitrate. The array was broadly responsive to analytes with different chemical functionalities due to the multiple sensing mechanisms that altered the QDs' fluorescence. The sensor array displayed excellent discrimination between members within both sets. Classification accuracy of more than 93% was achieved, including the complete discrimination of very similar dinitrobenzene isomers and three halogenated, substituted benzene compounds. The simple fabrication, broad responsivity, and high discrimination capacity of this type of cross-reactive array are ideal qualities for the development of sensors with excellent sensitivity to chemical and explosive threats while maintaining low false alarm rates.

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

PubMed

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 (C(11)H(10)Cl(6)N(2)O(6)) 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 P2(1)/c, with a=14.947Å, b=6.432Å, c=19.609Å 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. Copyright © 2012 Elsevier B.V. All rights reserved.

Instrument for the measurement and determination of chemical pulse column parameters

DOEpatents

Marchant, Norman J.; Morgan, John P.

1990-01-01

An instrument for monitoring and measuring pneumatic driving force pulse parameters applied to chemical separation pulse columns obtains real time pulse frequency and root mean square amplitude values, calculates column inch values and compares these values against preset limits to alert column operators to the variations of pulse column operational parameters beyond desired limits.

The relation between the quantum discord and quantum teleportation: The physical interpretation of the transition point between different quantum discord decay regimes

NASA Astrophysics Data System (ADS)

Roszak, K.; Cywiński, Ł.

2015-10-01

We study quantum teleportation via Bell-diagonal mixed states of two qubits in the context of the intrinsic properties of the quantum discord. We show that when the quantum-correlated state of the two qubits is used for quantum teleportation, the character of the teleportation efficiency changes substantially depending on the Bell-diagonal-state parameters, which can be seen when the worst-case-scenario or best-case-scenario fidelity is studied. Depending on the parameter range, one of two types of single-qubit states is hardest/easiest to teleport. The transition between these two parameter ranges coincides exactly with the transition between the range of classical correlation decay and quantum correlation decay characteristic for the evolution of the quantum discord. The correspondence provides a physical interpretation for the prominent feature of the decay of the quantum discord.

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

NASA Astrophysics Data System (ADS)

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

2014-05-01

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

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

NASA Astrophysics Data System (ADS)

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.

Quantum cascade transmitters for ultrasensitive chemical agent and explosives detection

NASA Astrophysics Data System (ADS)

Schultz, John F.; Taubman, Matthew S.; Harper, Warren W.; Williams, Richard M.; Myers, Tanya L.; Cannon, Bret D.; Sheen, David M.; Anheier, Norman C., Jr.; Allen, Paul J.; Sundaram, S. K.; Johnson, Bradley R.; Aker, Pamela M.; Wu, Ming C.; Lau, Erwin K.

2003-07-01

The small size, high power, promise of access to any wavelength between 3.5 and 16 microns, substantial tuning range about a chosen center wavelength, and general robustness of quantum cascade (QC) lasers provide opportunities for new approaches to ultra-sensitive chemical detection and other applications in the mid-wave infrared. PNNL is developing novel remote and sampling chemical sensing systems based on QC lasers, using QC lasers loaned by Lucent Technologies. In recent months laboratory cavity-enhanced sensing experiments have achieved absorption sensitivities of 8.5 x 10-11 cm-1 Hz-1/2, and the PNNL team has begun monostatic and bi-static frequency modulated, differential absorption lidar (FM DIAL) experiments at ranges of up to 2.5 kilometers. In related work, PNNL and UCLA are developing miniature QC laser transmitters with the multiplexed tunable wavelengths, frequency and amplitude stability, modulation characteristics, and power levels needed for chemical sensing and other applications. Current miniaturization concepts envision coupling QC oscillators, QC amplifiers, frequency references, and detectors with miniature waveguides and waveguide-based modulators, isolators, and other devices formed from chalcogenide or other types of glass. Significant progress has been made on QC laser stabilization and amplification, and on development and characterization of high-purity chalcogenide glasses, waveguide writing techniques, and waveguide metrology.

Environmental parameters of the Tennessee River in Alabama. 2: Physical, chemical, and biological parameters. [biological and chemical effects of thermal pollution from nuclear power plants on water quality

NASA Technical Reports Server (NTRS)

Rosing, L. M.

1976-01-01

Physical, chemical and biological water quality data from five sites in the Tennessee River, two in Guntersville Reservoir and three in Wheeler Reservoir were correlated with climatological data for three annual cycles. Two of the annual cycles are for the years prior to the Browns Ferry Nuclear Power Plant operations and one is for the first 14 months of Plant operations. A comparison of the results of the annual cycles indicates that two distinct physical conditions in the reservoirs occur, one during the warm months when the reservoirs are at capacity and one during the colder winter months when the reservoirs have been drawn-down for water storage during the rainy months and for weed control. The wide variations of physical and chemical parameters to which the biological organisms are subjected on an annual basis control the biological organisms and their population levels. A comparison of the parameters of the site below the Power plant indicates that the heated effluent from the plant operating with two of the three reactors has not had any effect on the organisms at this site. Recommendations given include the development of prediction mathematical models (statistical analysis) for the physical and chemical parameters under specific climatological conditions which affect biological organisms. Tabulated data of chemical analysis of water and organism populations studied is given.

An experimental and quantum chemical study of removal of utmostly quantified heavy metals in wastewater using coconut husk: A novel approach to mechanism.

PubMed

Malik, Reena; Dahiya, Shefali; Lata, Suman

2017-05-01

The present study explores the uptake capacity of low cost agricultural waste i.e.Unmodified Coconut (Cocos nucifera L.) Husk for the removal of heavy metal (Pb 2+ , Cu 2+ , Ni 2+ and Zn 2+ ) ions from industrial wastewater. The effect of various operational parameters such as adsorbent dose, high initial metal concentration (100mg/L-500mg/L), pH, temperature and agitation time on the removal of these ions has been investigated using batch experiments. The results showed that maximum uptake through adsorption occurred at 443.0mg/g (88.6%) for Cu, for Ni with 404.5mg/g (80.9%), 362.2mg/g (72.4%) for Pb 2+ and 338.0mg/g (67.6%) for Zn 2+ ion simultaneously. The adsorption capacity was found to be sensitive to the amount of adsorbent, heavy metal ion concentration, pH, temperature and contact time. The experimental statistics have been correlated and interpreted by a new proposed mechanism based upon quantum chemical study of the adsorbent. The theoretical study using quantum has provided the rich electron donation sites of Coconut Husk and hence proposed mechanism of removal. The various adsorption isotherms (Langmuir, Freundlich, Temkin, Dubinin-Radushkevich and Flory-Huggins), SEM study and physico-chemical properties of the ions suit well to the observed data. Copyright © 2017 Elsevier B.V. All rights reserved.

Quantum information transfer and entanglement with SQUID qubits in cavity QED: a dark-state scheme with tolerance for nonuniform device parameter.

PubMed

Yang, Chui-Ping; Chu, Shih-I; Han, Siyuan

2004-03-19

We investigate the experimental feasibility of realizing quantum information transfer (QIT) and entanglement with SQUID qubits in a microwave cavity via dark states. Realistic system parameters are presented. Our results show that QIT and entanglement with two-SQUID qubits can be achieved with a high fidelity. The present scheme is tolerant to device parameter nonuniformity. We also show that the strong coupling limit can be achieved with SQUID qubits in a microwave cavity. Thus, cavity-SQUID systems provide a new way for production of nonclassical microwave source and quantum communication.

Selecting the optimal synthesis parameters of InP/CdxZn1-xSe quantum dots for a hybrid remote phosphor white LED for general lighting applications.

PubMed

Ryckaert, Jana; Correia, António; Tessier, Mickael D; Dupont, Dorian; Hens, Zeger; Hanselaer, Peter; Meuret, Youri

2017-11-27

Quantum dots can be used in white LEDs for lighting applications to fill the spectral gaps in the combined emission spectrum of the blue pumping LED and a broad band phosphor, in order to improve the source color rendering properties. Because quantum dots are low scattering materials, their use can also reduce the amount of backscattered light which can increase the overall efficiency of the white LED. The absorption spectrum and narrow emission spectrum of quantum dots can be easily tuned by altering their synthesis parameters. Due to the re-absorption events between the different luminescent materials and the light interaction with the LED package, determining the optimal quantum dot properties is a highly non-trivial task. In this paper we propose a methodology to select the optimal quantum dot to be combined with a broad band phosphor in order to realize a white LED with optimal luminous efficacy and CRI. The methodology is based on accurate and efficient simulations using the extended adding-doubling approach that take into account all the optical interactions. The method is elaborated for the specific case of a hybrid, remote phosphor white LED with YAG:Ce phosphor in combination with InP/CdxZn 1-x Se type quantum dots. The absorption and emission spectrum of the quantum dots are generated in function of three synthesis parameters (core size, shell size and cadmium fraction) by a semi-empirical 'quantum dot model' to include the continuous tunability of these spectra. The sufficiently fast simulations allow to scan the full parameter space consisting of these synthesis parameters and luminescent material concentrations in terms of CRI and efficacy. A conclusive visualization of the final performance allows to make a well-considered trade-off between these performance parameters. For the hybrid white remote phosphor LED with YAG:Ce and InP/CdxZn 1-x Se quantum dots a CRI Ra = 90 (with R9>50) and an overall efficacy of 110 lm/W is found.

Quantum Chemical and Docking Insights into Bioavailability Enhancement of Curcumin by Piperine in Pepper.

PubMed

Patil, Vaishali M; Das, Sukanya; Balasubramanian, Krishnan

2016-05-26

We combine quantum chemical and molecular docking techniques to provide new insights into how piperine molecule in various forms of pepper enhances bioavailability of a number of drugs including curcumin in turmeric for which it increases its bioavailability by a 20-fold. We have carried out docking studies of quantum chemically optimized piperine structure binding to curcumin, CYP3A4 in cytochrome P450, p-Glycoprotein and UDP-glucuronosyltransferase (UGT), the enzyme responsible for glucuronosylation, which increases the solubility of curcumin. All of these studies establish that piperine binds to multiple sites on the enzymes and also intercalates with curcumin forming a hydrogen bonded complex with curcumin. The conjugated network of double bonds and the presence of multiple charge centers of piperine offer optimal binding sites for piperine to bind to enzymes such as UDP-GDH, UGT, and CYP3A4. Piperine competes for curcumin's intermolecular hydrogen bonding and its stacking propensity by hydrogen bonding with enolic proton of curcumin. This facilitates its metabolic transport, thereby increasing its bioavailability both through intercalation into curcumin layers through intermolecular hydrogen bonding, and by inhibiting enzymes that cause glucuronosylation of curcumin.

An investigation into the effective surface passivation of quantum dots by a photo-assisted chemical method

NASA Astrophysics Data System (ADS)

Joo, So-Yeong; Park, Hyun-Su; Kim, Do-yeon; Kim, Bum-Sung; Lee, Chan Gi; Kim, Woo-Byoung

2018-01-01

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%.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

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

PubMed

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.

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

PubMed

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.

Graphene-based quantum Hall resistance standards grown by chemical vapor deposition on silicon carbide

NASA Astrophysics Data System (ADS)

Ribeiro-Palau, Rebeca; Lafont, Fabien; Kazazis, Dimitris; Michon, Adrien; Couturaud, Olivier; Consejo, Christophe; Jouault, Benoit; Poirier, Wilfrid; Schopfer, Felicien

2015-03-01

Replace GaAs-based quantum Hall resistance standards (GaAs-QHRS) by a more convenient one, based on graphene (Gr-QHRS), is an ongoing goal in metrology. The new Gr-QHRS are expected to work in less demanding experimental conditions than GaAs ones. It will open the way to a broad dissemination of quantum standards, potentially towards industrial end-users, and it will support the implementation of a new International System of Units based on fixed fundamental constants. Here, we present accurate quantum Hall resistance measurements in large graphene Hall bars, grown by the hybrid scalable technique of propane/hydrogen chemical vapor deposition (CVD) on silicon carbide (SiC). This new Gr-QHRS shows a relative accuracy of 1 ×10-9 of the Hall resistance under the lowest magnetic field ever achieved in graphene. These experimental conditions surpass those of the most wildely used GaAs-QHRS. These results confirm the promises of graphene for resistance metrology applications and emphasizes the quality of the graphene produced by the CVD on SiC for applications as demanding as the resistance metrology.

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

PubMed

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.

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

PubMed Central

Zhang, Chenguang; Liu, Shaowen; Liu, Xingwei; Deng, Fei

2018-01-01

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 TiO2 mesoporous oxide film by successive ionic layer absorption and reaction. Mn2+ 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 Mn2+ incorporation, the PCE was increased from 3.4% to 4.9%. The effects of Mn2+ 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. PMID:29657776

Computational study of frontier orbitals, moments, chemical reactivity and thermodynamic parameters of sildenafil

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sachdeva, Ritika, E-mail: ritika.sachdeva21@gmail.com; Kaur, Prabhjot; Singh, V. P.

2016-05-06

Analysis of frontier orbitals of sildenafil has been carried using Density Functional Theory. On the basis of HOMO-LUMO energy, values of global chemical reactivity descriptors such as electronegativity, chemical hardness, softness, chemical potential, electrophilicity index have been calculated. Calculated values of dipole moment, polarizability, hyperpolarizability have also been reported for sildenafil along with its thermodynamic parameters.

Channel-parameter estimation for satellite-to-submarine continuous-variable quantum key distribution

NASA Astrophysics Data System (ADS)

Guo, Ying; Xie, Cailang; Huang, Peng; Li, Jiawei; Zhang, Ling; Huang, Duan; Zeng, Guihua

2018-05-01

This paper deals with a channel-parameter estimation for continuous-variable quantum key distribution (CV-QKD) over a satellite-to-submarine link. In particular, we focus on the channel transmittances and the excess noise which are affected by atmospheric turbulence, surface roughness, zenith angle of the satellite, wind speed, submarine depth, etc. The estimation method is based on proposed algorithms and is applied to low-Earth orbits using the Monte Carlo approach. For light at 550 nm with a repetition frequency of 1 MHz, the effects of the estimated parameters on the performance of the CV-QKD system are assessed by a simulation by comparing the secret key bit rate in the daytime and at night. Our results show the feasibility of satellite-to-submarine CV-QKD, providing an unconditionally secure approach to achieve global networks for underwater communications.

Quantum energy teleportation in a quantum Hall system

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yusa, Go; Izumida, Wataru; Hotta, Masahiro

2011-09-15

We propose an experimental method for a quantum protocol termed quantum energy teleportation (QET), which allows energy transportation to a remote location without physical carriers. Using a quantum Hall system as a realistic model, we discuss the physical significance of QET and estimate the order of energy gain using reasonable experimental parameters.

One-way quantum repeaters with quantum Reed-Solomon codes

NASA Astrophysics Data System (ADS)

Muralidharan, Sreraman; Zou, Chang-Ling; Li, Linshu; Jiang, Liang

2018-05-01

We show that quantum Reed-Solomon codes constructed from classical Reed-Solomon codes can approach the capacity on the quantum erasure channel of d -level systems for large dimension d . We study the performance of one-way quantum repeaters with these codes and obtain a significant improvement in key generation rate compared to previously investigated encoding schemes with quantum parity codes and quantum polynomial codes. We also compare the three generations of quantum repeaters using quantum Reed-Solomon codes and identify parameter regimes where each generation performs the best.

Constraining the loop quantum gravity parameter space from phenomenology

NASA Astrophysics Data System (ADS)

Brahma, Suddhasattwa; Ronco, Michele

2018-03-01

Development of quantum gravity theories rarely takes inputs from experimental physics. In this letter, we take a small step towards correcting this by establishing a paradigm for incorporating putative quantum corrections, arising from canonical quantum gravity (QG) theories, in deriving falsifiable modified dispersion relations (MDRs) for particles on a deformed Minkowski space-time. This allows us to differentiate and, hopefully, pick between several quantization choices via testable, state-of-the-art phenomenological predictions. Although a few explicit examples from loop quantum gravity (LQG) (such as the regularization scheme used or the representation of the gauge group) are shown here to establish the claim, our framework is more general and is capable of addressing other quantization ambiguities within LQG and also those arising from other similar QG approaches.

Long distance quantum communication with quantum Reed-Solomon codes

NASA Astrophysics Data System (ADS)

Muralidharan, Sreraman; Zou, Chang-Ling; Li, Linshu; Jiang, Liang; Jianggroup Team

We study the construction of quantum Reed Solomon codes from classical Reed Solomon codes and show that they achieve the capacity of quantum erasure channel for multi-level quantum systems. We extend the application of quantum Reed Solomon codes to long distance quantum communication, investigate the local resource overhead needed for the functioning of one-way quantum repeaters with these codes, and numerically identify the parameter regime where these codes perform better than the known quantum polynomial codes and quantum parity codes . Finally, we discuss the implementation of these codes into time-bin photonic states of qubits and qudits respectively, and optimize the performance for one-way quantum repeaters.

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

PubMed

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.

Chemical and quantum simulation of electron transfer through a polypeptide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ungar, L.W.; Voth, G.A.; Newton, M.D.

1999-08-26

Quantum rate theory, molecular dynamics simulations, and semiempirical electronic structure calculations are used to fully investigate electron transfer mediated by a solvated polypeptide for the first time. Using a stationary-phase approximation, the nonadiabatic electron-transfer rate constant is calculated from the nuclear free energies and the electronic coupling between the initial and final states. The former are obtained from quantum path integral and classical molecular dynamics simulations; the latter are calculated using semiempirical electronic structure calculations and the generalized Mulliken-Hush method. Importantly, no parameters are fit to kinetic data. The simulated system consists of a solvated four-proline polypeptide with a tris(bipyridine)rutheniummore » donor group and an oxypentamminecobalt acceptor group. From the simulation data entropy and energy contributions to the free energies are distinguished. Quantum suppression of the barrier, including important solvent contributions, is demonstrated. Although free energy profiles along the reaction coordinate are nearly parabolic, pronounced departures from harmonic behavior are found for the separate energy and entropy functions. Harmonic models of the system are compared to simulation results in order to quantify anharmonic effects. Electronic structure calculations show that electronic coupling elements vary considerably with system conformation, even when the effective donor-acceptor separation remains roughly constant. The calculations indicate that electron transfer in a significant range of conformations linking the polypeptide to the acceptor may contribute to the overall rate constant. After correction for limitations of the solvent model, the simulations and calculations agree well with the experimental activation energy and Arrhenius prefactor.« less

Parameter estimation of qubit states with unknown phase parameter

NASA Astrophysics Data System (ADS)

Suzuki, Jun

2015-02-01

We discuss a problem of parameter estimation for quantum two-level system, qubit system, in presence of unknown phase parameter. We analyze trade-off relations for mean square errors (MSEs) when estimating relevant parameters with separable measurements based on known precision bounds; the symmetric logarithmic derivative (SLD) Cramér-Rao (CR) bound and Hayashi-Gill-Massar (HGM) bound. We investigate the optimal measurement which attains the HGM bound and discuss its properties. We show that the HGM bound for relevant parameters can be attained asymptotically by using some fraction of given n quantum states to estimate the phase parameter. We also discuss the Holevo bound which can be attained asymptotically by a collective measurement.

Experimental and quantum-chemical studies on the three-particle fragmentation of neutral triatomic hydrogen

DOE Office of Scientific and Technical Information (OSTI.GOV)

Galster, Ulrich; Baumgartner, Frank; Mueller, Ulrich

2005-12-15

Dissociation of well-defined H{sub 3} Rydberg states into three ground state hydrogen atoms reveals characteristic correlation patterns in the center-of-mass motion of the three fragments. We present an extensive experimental dataset of momentum correlation maps for all lower Rydberg states of H{sub 3} and D{sub 3}. In particular the states with principal quantum number n=2 feature simple correlation patterns with regular occurence of mutual affinities. Energetically higher-lying states typically show more complex patterns which are unique for each state. Quantum-chemical calculations on adiabatic potential energy surfaces of H{sub 3} Rydberg states are presented to illuminate the likely origin of thesemore » differences. We discuss the likely dissociation mechanisms and paths which are responsible for the observed continuum correlation.« less

Chemical reaction mechanisms in solution from brute force computational Arrhenius plots.

PubMed

Kazemi, Masoud; Åqvist, Johan

2015-06-01

Decomposition of activation free energies of chemical reactions, into enthalpic and entropic components, can provide invaluable signatures of mechanistic pathways both in solution and in enzymes. Owing to the large number of degrees of freedom involved in such condensed-phase reactions, the extensive configurational sampling needed for reliable entropy estimates is still beyond the scope of quantum chemical calculations. Here we show, for the hydrolytic deamination of cytidine and dihydrocytidine in water, how direct computer simulations of the temperature dependence of free energy profiles can be used to extract very accurate thermodynamic activation parameters. The simulations are based on empirical valence bond models, and we demonstrate that the energetics obtained is insensitive to whether these are calibrated by quantum mechanical calculations or experimental data. The thermodynamic activation parameters are in remarkable agreement with experiment results and allow discrimination among alternative mechanisms, as well as rationalization of their different activation enthalpies and entropies.

Chemical reaction mechanisms in solution from brute force computational Arrhenius plots

PubMed Central

Kazemi, Masoud; Åqvist, Johan

2015-01-01

Decomposition of activation free energies of chemical reactions, into enthalpic and entropic components, can provide invaluable signatures of mechanistic pathways both in solution and in enzymes. Owing to the large number of degrees of freedom involved in such condensed-phase reactions, the extensive configurational sampling needed for reliable entropy estimates is still beyond the scope of quantum chemical calculations. Here we show, for the hydrolytic deamination of cytidine and dihydrocytidine in water, how direct computer simulations of the temperature dependence of free energy profiles can be used to extract very accurate thermodynamic activation parameters. The simulations are based on empirical valence bond models, and we demonstrate that the energetics obtained is insensitive to whether these are calibrated by quantum mechanical calculations or experimental data. The thermodynamic activation parameters are in remarkable agreement with experiment results and allow discrimination among alternative mechanisms, as well as rationalization of their different activation enthalpies and entropies. PMID:26028237

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

NASA Astrophysics Data System (ADS)

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

2015-04-01

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

Spatial variability versus parameter uncertainty in freshwater fate and exposure factors of chemicals.

PubMed

Nijhof, Carl O P; Huijbregts, Mark A J; Golsteijn, Laura; van Zelm, Rosalie

2016-04-01

We compared the influence of spatial variability in environmental characteristics and the uncertainty in measured substance properties of seven chemicals on freshwater fate factors (FFs), representing the residence time in the freshwater environment, and on exposure factors (XFs), representing the dissolved fraction of a chemical. The influence of spatial variability was quantified using the SimpleBox model in which Europe was divided in 100 × 100 km regions, nested in a regional (300 × 300 km) and supra-regional (500 × 500 km) scale. Uncertainty in substance properties was quantified by means of probabilistic modelling. Spatial variability and parameter uncertainty were expressed by the ratio k of the 95%ile and 5%ile of the FF and XF. Our analysis shows that spatial variability ranges in FFs of persistent chemicals that partition predominantly into one environmental compartment was up to 2 orders of magnitude larger compared to uncertainty. For the other (less persistent) chemicals, uncertainty in the FF was up to 1 order of magnitude larger than spatial variability. Variability and uncertainty in freshwater XFs of the seven chemicals was negligible (k < 1.5). We found that, depending on the chemical and emission scenario, accounting for region-specific environmental characteristics in multimedia fate modelling, as well as accounting for parameter uncertainty, can have a significant influence on freshwater fate factor predictions. Therefore, we conclude that it is important that fate factors should not only account for parameter uncertainty, but for spatial variability as well, as this further increases the reliability of ecotoxicological impacts in LCA. Copyright © 2016 Elsevier Ltd. All rights reserved.

Quantum chemical determination of young?s modulus of lignin. Calculations on ß-O-4' model compound

Treesearch

Thomas Elder

2007-01-01

The calculation of Young?s modulus of lignin has been examined by subjecting a dimeric model compound to strain, coupled with the determination of energy and stress. The computational results, derived from quantum chemical calculations, are in agreement with available experimental results. Changes in geometry indicate that modifications in dihedral angles occur in...

ESTIMATION OF PHYSICAL PROPERTIES AND CHEMICAL REACTIVITY PARAMETERS OF ORGANIC COMPOUNDS

EPA Science Inventory

The computer program SPARC (Sparc Performs Automated Reasoning in Chemistry)has been under development for several years to estimate physical properties and chemical reactivity parameters of organic compounds strictly from molecular structure. SPARC uses computational algorithms ...

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

PubMed

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.

Are Quantum Models for Order Effects Quantum?

NASA Astrophysics Data System (ADS)

Moreira, Catarina; Wichert, Andreas

2017-12-01

The application of principles of Quantum Mechanics in areas outside of physics has been getting increasing attention in the scientific community in an emergent disciplined called Quantum Cognition. These principles have been applied to explain paradoxical situations that cannot be easily explained through classical theory. In quantum probability, events are characterised by a superposition state, which is represented by a state vector in a N-dimensional vector space. The probability of an event is given by the squared magnitude of the projection of this superposition state into the desired subspace. This geometric approach is very useful to explain paradoxical findings that involve order effects, but do we really need quantum principles for models that only involve projections? This work has two main goals. First, it is still not clear in the literature if a quantum projection model has any advantage towards a classical projection. We compared both models and concluded that the Quantum Projection model achieves the same results as its classical counterpart, because the quantum interference effects play no role in the computation of the probabilities. Second, it intends to propose an alternative relativistic interpretation for rotation parameters that are involved in both classical and quantum models. In the end, instead of interpreting these parameters as a similarity measure between questions, we propose that they emerge due to the lack of knowledge concerned with a personal basis state and also due to uncertainties towards the state of world and towards the context of the questions.

Quantum parameter estimation in the Unruh–DeWitt detector model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hao, Xiang, E-mail: xhao@phas.ubc.ca; Pacific Institute of Theoretical Physics, Department of Physics and Astronomy, University of British Columbia, 6224 Agriculture Rd., Vancouver B.C., Canada V6T 1Z1; Wu, Yinzhong

2016-09-15

Relativistic effects on the precision of quantum metrology for particle detectors, such as two-level atoms are studied. The quantum Fisher information is used to estimate the phase sensitivity of atoms in non-inertial motions or in gravitational fields. The Unruh–DeWitt model is applicable to the investigation of the dynamics of a uniformly accelerated atom weakly coupled to a massless scalar vacuum field. When a measuring device is in the same relativistic motion as the atom, the dynamical behavior of quantum Fisher information as a function of Rindler proper time is obtained. It is found out that monotonic decrease in phase sensitivitymore » is characteristic of dynamics of relativistic quantum estimation. The origin of the decay of quantum Fisher information is the thermal bath that the accelerated detector finds itself in due to the Unruh effect. To improve relativistic quantum metrology, we reasonably take into account two reflecting plane boundaries perpendicular to each other. The presence of the reflecting boundary can shield the detector from the thermal bath in some sense.« less

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.

PubMed

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.

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

PubMed

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.

Quantum chemistry simulation on quantum computers: theories and experiments.

PubMed

Lu, Dawei; Xu, Boruo; Xu, Nanyang; Li, Zhaokai; Chen, Hongwei; Peng, Xinhua; Xu, Ruixue; Du, Jiangfeng

2012-07-14

It has been claimed that quantum computers can mimic quantum systems efficiently in the polynomial scale. Traditionally, those simulations are carried out numerically on classical computers, which are inevitably confronted with the exponential growth of required resources, with the increasing size of quantum systems. Quantum computers avoid this problem, and thus provide a possible solution for large quantum systems. In this paper, we first discuss the ideas of quantum simulation, the background of quantum simulators, their categories, and the development in both theories and experiments. We then present a brief introduction to quantum chemistry evaluated via classical computers followed by typical procedures of quantum simulation towards quantum chemistry. Reviewed are not only theoretical proposals but also proof-of-principle experimental implementations, via a small quantum computer, which include the evaluation of the static molecular eigenenergy and the simulation of chemical reaction dynamics. Although the experimental development is still behind the theory, we give prospects and suggestions for future experiments. We anticipate that in the near future quantum simulation will become a powerful tool for quantum chemistry over classical computations.

Chemically assembled double-dot single-electron transistor analyzed by the orthodox model considering offset charge

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kano, Shinya; Maeda, Kosuke; Majima, Yutaka, E-mail: majima@msl.titech.ac.jp

2015-10-07

We present the analysis of chemically assembled double-dot single-electron transistors using orthodox model considering offset charges. First, we fabricate chemically assembled single-electron transistors (SETs) consisting of two Au nanoparticles between electroless Au-plated nanogap electrodes. Then, extraordinary stable Coulomb diamonds in the double-dot SETs are analyzed using the orthodox model, by considering offset charges on the respective quantum dots. We determine the equivalent circuit parameters from Coulomb diamonds and drain current vs. drain voltage curves of the SETs. The accuracies of the capacitances and offset charges on the quantum dots are within ±10%, and ±0.04e (where e is the elementary charge),more » respectively. The parameters can be explained by the geometrical structures of the SETs observed using scanning electron microscopy images. Using this approach, we are able to understand the spatial characteristics of the double quantum dots, such as the relative distance from the gate electrode and the conditions for adsorption between the nanogap electrodes.« less

Effects of two successive parity-invariant point interactions on one-dimensional quantum transmission: Resonance conditions for the parameter space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Konno, Kohkichi, E-mail: kohkichi@tomakomai-ct.ac.jp; Nagasawa, Tomoaki, E-mail: nagasawa@tomakomai-ct.ac.jp; Takahashi, Rohta, E-mail: takahashi@tomakomai-ct.ac.jp

We consider the scattering of a quantum particle by two independent, successive parity-invariant point interactions in one dimension. The parameter space for the two point interactions is given by the direct product of two tori, which is described by four parameters. By investigating the effects of the two point interactions on the transmission probability of plane wave, we obtain the conditions for the parameter space under which perfect resonant transmission occur. The resonance conditions are found to be described by symmetric and anti-symmetric relations between the parameters.

Theoretical calculations of physico-chemical and spectroscopic properties of bioinorganic systems: current limits and perspectives.

PubMed

Rokob, Tibor András; Srnec, Martin; Rulíšek, Lubomír

2012-05-21

In the last decade, we have witnessed substantial progress in the development of quantum chemical methodologies. Simultaneously, robust solvation models and various combined quantum and molecular mechanical (QM/MM) approaches have become an integral part of quantum chemical programs. Along with the steady growth of computer power and, more importantly, the dramatic increase of the computer performance to price ratio, this has led to a situation where computational chemistry, when exercised with the proper amount of diligence and expertise, reproduces, predicts, and complements the experimental data. In this perspective, we review some of the latest achievements in the field of theoretical (quantum) bioinorganic chemistry, concentrating mostly on accurate calculations of the spectroscopic and physico-chemical properties of open-shell bioinorganic systems by wave-function (ab initio) and DFT methods. In our opinion, the one-to-one mapping between the calculated properties and individual molecular structures represents a major advantage of quantum chemical modelling since this type of information is very difficult to obtain experimentally. Once (and only once) the physico-chemical, thermodynamic and spectroscopic properties of complex bioinorganic systems are quantitatively reproduced by theoretical calculations may we consider the outcome of theoretical modelling, such as reaction profiles and the various decompositions of the calculated parameters into individual spatial or physical contributions, to be reliable. In an ideal situation, agreement between theory and experiment may imply that the practical problem at hand, such as the reaction mechanism of the studied metalloprotein, can be considered as essentially solved.

Quantum chaos in nuclear physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bunakov, V. E., E-mail: bunakov@VB13190.spb.edu

A definition of classical and quantum chaos on the basis of the Liouville–Arnold theorem is proposed. According to this definition, a chaotic quantum system that has N degrees of freedom should have M < N independent first integrals of motion (good quantum numbers) that are determined by the symmetry of the Hamiltonian for the system being considered. Quantitative measures of quantum chaos are established. In the classical limit, they go over to the Lyapunov exponent or the classical stability parameter. The use of quantum-chaos parameters in nuclear physics is demonstrated.

Quantum mechanical force field for hydrogen fluoride with explicit electronic polarization.

PubMed

Mazack, Michael J M; Gao, Jiali

2014-05-28

The explicit polarization (X-Pol) theory is a fragment-based quantum chemical method that explicitly models the internal electronic polarization and intermolecular interactions of a chemical system. X-Pol theory provides a framework to construct a quantum mechanical force field, which we have extended to liquid hydrogen fluoride (HF) in this work. The parameterization, called XPHF, is built upon the same formalism introduced for the XP3P model of liquid water, which is based on the polarized molecular orbital (PMO) semiempirical quantum chemistry method and the dipole-preserving polarization consistent point charge model. We introduce a fluorine parameter set for PMO, and find good agreement for various gas-phase results of small HF clusters compared to experiments and ab initio calculations at the M06-2X/MG3S level of theory. In addition, the XPHF model shows reasonable agreement with experiments for a variety of structural and thermodynamic properties in the liquid state, including radial distribution functions, interaction energies, diffusion coefficients, and densities at various state points.

Multivariate analysis and extraction of parameters in resistive RAMs using the Quantum Point Contact model

NASA Astrophysics Data System (ADS)

Roldán, J. B.; Miranda, E.; González-Cordero, G.; García-Fernández, P.; Romero-Zaliz, R.; González-Rodelas, P.; Aguilera, A. M.; González, M. B.; Jiménez-Molinos, F.

2018-01-01

A multivariate analysis of the parameters that characterize the reset process in Resistive Random Access Memory (RRAM) has been performed. The different correlations obtained can help to shed light on the current components that contribute in the Low Resistance State (LRS) of the technology considered. In addition, a screening method for the Quantum Point Contact (QPC) current component is presented. For this purpose, the second derivative of the current has been obtained using a novel numerical method which allows determining the QPC model parameters. Once the procedure is completed, a whole Resistive Switching (RS) series of thousands of curves is studied by means of a genetic algorithm. The extracted QPC parameter distributions are characterized in depth to get information about the filamentary pathways associated with LRS in the low voltage conduction regime.

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

PubMed

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.

Protein Structure Validation and Refinement Using Amide Proton Chemical Shifts Derived from Quantum Mechanics

PubMed Central

Christensen, Anders S.; Linnet, Troels E.; Borg, Mikael; Boomsma, Wouter; Lindorff-Larsen, Kresten; Hamelryck, Thomas; Jensen, Jan H.

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 QM results obtained for a small protein with an RMSD of 0.25 ppm (r = 0.94). ProCS is interfaced with the PHAISTOS protein simulation program and is used to infer statistical protein ensembles that reflect experimentally measured amide proton chemical shift values. Such chemical shift-based structural refinements, starting from high-resolution X-ray structures of Protein G, ubiquitin, and SMN Tudor Domain, result in average chemical shifts, hydrogen bond geometries, and trans-hydrogen bond (h3 JNC') spin-spin coupling constants that are in excellent agreement with experiment. We show that the structural sensitivity of the QM-based amide proton chemical shift predictions is needed to obtain this agreement. The ProCS method thus offers a powerful new tool for refining the structures of hydrogen bonding networks to high accuracy with many potential applications such as protein flexibility in ligand binding. PMID:24391900

Quantum-mechanical parameters for the risk assessment of multi-walled carbon-nanotubes: A study using adsorption of probe compounds and its application to biomolecules.

PubMed

Chayawan; Vikas

2016-11-01

This work forwards new insights into the risk-assessment of multi-walled carbon-nanotubes (MWCNTs) while analysing the role of quantum-mechanical interactions between the electrons in the adsorption of probe compounds and biomolecules by MWCNTs. For this, the quantitative models are developed using quantum-chemical descriptors and their electron-correlation contribution. The major quantum-chemical factors contributing to the adsorption are found to be mean polarizability, electron-correlation energy, and electron-correlation contribution to the absolute electronegativity and LUMO energy. The proposed models, based on only three quantum-chemical factors, are found to be even more robust and predictive than the previously known five or four factors based linear free-energy and solvation-energy relationships. The proposed models are employed to predict the adsorption of biomolecules including steroid hormones and DNA bases. The steroid hormones are predicted to be strongly adsorbed by the MWCNTs, with the order: hydrocortisone > aldosterone > progesterone > ethinyl-oestradiol > testosterone > oestradiol, whereas the DNA bases are found to be relatively less adsorbed but follow the order as: guanine > adenine > thymine > cytosine > uracil. Besides these, the developed electron-correlation based models predict several insecticides, pesticides, herbicides, fungicides, plasticizers and antimicrobial agents in cosmetics, to be strongly adsorbed by the carbon-nanotubes. The present study proposes that the instantaneous inter-electronic interactions may be quite significant in various physico-chemical processes involving MWCNTs, and can be used as a reliable predictor for their risk assessment. Copyright © 2016 Elsevier Ltd. All rights reserved.

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

PubMed

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.

The quantum dynamics of electronically nonadiabatic chemical reactions

NASA Technical Reports Server (NTRS)

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

Chemical Shifts of the Carbohydrate Binding Domain of Galectin-3 from Magic Angle Spinning NMR and Hybrid Quantum Mechanics/Molecular Mechanics Calculations.

PubMed

Kraus, Jodi; Gupta, Rupal; Yehl, Jenna; Lu, Manman; Case, David A; Gronenborn, Angela M; Akke, Mikael; Polenova, Tatyana

2018-03-22

Magic angle spinning NMR spectroscopy is uniquely suited to probe the structure and dynamics of insoluble proteins and protein assemblies at atomic resolution, with NMR chemical shifts containing rich information about biomolecular structure. Access to this information, however, is problematic, since accurate quantum mechanical calculation of chemical shifts in proteins remains challenging, particularly for 15 N H . Here we report on isotropic chemical shift predictions for the carbohydrate recognition domain of microcrystalline galectin-3, obtained from using hybrid quantum mechanics/molecular mechanics (QM/MM) calculations, implemented using an automated fragmentation approach, and using very high resolution (0.86 Å lactose-bound and 1.25 Å apo form) X-ray crystal structures. The resolution of the X-ray crystal structure used as an input into the AF-NMR program did not affect the accuracy of the chemical shift calculations to any significant extent. Excellent agreement between experimental and computed shifts is obtained for 13 C α , while larger scatter is observed for 15 N H chemical shifts, which are influenced to a greater extent by electrostatic interactions, hydrogen bonding, and solvation.

Quantum mechanics on the h-deformed quantum plane

NASA Astrophysics Data System (ADS)

Cho, Sunggoo

1999-03-01

We find the covariant deformed Heisenberg algebra and the Laplace-Beltrami operator on the extended h-deformed quantum plane and solve the Schrödinger equations explicitly for some physical systems on the quantum plane. In the commutative limit the behaviour of a quantum particle on the quantum plane becomes that of the quantum particle on the Poincaré half-plane, a surface of constant negative Gaussian curvature. We show that the bound state energy spectra for particles under specific potentials depend explicitly on the deformation parameter h. Moreover, it is shown that bound states can survive on the quantum plane in a limiting case where bound states on the Poincaré half-plane disappear.

Global chemical reactivity parameters for several chiral beta-blockers from the Density Functional Theory viewpoint

PubMed Central

TALMACIU, MONA MARIA; BODOKI, EDE; OPREAN, RADU

2016-01-01

Background and aim Beta-adrenergic antagonists have been established as first line treatment in the medical management of hypertension, acute coronary syndrome and other cardiovascular diseases, as well as for the prevention of initial episodes of gastrointestinal bleeding in patients with cirrhosis and esophageal varices, glaucoma, and have recently become the main form of treatment of infantile hemangiomas. The aim of the present study is to calculate for 14 beta-blockers several quantum chemical descriptors in order to interpret various molecular properties such as electronic structure, conformation, reactivity, in the interest of determining how such descriptors could have an impact on our understanding of the experimental observations and describing various aspects of chemical binding of beta-blockers in terms of these descriptors. Methods The 2D chemical structures of the beta-blockers (14 molecules with one stereogenic center) were cleaned in 3D, their geometry was preoptimized using the software MOPAC2012, by PM6 method, and then further refined using standard settings in MOE; HOMO and LUMO descriptors were calculated using semi-empirical molecular orbital methods AM1, MNDO and PM3, for the lowest energy conformers and the quantum chemical descriptors (HLG, electronegativity, chemical potential, hardness and softness, electrophilicity) were then calculated. Results According to HOMO-LUMO gap and the chemical hardness the most stable compounds are alprenolol, bisoprolol and esmolol. The softness values calculated for the study molecules revolve around 0.100. Propranolol, sotalol and timolol have among the highest electrophilicity index of the studied beta-blocker molecules. Results obtained from calculations showed that acebutolol, atenolol, timolol and sotalol have the highest values for the electronegativity index. Conclusions The future aim is to determine whether it is possible to find a valid correlation between these descriptors and the physicochemical

The GUP and quantum Raychaudhuri equation

NASA Astrophysics Data System (ADS)

Vagenas, Elias C.; Alasfar, Lina; Alsaleh, Salwa M.; Ali, Ahmed Farag

2018-06-01

In this paper, we compare the quantum corrections to the Schwarzschild black hole temperature due to quadratic and linear-quadratic generalised uncertainty principle, with the corrections from the quantum Raychaudhuri equation. The reason for this comparison is to connect the deformation parameters β0 and α0 with η which is the parameter that characterises the quantum Raychaudhuri equation. The derived relation between the parameters appears to depend on the relative scale of the system (black hole), which could be read as a beta function equation for the quadratic deformation parameter β0. This study shows a correspondence between the two phenomenological approaches and indicates that quantum Raychaudhuri equation implies the existence of a crystal-like structure of spacetime.

Epitaxial Zn quantum dots coherently grown on Si(1 1 1): growth mechanism, nonlinear optical and chemical states analyses

NASA Astrophysics Data System (ADS)

Huang, Bo-Jia; Kao, Li-Chi; Brahma, Sanjaya; Jeng, Yu-En; Chiu, Shang-Jui; Ku, Ching-Shun; Lo, Kuang-Yao

2017-05-01

Oxide- and defect-free metal/semiconductor interface is important to improve Ohmic contact for the suppression of electron scattering and the avoidance of an extrinsic surface state in estimating the barrier of the Schottky contact at the nanodevice interface. This study reports the growth mechanism of Zn quantum dots coherently grown on Si(1 1 1) and the physical phenomena of the crystalline, nonlinear optics, and the chemical states of Zn quantum dots. Epitaxial Zn quantum dots were coherently formed on a non-oxide Si(1 1 1) surface through the liquid- to solid-phase transformation as a result of pattern matching between the Zn(0 0 2) and Si(1 1 1) surfaces. The growth mechanism of constrained Zn quantum dots grown through strategic magnetron radio frequency sputtering is complex. Some factors, such as substrate temperature, hydrogen gas flow, and negative DC bias, influence the configuration of epitaxial Zn quantum dots. In particular, hydrogen gas plays an important role in reducing the ZnO+ and native oxide that is bombarded by accelerated ions, thereby enhancing the Zn ion surface diffusion. The reduction reaction can be inspected by distinguishing the chemical states of ZnO/Zn quantum dots from natural oxidation or the states of Zn 3d through the analysis of x-ray absorption near the edge structure spectrum. The complex growth mechanism can be systematically understood by analyzing a noncancelled anisotropic 3 m dipole from reflective second harmonic generation and inspecting the evolution between the Zn(0 0 2) and Zn(1 1 1) peaks of the collective ZnO/Zn quantum dots in synchrotron XRD.

Use of external cavity quantum cascade laser compliance voltage in real-time trace gas sensing of multiple chemicals

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Mark C.; Taubman, Matthew S.; Kriesel, Jason M.

2015-02-08

We describe a prototype trace gas sensor designed for real-time detection of multiple chemicals. The sensor uses an external cavity quantum cascade laser (ECQCL) swept over its tuning range of 940-1075 cm-1 (9.30-10.7 µm) at a 10 Hz repetition rate.

Channel Simulation in Quantum Metrology

NASA Astrophysics Data System (ADS)

Laurenza, Riccardo; Lupo, Cosmo; Spedalieri, Gaetana; Braunstein, Samuel L.; Pirandola, Stefano

2018-04-01

In this review we discuss how channel simulation can be used to simplify the most general protocols of quantum parameter estimation, where unlimited entanglement and adaptive joint operations may be employed. Whenever the unknown parameter encoded in a quantum channel is completely transferred in an environmental program state simulating the channel, the optimal adaptive estimation cannot beat the standard quantum limit. In this setting, we elucidate the crucial role of quantum teleportation as a primitive operation which allows one to completely reduce adaptive protocols over suitable teleportation-covariant channels and derive matching upper and lower bounds for parameter estimation. For these channels,wemay express the quantum Cramér Rao bound directly in terms of their Choi matrices. Our review considers both discrete- and continuous-variable systems, also presenting some new results for bosonic Gaussian channels using an alternative sub-optimal simulation. It is an open problem to design simulations for quantum channels that achieve the Heisenberg limit.

Quantum chemical characterization of zwitterionic structures: Supramolecular complexes for modifying the wettability of oil-water-limestone system.

PubMed

Lopez-Chavez, Ernesto; Garcia-Quiroz, Alberto; Gonzalez-Garcia, Gerardo; Orozco-Duran, Gabriela E; Zamudio-Rivera, Luis S; Martinez-Magadan, José M; Buenrostro-Gonzalez, Eduardo; Hernandez-Altamirano, Raul

2014-06-01

In this work, we present a quantum chemical study pertaining to some supramolecular complexes acting as wettability modifiers of oil-water-limestone system. The complexes studied are derived from zwitterionic liquids of the types N'-alkyl-bis, N-alquenil, N-cycloalkyl, N-amyl-bis-beta amino acid or salts acting as sparkling agents. We studied two molecules of zwitterionic liquids (ZL10 and ZL13), HOMO and LUMO levels, and the energy gap between them, were calculated, as well as the electron affinity (EA) and ionization potential (IP), chemical potential, chemical hardness, chemical electrophilicity index and selectivity descriptors such Fukui indices. In this work, electrochemical comparison was realized with cocamidopropyl betaine (CPB), which is a structure zwitterionic liquid type, nowadays widely applied in enhanced recovery processes. Copyright © 2014 Elsevier Inc. All rights reserved.

Quantum Discord Determines the Interferometric Power of Quantum States

NASA Astrophysics Data System (ADS)

Girolami, Davide; Souza, Alexandre M.; Giovannetti, Vittorio; Tufarelli, Tommaso; Filgueiras, Jefferson G.; Sarthour, Roberto S.; Soares-Pinto, Diogo O.; Oliveira, Ivan S.; Adesso, Gerardo

2014-05-01

Quantum metrology exploits quantum mechanical laws to improve the precision in estimating technologically relevant parameters such as phase, frequency, or magnetic fields. Probe states are usually tailored to the particular dynamics whose parameters are being estimated. Here we consider a novel framework where quantum estimation is performed in an interferometric configuration, using bipartite probe states prepared when only the spectrum of the generating Hamiltonian is known. We introduce a figure of merit for the scheme, given by the worst-case precision over all suitable Hamiltonians, and prove that it amounts exactly to a computable measure of discord-type quantum correlations for the input probe. We complement our theoretical results with a metrology experiment, realized in a highly controllable room-temperature nuclear magnetic resonance setup, which provides a proof-of-concept demonstration for the usefulness of discord in sensing applications. Discordant probes are shown to guarantee a nonzero phase sensitivity for all the chosen generating Hamiltonians, while classically correlated probes are unable to accomplish the estimation in a worst-case setting. This work establishes a rigorous and direct operational interpretation for general quantum correlations, shedding light on their potential for quantum technology.

High-School Students' Conceptual Difficulties and Attempts at Conceptual Change: The Case of Basic Quantum Chemical Concepts

ERIC Educational Resources Information Center

Tsaparlis, Georgios; Papaphotis, Georgios

2009-01-01

This study tested for deep understanding and critical thinking about basic quantum chemical concepts taught at 12th grade (age 17-18). Our aim was to achieve conceptual change in students. A quantitative study was conducted first (n = 125), and following this 23 selected students took part in semi-structured interviews either individually or in…

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

ERIC Educational Resources Information Center

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…

Chemical potential and compressibility of quantum Hall bilayer excitons,.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Skinner, Brian

2016-02-25

I consider a system of two parallel quantum Hall layers with total filling factor 0 or 1. When the distance between the layers is small enough, electrons and holes in opposite layers can form inter-layer excitons, which have a finite effective mass and interact via a dipole-dipole potential. I present results for the chemical potential u of the resulting bosonic system as a function of the exciton concentration n and the interlayer separation d. I show that both u and the interlayer capacitance have an unusual nonmonotonic dependence on d, owing to the interplay between an increasing dipole moment andmore » an increasing effective mass with increasing d. Finally, I discuss the transition between the superfluid and Wigner crystal phases, which is shown to occur at d x n-1/10. Results are derived first via simple intuitive arguments, and then verified with more careful analytic derivations and numeric calculations.« less

Teleportation of quantum resources and quantum Fisher information under Unruh effect

NASA Astrophysics Data System (ADS)

Jafarzadeh, M.; Rangani Jahromi, H.; Amniat-Talab, M.

2018-07-01

Considering a pair of Unruh-DeWitt detectors, when one of them is kept inertial and the other one is accelerated and coupled to a scalar field, we address the teleportation of a two-qubit entangled state ( |ψ _in> = {cos} θ /2 |10> +e^{iφ} {sin} θ /2 |01> ) through the quantum channel created by the above system and investigate how thermal noise induced by Unruh effect affects the quantum resources and quantum Fisher information (QFI) teleportation. Our results showed while the teleported quantum resources and QFI with respect to phase parameter φ( F_{ {out}}( φ ) ) reduce with increasing acceleration and effective coupling, QFI with respect to weight parameter θ ( F_{ {out}}( θ ) ) interestingly increases after a specified value of acceleration and effective coupling. We also find that the teleported quantum resources and the precision of estimating phase parameter φ can be improved by a more entangled input state and more entangled channel. Moreover, the precision of estimating weight parameter θ increases for a maximally entangled input state only in large acceleration regime, while it does not change considerably for both maximally and partially entangled states of the channel. The influence of Unruh effect on fidelity of teleportation is also investigated. We showed that for small effective coupling the average fidelity is always larger than 2/3.

Molecular nanomagnets with switchable coupling for quantum simulation

DOE PAGES

Chiesa, Alessandro; Whitehead, George F. S.; Carretta, Stefano; ...

2014-12-11

Molecular nanomagnets are attractive candidate qubits because of their wide inter- and intra-molecular tunability. Uniform magnetic pulses could be exploited to implement one- and two-qubit gates in presence of a properly engineered pattern of interactions, but the synthesis of suitable and potentially scalable supramolecular complexes has proven a very hard task. Indeed, no quantum algorithms have ever been implemented, not even a proof-of-principle two-qubit gate. In this paper we show that the magnetic couplings in two supramolecular {Cr7Ni}-Ni-{Cr7Ni} assemblies can be chemically engineered to fit the above requisites for conditional gates with no need of local control. Microscopic parameters aremore » determined by a recently developed many-body ab-initio approach and used to simulate quantum gates. We find that these systems are optimal for proof-of-principle two-qubit experiments and can be exploited as building blocks of scalable architectures for quantum simulation.« less

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

PubMed

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.

The quantum chemical study of the electronic states of S2Cl and its monovalent ions.

PubMed

Czernek, Jiří; Zivný, Oldřich

2012-09-01

High-level quantum chemical techniques have been utilized to accurately describe the geometrical parameters, vibrational frequencies and dissociation pathways of the X (2)A″, 1 (2)A', 2 (2)A', 2 (2)A″ states of S(2)Cl; X (1)A', 1 (3)A″, 1 (1)A″, 1 (3)A' states of S(2)Cl(+); X (1)A', 1 (3)A', (1)A″ states of S(2)Cl(-), and the corresponding excitation energies have been obtained from the energies extrapolated to their complete basis set limits. It has been established that the 2 (2)A' and 2 (2)A″ terms of S(2)Cl exhibit a strong multi-reference character, while all the remaining excited states are dominated by the single replacements from the reference determinants. The enthalpies of the decomposition reactions have been obtained to aid in the investigations into the photolysis of S(2)Cl(2) and related systems. The value of the ionization potential of S(2)Cl has been found within the error bars of the experiment, and a reliable estimate of its electron affinity, EA (0) = -2.352 eV, has been proposed.

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

NASA Astrophysics Data System (ADS)

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.

Demonstration of a rapidly-swept external cavity quantum cascade laser for rapid and sensitive quantification of chemical mixtures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brumfield, Brian E.; Taubman, Matthew S.; Phillips, Mark C.

2016-02-13

A rapidly-swept external cavity quantum cascade laser (ECQCL) system for fast open-path quantification of multiple chemicals and mixtures is presented. The ECQCL system is swept over its entire tuning range (>100 cm-1) at frequencies up to 200 Hz. At 200 Hz the wavelength tuning rate and spectral resolution are 2x104 cm-1/sec and < 0.2 cm-1, respectively. The capability of the current system to quantify changes in chemical concentrations on millesecond timescales is demonstrated at atmospheric pressure using an open-path multi-pass cell. The detection limits for chemicals ranged from ppb to ppm levels depending on the absorption cross-section.

The Nature of the Chemical Bond--1990.

ERIC Educational Resources Information Center

Ogilvie, J. F.

1990-01-01

Three aspects of quantum mechanics in modern chemistry are stressed: the fundamental structure of quantum mechanics as a basis of chemical applications, the relationship of quantum mechanics to atomic and molecular structure, and the consequent implications for chemical education. A list of 64 references is included. (CW)

Hybrid Quantum-Classical Approach to Quantum Optimal Control.

PubMed

Li, Jun; Yang, Xiaodong; Peng, Xinhua; Sun, Chang-Pu

2017-04-14

A central challenge in quantum computing is to identify more computational problems for which utilization of quantum resources can offer significant speedup. Here, we propose a hybrid quantum-classical scheme to tackle the quantum optimal control problem. We show that the most computationally demanding part of gradient-based algorithms, namely, computing the fitness function and its gradient for a control input, can be accomplished by the process of evolution and measurement on a quantum simulator. By posing queries to and receiving answers from the quantum simulator, classical computing devices update the control parameters until an optimal control solution is found. To demonstrate the quantum-classical scheme in experiment, we use a seven-qubit nuclear magnetic resonance system, on which we have succeeded in optimizing state preparation without involving classical computation of the large Hilbert space evolution.

Separating strain from composition in unit cell parameter maps obtained from aberration corrected high resolution transmission electron microscopy imaging

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schulz, T.; Remmele, T.; Korytov, M.

2014-01-21

Based on the evaluation of lattice parameter maps in aberration corrected high resolution transmission electron microscopy images, we propose a simple method that allows quantifying the composition and disorder of a semiconductor alloy at the unit cell scale with high accuracy. This is realized by considering, next to the out-of-plane, also the in-plane lattice parameter component allowing to separate the chemical composition from the strain field. Considering only the out-of-plane lattice parameter component not only yields large deviations from the true local alloy content but also carries the risk of identifying false ordering phenomena like formations of chains or platelets.more » Our method is demonstrated on image simulations of relaxed supercells, as well as on experimental images of an In{sub 0.20}Ga{sub 0.80}N quantum well. Principally, our approach is applicable to all epitaxially strained compounds in the form of quantum wells, free standing islands, quantum dots, or wires.« less

Quantum chemical calculations of glycine glutaric acid

NASA Astrophysics Data System (ADS)

Arioǧlu, ćaǧla; Tamer, Ömer; Avci, Davut; Atalay, Yusuf

2017-02-01

Density functional theory (DFT) calculations of glycine glutaric acid were performed by using B3LYP levels with 6-311++G(d,p) basis set. The theoretical structural parameters such as bond lengths and bond angles are in a good agreement with the experimental values of the title compound. HOMO and LUMO energies were calculated, and the obtained energy gap shows that charge transfer occurs in the title compound. Vibrational frequencies were calculated and compare with experimental ones. 3D molecular surfaces of the title compound were simulated using the same level and basis set. Finally, the 13C and 1H NMR chemical shift values were calculated by the application of the gauge independent atomic orbital (GIAO) method.

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed

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.

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

PubMed

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

2016-01-07

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

Advances in Quantum Mechanochemistry: Electronic Structure Methods and Force Analysis.

PubMed

Stauch, Tim; Dreuw, Andreas

2016-11-23

In quantum mechanochemistry, quantum chemical methods are used to describe molecules under the influence of an external force. The calculation of geometries, energies, transition states, reaction rates, and spectroscopic properties of molecules on the force-modified potential energy surfaces is the key to gain an in-depth understanding of mechanochemical processes at the molecular level. In this review, we present recent advances in the field of quantum mechanochemistry and introduce the quantum chemical methods used to calculate the properties of molecules under an external force. We place special emphasis on quantum chemical force analysis tools, which can be used to identify the mechanochemically relevant degrees of freedom in a deformed molecule, and spotlight selected applications of quantum mechanochemical methods to point out their synergistic relationship with experiments.

Rapid prediction of chemical metabolism by human UDP-glucuronosyltransferase isoforms using quantum chemical descriptors derived with the electronegativity equalization method.

PubMed

Sorich, Michael J; McKinnon, Ross A; Miners, John O; Winkler, David A; Smith, Paul A

2004-10-07

This study aimed to evaluate in silico models based on quantum chemical (QC) descriptors derived using the electronegativity equalization method (EEM) and to assess the use of QC properties to predict chemical metabolism by human UDP-glucuronosyltransferase (UGT) isoforms. Various EEM-derived QC molecular descriptors were calculated for known UGT substrates and nonsubstrates. Classification models were developed using support vector machine and partial least squares discriminant analysis. In general, the most predictive models were generated with the support vector machine. Combining QC and 2D descriptors (from previous work) using a consensus approach resulted in a statistically significant improvement in predictivity (to 84%) over both the QC and 2D models and the other methods of combining the descriptors. EEM-derived QC descriptors were shown to be both highly predictive and computationally efficient. It is likely that EEM-derived QC properties will be generally useful for predicting ADMET and physicochemical properties during drug discovery.

Computer-Aided Construction of Chemical Kinetic Models

DOE Office of Scientific and Technical Information (OSTI.GOV)

Green, William H.

2014-12-31

The combustion chemistry of even simple fuels can be extremely complex, involving hundreds or thousands of kinetically significant species. The most reasonable way to deal with this complexity is to use a computer not only to numerically solve the kinetic model, but also to construct the kinetic model in the first place. Because these large models contain so many numerical parameters (e.g. rate coefficients, thermochemistry) one never has sufficient data to uniquely determine them all experimentally. Instead one must work in “predictive” mode, using theoretical rather than experimental values for many of the numbers in the model, and as appropriatemore » refining the most sensitive numbers through experiments. Predictive chemical kinetics is exactly what is needed for computer-aided design of combustion systems based on proposed alternative fuels, particularly for early assessment of the value and viability of proposed new fuels before those fuels are commercially available. This project was aimed at making accurate predictive chemical kinetics practical; this is a challenging goal which requires a range of science advances. The project spanned a wide range from quantum chemical calculations on individual molecules and elementary-step reactions, through the development of improved rate/thermo calculation procedures, the creation of algorithms and software for constructing and solving kinetic simulations, the invention of methods for model-reduction while maintaining error control, and finally comparisons with experiment. Many of the parameters in the models were derived from quantum chemistry calculations, and the models were compared with experimental data measured in our lab or in collaboration with others.« less

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

PubMed

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.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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°.

Optimization of enzyme parameters for fermentative production of biorenewable fuels and chemicals

PubMed Central

Jarboe, Laura R.; Liu, Ping; Kautharapu, Kumar Babu; Ingram, Lonnie O.

2012-01-01

Microbial biocatalysts such as Escherichia coli and Saccharomyces cerevisiae have been extensively subjected to Metabolic Engineering for the fermentative production of biorenewable fuels and chemicals. This often entails the introduction of new enzymes, deletion of unwanted enzymes and efforts to fine-tune enzyme abundance in order to attain the desired strain performance. Enzyme performance can be quantitatively described in terms of the Michaelis-Menten type parameters Km, turnover number kcat and Ki, which roughly describe the affinity of an enzyme for its substrate, the speed of a reaction and the enzyme sensitivity to inhibition by regulatory molecules. Here we describe examples of where knowledge of these parameters have been used to select, evolve or engineer enzymes for the desired performance and enabled increased production of biorenewable fuels and chemicals. Examples include production of ethanol, isobutanol, 1-butanol and tyrosine and furfural tolerance. The Michaelis-Menten parameters can also be used to judge the cofactor dependence of enzymes and quantify their preference for NADH or NADPH. Similarly, enzymes can be selected, evolved or engineered for the preferred cofactor preference. Examples of exporter engineering and selection are also discussed in the context of production of malate, valine and limonene. PMID:24688665

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

PubMed Central

Jhin, Changho; Hwang, Keum Taek

2014-01-01

Radical scavenging activity of anthocyanins is well known, but only a few studies have been conducted by quantum chemical approach. The adaptive neuro-fuzzy inference system (ANFIS) is an effective technique for solving problems with uncertainty. The purpose of this study was to construct and evaluate quantitative structure-activity relationship (QSAR) models for predicting radical scavenging activities of anthocyanins with good prediction efficiency. ANFIS-applied QSAR models were developed by using quantum chemical descriptors of anthocyanins calculated by semi-empirical PM6 and PM7 methods. Electron affinity (A) and electronegativity (χ) of flavylium cation, and ionization potential (I) of quinoidal base were significantly correlated with radical scavenging activities of anthocyanins. These descriptors were used as independent variables for QSAR models. ANFIS models with two triangular-shaped input fuzzy functions for each independent variable were constructed and optimized by 100 learning epochs. The constructed models using descriptors calculated by both PM6 and PM7 had good prediction efficiency with Q-square of 0.82 and 0.86, respectively. PMID:25153627

Quantum optics, cavity QED, and quantum optomechanics

NASA Astrophysics Data System (ADS)

Meystre, Pierre

2013-05-01

Quantum optomechanics provides a universal tool to achieve the quantum control of mechanical motion. It does that in devices spanning a vast range of parameters, with mechanical frequencies from a few Hertz to GHz, and with masses from 10-20 g to several kilos. Its underlying ideas can be traced back to the study of gravitational wave antennas, quantum optics, cavity QED and laser cooling which, when combined with the recent availability of advanced micromechanical and nanomechanical devices, opens a path to the realization of macroscopic mechanical systems that operate deep in the quantum regime. At the fundamental level this development paves the way to experiments that will lead to a more profound understanding of quantum mechanics; and from the point of view of applications, quantum optomechanical techniques will provide motion and force sensing near the fundamental limit imposed by quantum mechanics (quantum metrology) and significantly expand the toolbox of quantum information science. After a brief summary of key historical developments, the talk will give a broad overview of the current state of the art of quantum optomechanics, and comment on future prospects both in applied and in fundamental science. Work supported by NSF, ARO and the DARPA QuASAR and ORCHID programs.

Cryo-mediated exfoliation and fracturing of layered materials into 2D quantum dots

PubMed Central

Wang, Yan; Liu, Yang; Zhang, Jianfang; Wu, Jingjie; Xu, Hui; Wen, Xiewen; Zhang, Xiang; Tiwary, Chandra Sekhar; Yang, Wei; Vajtai, Robert; Zhang, Yong; Chopra, Nitin; Odeh, Ihab Nizar; Wu, Yucheng; Ajayan, Pulickel M.

2017-01-01

Atomically thin quantum dots from layered materials promise new science and applications, but their scalable synthesis and separation have been challenging. We demonstrate a universal approach for the preparation of quantum dots from a series of materials, such as graphite, MoS2, WS2, h-BN, TiS2, NbS2, Bi2Se3, MoTe2, Sb2Te3, etc., using a cryo-mediated liquid-phase exfoliation and fracturing process. The method relies on liquid nitrogen pretreatment of bulk layered materials before exfoliation and breakdown into atomically thin two-dimensional quantum dots of few-nanometer lateral dimensions, exhibiting size-confined optical properties. This process is efficient for a variety of common solvents with a wide range of surface tension parameters and eliminates the use of surfactants, resulting in pristine quantum dots without surfactant covering or chemical modification. PMID:29250597

Portable open-path chemical sensor using a quantum cascade laser

NASA Astrophysics Data System (ADS)

Corrigan, Paul; Lwin, Maung; Huntley, Reuven; Chhabra, Amandeep; Moshary, Fred; Gross, Barry; Ahmed, Samir

2009-05-01

Remote sensing of enemy installations or their movements by trace gas detection is a critical but challenging military objective. Open path measurements over ranges of a few meters to many kilometers with sensitivity in the parts per million or billion regime are crucial in anticipating the presence of a threat. Previous approaches to detect ground level chemical plumes, explosive constituents, or combustion have relied on low-resolution, short range Fourier transform infrared spectrometer (FTIR), or low-sensitivity near-infrared differential optical absorption spectroscopy (DOAS). As mid-infrared quantum cascade laser (QCL) sources have improved in cost and performance, systems based on QCL's that can be tailored to monitor multiple chemical species in real time are becoming a viable alternative. We present the design of a portable, high-resolution, multi-kilometer open path trace gas sensor based on QCL technology. Using a tunable (1045-1047cm-1) QCL, a modeled atmosphere and link-budget analysis with commercial component specifications, we show that with this approach, accuracy in parts per billion ozone or ammonia can be obtained in seconds at path lengths up to 10 km. We have assembled an open-path QCL sensor based on this theoretical approach at City College of New York, and we present preliminary results demonstrating the potential of QCLs in open-path sensing applications.

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

PubMed Central

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

2011-01-01

enhancement of their size. In concentrations <2.5 nmol/kg bodyweight, these quantum dots did not affect the main physiological variables. It was possible to visualize capillaries, which makes this quantum dot probe appropriate for investigation of mediators of vasoconstriction, vasodilatation, and brain circulation in intact animals in vivo. The multimodal silica-shelled quantum dots allowed visualization of tumor tissue in an early stage of its development, using magnetic resonance imaging. Conclusion: The present study shows that the type and structure of organic/bioorganic shells of quantum dots determine their biocompatibility and are crucial for their application in imaging in vivo, due to the effects of the shell on the following properties: colloidal stability, solubility in physiological fluids, influence of the basic physiological parameters, and cytotoxicity. PMID:21980235

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

PubMed Central

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

Chemical reaction CO+OH • → CO 2+H • autocatalyzed by carbon dioxide: Quantum chemical study of the potential energy surfaces

DOE PAGES

Masunov, Artem E.; Wait, Elizabeth; Vasu, Subith S.

2016-06-28

The supercritical carbon dioxide medium, used to increase efficiency in oxy combustion fossil energy technology, may drastically alter both rates and mechanisms of chemical reactions. Here we investigate potential energy surface of the second most important combustion reaction with quantum chemistry methods. Two types of effects are reported: formation of the covalent intermediates and formation of van der Waals complexes by spectator CO 2 molecule. While spectator molecule alter the activation barrier only slightly, the covalent bonding opens a new reaction pathway. The mechanism includes sequential covalent binding of CO 2 to OH radical and CO molecule, hydrogen transfer frommore » oxygen to carbon atoms, and CH bond dissociation. This reduces the activation barrier by 11 kcal/mol at the rate-determining step and is expected to accelerate the reaction rate. The finding of predicted catalytic effect is expected to play an important role not only in combustion but also in a broad array of chemical processes taking place in supercritical CO 2 medium. Furthermore, tt may open a new venue for controlling reaction rates for chemical manufacturing.« less

Identification of open quantum systems from observable time traces

DOE PAGES

Zhang, Jun; Sarovar, Mohan

2015-05-27

Estimating the parameters that dictate the dynamics of a quantum system is an important task for quantum information processing and quantum metrology, as well as fundamental physics. In our paper we develop a method for parameter estimation for Markovian open quantum systems using a temporal record of measurements on the system. Furthermore, the method is based on system realization theory and is a generalization of our previous work on identification of Hamiltonian parameters.

Clinical, chemical, and hematological parameters in cattle kept in a cadmium-contaminated area

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kessels, B.G.F.; Wensing, Th.; Schotman, A.J.H.

1990-02-01

In cattle exposure to cadmium may effect various clinical abnormalities such as loss of appetite, anemia, poor growth, abortions and teratogenic lesions or may pass without clinical abnormalities. Considerably less is known about the effects of chronic exposure to low levels of cadmium on clinical, chemical and hematological parameters. With respect to the way cattle can ingest cadmium from the environment, a relationship was demonstrated between cadmium content of the organs and soil cadmium content. This demonstration that, raising roughage on cadmium contaminated soil or in fields treated with cadmium containing fertilizers like sewage sludge can lead to accumulation ofmore » cadmium in the cattle in question. This study aims to investigate whether a low, chronic exposure to cadmium effects changes in some hematological, clinical and chemical parameters in cattle.« less

Evaluation of eutrophication of Ostravice river depending on the chemical and physical parameters

NASA Astrophysics Data System (ADS)

Hlavac, A.; Melcakova, I.; Novakova, J.; Svehlakova, H.; Slavikova, L.; Klimsa, L.; Bartkova, M.

2017-10-01

The main objective of this study was to evaluate which selected environmental parameters in rivers affect the concentration of chlorophyll a and the distribution of macrozoobenthos. The data were collected on selected profiles of the Ostravice mountain river in the Moravian-Silesian Region. The examined chemical and physical parameters include dissolved oxygen (DO), flow rate, oxidation-reduction potential (ORP), conductivity, temperature, pH, total nitrogen and phosphorus concentration.

Intramolecular hydrogen bonding in myricetin and myricitrin. Quantum chemical calculations and vibrational spectroscopy

NASA Astrophysics Data System (ADS)

Vojta, Danijela; Dominković, Katarina; Miljanić, Snežana; Spanget-Larsen, Jens

2017-03-01

The molecular structures of myricetin (3,3‧,4‧,5,5‧,7-hexahydroxyflavone; MCE) and myricitrin (myricetin 3-O-rhamnoside; MCI) are investigated by quantum chemical calculations (B3LYP/6-311G**). Two preferred molecular rotamers of MCI are predicted, corresponding to different conformations of the O-rhamnoside subunit. The rotamers are characterized by different hydrogen bonded cross-links between the hydroxy groups of the rhamnoside substituent and the parent MCE moiety. The predicted OH stretching frequencies are compared with vibrational spectra of MCE and MCI recorded for the sake of this investigation (IR and Raman). In addition, a reassignment of the Cdbnd O stretching bands is suggested.

Wavy carbon: A new series of carbon structures explored by quantum chemical calculations

NASA Astrophysics Data System (ADS)

Ohno, Koichi; Satoh, Hiroko; Iwamoto, Takeaki; Tokoyama, Hiroaki; Yamakado, Hideo

2015-10-01

A new carbon family adopting wavy structures has been found by quantum chemical calculations. The key motif of this family is a condensed four-membered ring. Periodically wavy-carbon sheets (wavy-Cn sheets, n = 2, 6, and 8) as well as wavy-C36 tube were found to be very similar to the previously reported prism-Cn carbon tubes (n = 5, 6, and 8) in several respects, including the relative energies per one carbon atom with respect to graphene, CC bond lengths, and CCC bond angles. Because of very high relative energies with respect to graphene (206-253 kJ mol-1), the wavy-carbons may behave as energy reserving materials.

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

DOE PAGES

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

2018-03-22

Here, 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 precomputedmore » 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.« less

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

NASA Astrophysics Data System (ADS)

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.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

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

Here, 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 precomputedmore » 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.« less

Quantum Hall resistance standards from graphene grown by chemical vapour deposition on silicon carbide

NASA Astrophysics Data System (ADS)

Lafont, F.; Ribeiro-Palau, R.; Kazazis, D.; Michon, A.; Couturaud, O.; Consejo, C.; Chassagne, T.; Zielinski, M.; Portail, M.; Jouault, B.; Schopfer, F.; Poirier, W.

2015-04-01

Replacing GaAs by graphene to realize more practical quantum Hall resistance standards (QHRS), accurate to within 10-9 in relative value, but operating at lower magnetic fields than 10 T, is an ongoing goal in metrology. To date, the required accuracy has been reported, only few times, in graphene grown on SiC by Si sublimation, under higher magnetic fields. Here, we report on a graphene device grown by chemical vapour deposition on SiC, which demonstrates such accuracies of the Hall resistance from 10 T up to 19 T at 1.4 K. This is explained by a quantum Hall effect with low dissipation, resulting from strongly localized bulk states at the magnetic length scale, over a wide magnetic field range. Our results show that graphene-based QHRS can replace their GaAs counterparts by operating in as-convenient cryomagnetic conditions, but over an extended magnetic field range. They rely on a promising hybrid and scalable growth method and a fabrication process achieving low-electron-density devices.

Quantum Hall resistance standards from graphene grown by chemical vapour deposition on silicon carbide

PubMed Central

Lafont, F.; Ribeiro-Palau, R.; Kazazis, D.; Michon, A.; Couturaud, O.; Consejo, C.; Chassagne, T.; Zielinski, M.; Portail, M.; Jouault, B.; Schopfer, F.; Poirier, W.

2015-01-01

Replacing GaAs by graphene to realize more practical quantum Hall resistance standards (QHRS), accurate to within 10−9 in relative value, but operating at lower magnetic fields than 10 T, is an ongoing goal in metrology. To date, the required accuracy has been reported, only few times, in graphene grown on SiC by Si sublimation, under higher magnetic fields. Here, we report on a graphene device grown by chemical vapour deposition on SiC, which demonstrates such accuracies of the Hall resistance from 10 T up to 19 T at 1.4 K. This is explained by a quantum Hall effect with low dissipation, resulting from strongly localized bulk states at the magnetic length scale, over a wide magnetic field range. Our results show that graphene-based QHRS can replace their GaAs counterparts by operating in as-convenient cryomagnetic conditions, but over an extended magnetic field range. They rely on a promising hybrid and scalable growth method and a fabrication process achieving low-electron-density devices. PMID:25891533

Mid-Infrared Quantum-Dot Quantum Cascade Laser: A Theoretical Feasibility Study

DOE PAGES

Michael, Stephan; Chow, Weng; Schneider, Hans

2016-05-01

In the framework of a microscopic model for intersubband gain from electrically pumped quantum-dot structures we investigate electrically pumped quantum-dots as active material for a mid-infrared quantum cascade laser. Our previous calculations have indicated that these structures could operate with reduced threshold current densities while also achieving a modal gain comparable to that of quantum well active materials. We study the influence of two important quantum-dot material parameters, here, namely inhomogeneous broadening and quantum-dot sheet density, on the performance of a proposed quantum cascade laser design. In terms of achieving a positive modal net gain, a high quantum-dot density canmore » compensate for moderately high inhomogeneous broadening, but at a cost of increased threshold current density. By minimizing quantum-dot density with presently achievable inhomogeneous broadening and total losses, significantly lower threshold densities than those reported in quantum-well quantum-cascade lasers are predicted by our theory.« less

Quantum crystallographic charge density of urea

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wall, Michael E.

Standard X-ray crystallography methods use free-atom models to calculate mean unit-cell charge densities. Real molecules, however, have shared charge that is not captured accurately using free-atom models. To address this limitation, a charge density model of crystalline urea was calculated using high-level quantum theory and was refined against publicly available ultra-high-resolution experimental Bragg data, including the effects of atomic displacement parameters. The resulting quantum crystallographic model was compared with models obtained using spherical atom or multipole methods. Despite using only the same number of free parameters as the spherical atom model, the agreement of the quantum model with the datamore » is comparable to the multipole model. The static, theoretical crystalline charge density of the quantum model is distinct from the multipole model, indicating the quantum model provides substantially new information. Hydrogen thermal ellipsoids in the quantum model were very similar to those obtained using neutron crystallography, indicating that quantum crystallography can increase the accuracy of the X-ray crystallographic atomic displacement parameters. Lastly, the results demonstrate the feasibility and benefits of integrating fully periodic quantum charge density calculations into ultra-high-resolution X-ray crystallographic model building and refinement.« less

Quantum crystallographic charge density of urea

DOE PAGES

Wall, Michael E.

2016-06-08

Standard X-ray crystallography methods use free-atom models to calculate mean unit-cell charge densities. Real molecules, however, have shared charge that is not captured accurately using free-atom models. To address this limitation, a charge density model of crystalline urea was calculated using high-level quantum theory and was refined against publicly available ultra-high-resolution experimental Bragg data, including the effects of atomic displacement parameters. The resulting quantum crystallographic model was compared with models obtained using spherical atom or multipole methods. Despite using only the same number of free parameters as the spherical atom model, the agreement of the quantum model with the datamore » is comparable to the multipole model. The static, theoretical crystalline charge density of the quantum model is distinct from the multipole model, indicating the quantum model provides substantially new information. Hydrogen thermal ellipsoids in the quantum model were very similar to those obtained using neutron crystallography, indicating that quantum crystallography can increase the accuracy of the X-ray crystallographic atomic displacement parameters. Lastly, the results demonstrate the feasibility and benefits of integrating fully periodic quantum charge density calculations into ultra-high-resolution X-ray crystallographic model building and refinement.« less

Quantum Chemical Molecular Dynamics Simulations of 1,3-Dichloropropene Combustion.

PubMed

Ahubelem, Nwakamma; Shah, Kalpit; Moghtaderi, Behdad; Page, Alister J

2015-09-03

Oxidative decomposition of 1,3-dichloropropene was investigated using quantum chemical molecular dynamics (QM/MD) at 1500 and 3000 K. Thermal oxidation of 1,3-dichloropropene was initiated by (1) abstraction of allylic H/Cl by O2 and (2) intra-annular C-Cl bond scission and elimination of allylic Cl. A kinetic analysis shows that (2) is the more dominant initiation pathway, in agreement with QM/MD results. These QM/MD simulations reveal new routes to the formation of major products (H2O, CO, HCl, CO2), which are propagated primarily by the chloroperoxy (ClO2), OH, and 1,3-dichloropropene derived radicals. In particular, intra-annular C-C/C-H bond dissociation reactions of intermediate aldehydes/ketones are shown to play a dominant role in the formation of CO and CO2. Our simulations demonstrate that both combustion temperature and radical concentration can influence the product yield, however not the combustion mechanism.

Quantum-to-classical crossover near quantum critical point

DOE PAGES

Vasin, M.; Ryzhov, V.; Vinokur, V. M.

2015-12-21

A quantum phase transition (QPT) is an inherently dynamic phenomenon. However, while non-dissipative quantum dynamics is described in detail, the question, that is not thoroughly understood is how the omnipresent dissipative processes enter the critical dynamics near a quantum critical point (QCP). Here we report a general approach enabling inclusion of both adiabatic and dissipative processes into the critical dynamics on the same footing. We reveal three distinct critical modes, the adiabatic quantum mode (AQM), the dissipative classical mode [classical critical dynamics mode (CCDM)], and the dissipative quantum critical mode (DQCM). We find that as a result of the transitionmore » from the regime dominated by thermal fluctuations to that governed by the quantum ones, the system acquires effective dimension d+zΛ(T), where z is the dynamical exponent, and temperature-depending parameter Λ(T)ε[0, 1] decreases with the temperature such that Λ(T=0) = 1 and Λ(T →∞) = 0. Lastly, our findings lead to a unified picture of quantum critical phenomena including both dissipation- and dissipationless quantum dynamic effects and offer a quantitative description of the quantum-to-classical crossover.« less

Relativistic quantum metrology: exploiting relativity to improve quantum measurement technologies.

PubMed

Ahmadi, Mehdi; Bruschi, David Edward; Sabín, Carlos; Adesso, Gerardo; Fuentes, Ivette

2014-05-22

We present a framework for relativistic quantum metrology that is useful for both Earth-based and space-based technologies. Quantum metrology has been so far successfully applied to design precision instruments such as clocks and sensors which outperform classical devices by exploiting quantum properties. There are advanced plans to implement these and other quantum technologies in space, for instance Space-QUEST and Space Optical Clock projects intend to implement quantum communications and quantum clocks at regimes where relativity starts to kick in. However, typical setups do not take into account the effects of relativity on quantum properties. To include and exploit these effects, we introduce techniques for the application of metrology to quantum field theory. Quantum field theory properly incorporates quantum theory and relativity, in particular, at regimes where space-based experiments take place. This framework allows for high precision estimation of parameters that appear in quantum field theory including proper times and accelerations. Indeed, the techniques can be applied to develop a novel generation of relativistic quantum technologies for gravimeters, clocks and sensors. As an example, we present a high precision device which in principle improves the state-of-the-art in quantum accelerometers by exploiting relativistic effects.

Compressed quantum computation using a remote five-qubit quantum computer

NASA Astrophysics Data System (ADS)

Hebenstreit, M.; Alsina, D.; Latorre, J. I.; Kraus, B.

2017-05-01

The notion of compressed quantum computation is employed to simulate the Ising interaction of a one-dimensional chain consisting of n qubits using the universal IBM cloud quantum computer running on log2(n ) qubits. The external field parameter that controls the quantum phase transition of this model translates into particular settings of the quantum gates that generate the circuit. We measure the magnetization, which displays the quantum phase transition, on a two-qubit system, which simulates a four-qubit Ising chain, and show its agreement with the theoretical prediction within a certain error. We also discuss the relevant point of how to assess errors when using a cloud quantum computer with a limited amount of runs. As a solution, we propose to use validating circuits, that is, to run independent controlled quantum circuits of similar complexity to the circuit of interest.

Parameter optimization in biased decoy-state quantum key distribution with both source errors and statistical fluctuations

NASA Astrophysics Data System (ADS)

Zhu, Jian-Rong; Li, Jian; Zhang, Chun-Mei; Wang, Qin

2017-10-01

The decoy-state method has been widely used in commercial quantum key distribution (QKD) systems. In view of the practical decoy-state QKD with both source errors and statistical fluctuations, we propose a universal model of full parameter optimization in biased decoy-state QKD with phase-randomized sources. Besides, we adopt this model to carry out simulations of two widely used sources: weak coherent source (WCS) and heralded single-photon source (HSPS). Results show that full parameter optimization can significantly improve not only the secure transmission distance but also the final key generation rate. And when taking source errors and statistical fluctuations into account, the performance of decoy-state QKD using HSPS suffered less than that of decoy-state QKD using WCS.

The role of the interface in germanium quantum dots: when not only size matters for quantum confinement effects.

PubMed

Cosentino, S; Mio, A M; Barbagiovanni, E G; Raciti, R; Bahariqushchi, R; Miritello, M; Nicotra, G; Aydinli, A; Spinella, C; Terrasi, A; Mirabella, S

2015-07-14

Quantum confinement (QC) typically assumes a sharp interface between a nanostructure and its environment, leading to an abrupt change in the potential for confined electrons and holes. When the interface is not ideally sharp and clean, significant deviations from the QC rule appear and other parameters beyond the nanostructure size play a considerable role. In this work we elucidate the role of the interface on QC in Ge quantum dots (QDs) synthesized by rf-magnetron sputtering or plasma enhanced chemical vapor deposition (PECVD). Through a detailed electron energy loss spectroscopy (EELS) analysis we investigated the structural and chemical properties of QD interfaces. PECVD QDs exhibit a sharper interface compared to sputter ones, which also evidences a larger contribution of mixed Ge-oxide states. Such a difference strongly modifies the QC strength, as experimentally verified by light absorption spectroscopy. A large size-tuning of the optical bandgap and an increase in the oscillator strength occur when the interface is sharp. A spatially dependent effective mass (SPDEM) model is employed to account for the interface difference between Ge QDs, pointing out a larger reduction in the exciton effective mass in the sharper interface case. These results add new insights into the role of interfaces on confined systems, and open the route for reliable exploitation of QC effects.

Quantum autoencoders for efficient compression of quantum data

NASA Astrophysics Data System (ADS)

Romero, Jonathan; Olson, Jonathan P.; Aspuru-Guzik, Alan

2017-12-01

Classical autoencoders are neural networks that can learn efficient low-dimensional representations of data in higher-dimensional space. The task of an autoencoder is, given an input x, to map x to a lower dimensional point y such that x can likely be recovered from y. The structure of the underlying autoencoder network can be chosen to represent the data on a smaller dimension, effectively compressing the input. Inspired by this idea, we introduce the model of a quantum autoencoder to perform similar tasks on quantum data. The quantum autoencoder is trained to compress a particular data set of quantum states, where a classical compression algorithm cannot be employed. The parameters of the quantum autoencoder are trained using classical optimization algorithms. We show an example of a simple programmable circuit that can be trained as an efficient autoencoder. We apply our model in the context of quantum simulation to compress ground states of the Hubbard model and molecular Hamiltonians.

Algorithms Bridging Quantum Computation and Chemistry

NASA Astrophysics Data System (ADS)

McClean, Jarrod Ryan

The design of new materials and chemicals derived entirely from computation has long been a goal of computational chemistry, and the governing equation whose solution would permit this dream is known. Unfortunately, the exact solution to this equation has been far too expensive and clever approximations fail in critical situations. Quantum computers offer a novel solution to this problem. In this work, we develop not only new algorithms to use quantum computers to study hard problems in chemistry, but also explore how such algorithms can help us to better understand and improve our traditional approaches. In particular, we first introduce a new method, the variational quantum eigensolver, which is designed to maximally utilize the quantum resources available in a device to solve chemical problems. We apply this method in a real quantum photonic device in the lab to study the dissociation of the helium hydride (HeH+) molecule. We also enhance this methodology with architecture specific optimizations on ion trap computers and show how linear-scaling techniques from traditional quantum chemistry can be used to improve the outlook of similar algorithms on quantum computers. We then show how studying quantum algorithms such as these can be used to understand and enhance the development of classical algorithms. In particular we use a tool from adiabatic quantum computation, Feynman's Clock, to develop a new discrete time variational principle and further establish a connection between real-time quantum dynamics and ground state eigenvalue problems. We use these tools to develop two novel parallel-in-time quantum algorithms that outperform competitive algorithms as well as offer new insights into the connection between the fermion sign problem of ground states and the dynamical sign problem of quantum dynamics. Finally we use insights gained in the study of quantum circuits to explore a general notion of sparsity in many-body quantum systems. In particular we use

The Molecular Structure of Phenetole Studied by Microwave Spectroscopy and Quantum Chemical Calculations

NASA Astrophysics Data System (ADS)

Ferres, Lynn; Stahl, Wolfgang; Nguyen, Ha Vinh Lam

2016-06-01

A pulsed molecular beam Fourier transform microwave spectrometer operating in the frequency range 2 - 26.5 GHz was used to measure the spectrum of phenetole (ethyl phenyl ether or ethoxybenzene, C6H5OC2H5). The conformational landscape is completely determined by the orientations of the phenyl ring and the ethyl group. A two-dimensional potential energy surface was calculated at the MP2/6-311++G(d,p) level of theory. Two conformers were found: The trans conformer has a Cs symmetry, and the gauche conformer has the ethyl group tilted out of the phenyl plane by about 70°. Totally 186 rotational transitions were assigned to the more stable planar trans conformer, and fitted using a semi-rigid rotor model to measurement accuracy of 2 kHz. Highly accurate rotational and centrifugal distortion constants were determined. Several method and basis set combinations were applied to check for convergence and to compare with the experimentally deduced molecular parameters. The inertial defect of the observed conformer Δc = (Ic - Ia - Ib) = -6.718 uÅ2 confirms that the heavy atom skeleton is planar with two pairs of hydrogen atoms out of plane. All lines in the spectrum could be assigned to the trans conformer, which confirms that the gauche conformer cannot be observed under our measurement conditions. In agreement with the rather high torsional barrier of the methyl group (V3 = 1168 wn) calculated by quantum chemical methods, all assigned lines appeared sharp and no signs of splittings were observed for the methyl internal rotation.

Tsallis entropy and decoherence of CsI quantum pseudo dot qubit

NASA Astrophysics Data System (ADS)

Tiotsop, M.; Fotue, A. J.; Fotsin, H. B.; Fai, L. C.

2017-05-01

Polaron in CsI quantum pseudo dot under an electromagnetic field was considered, and the ground and first excited state energies were derived by employing the combining Pekar variational and unitary transformation methods. With the two-level system obtained, single qubit was envisioned and the decoherence was studied using non-extensive entropy (Tsallis entropy). Numerical results showed: (i) the increase (decrease) of the energy levels (period of oscillation) with the increase of chemical potential, the zero point of pseudo dot, cyclotron frequency, and transverse and longitudinal confinements; (ii) the Tsallis entropy evolved as a wave envelop that increase with the increase of non-extenxive parameter and with the increase of electric field strength, zero point of pseudo dot and cyclotron frequency the wave envelop evolve periodically with reduction of period; (iii) The transition probability increases from the boundary to the centre of the dot where it has its maximum value. It was also noted that the probability density oscillate with period T0 = ℏ / Δ Ε with the tunnelling of the chemical potential and zero point of the pseudo dot. These results are helpful in the control of decoherence in quantum systems and may also be useful for the design of quantum computers.

Molecular basis of quantitative structure-properties relationships (QSPR): a quantum similarity approach.

PubMed

Ponec, R; Amat, L; Carbó-Dorca, R

1999-05-01

Since the dawn of quantitative structure-properties relationships (QSPR), empirical parameters related to structural, electronic and hydrophobic molecular properties have been used as molecular descriptors to determine such relationships. Among all these parameters, Hammett sigma constants and the logarithm of the octanol-water partition coefficient, log P, have been massively employed in QSPR studies. In the present paper, a new molecular descriptor, based on quantum similarity measures (QSM), is proposed as a general substitute of these empirical parameters. This work continues previous analyses related to the use of QSM to QSPR, introducing molecular quantum self-similarity measures (MQS-SM) as a single working parameter in some cases. The use of MQS-SM as a molecular descriptor is first confirmed from the correlation with the aforementioned empirical parameters. The Hammett equation has been examined using MQS-SM for a series of substituted carboxylic acids. Then, for a series of aliphatic alcohols and acetic acid esters, log P values have been correlated with the self-similarity measure between density functions in water and octanol of a given molecule. And finally, some examples and applications of MQS-SM to determine QSAR are presented. In all studied cases MQS-SM appeared to be excellent molecular descriptors usable in general QSPR applications of chemical interest.

Molecular basis of quantitative structure-properties relationships (QSPR): A quantum similarity approach

NASA Astrophysics Data System (ADS)

Ponec, Robert; Amat, Lluís; Carbó-dorca, Ramon

1999-05-01

Since the dawn of quantitative structure-properties relationships (QSPR), empirical parameters related to structural, electronic and hydrophobic molecular properties have been used as molecular descriptors to determine such relationships. Among all these parameters, Hammett σ constants and the logarithm of the octanol- water partition coefficient, log P, have been massively employed in QSPR studies. In the present paper, a new molecular descriptor, based on quantum similarity measures (QSM), is proposed as a general substitute of these empirical parameters. This work continues previous analyses related to the use of QSM to QSPR, introducing molecular quantum self-similarity measures (MQS-SM) as a single working parameter in some cases. The use of MQS-SM as a molecular descriptor is first confirmed from the correlation with the aforementioned empirical parameters. The Hammett equation has been examined using MQS-SM for a series of substituted carboxylic acids. Then, for a series of aliphatic alcohols and acetic acid esters, log P values have been correlated with the self-similarity measure between density functions in water and octanol of a given molecule. And finally, some examples and applications of MQS-SM to determine QSAR are presented. In all studied cases MQS-SM appeared to be excellent molecular descriptors usable in general QSPR applications of chemical interest.

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

DOE Office of Scientific and Technical Information (OSTI.GOV)

Phillips, Mark C.; Brumfield, Brian E.

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 reducemore » 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.« less

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

NASA Astrophysics Data System (ADS)

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.

Chemical bonding in TiSb(2) and VSb(2): a quantum chemical and experimental study.

PubMed

Armbrüster, Marc; Schnelle, Walter; Schwarz, Ulrich; Grin, Yuri

2007-08-06

The chemical bonding in the isostructural intermetallic compounds TiSb2 and VSb2, crystallizing in the CuAl2 type, was investigated by means of quantum chemical calculations, particularly the electron localization function (ELF), as well as by Raman spectroscopy, Hall effect and conductivity measurements on oriented single crystals, and high-pressure X-ray powder diffraction. The homogeneity ranges of the compounds were determined by powder X-ray diffraction, WDXS, and DSC measurements. TiSb2 exhibits no significant homogeneity range, while VSb2 shows a small homogeneity range of approximately 0.3 at. %. According to the ELF calculations, the Sb atoms form dumbbells via a two-center two-electron bond, while the T atoms (T = Ti, V) build up chains along the crystallographic c-axis. Both building units are connected by covalent T-Sb-T three-center bonds, thus forming a three-dimensional network. The strength of the bonds involving Sb was determined by fitting a force constant model to the vibrational mode frequencies observed by polarized Raman measurements on oriented single crystals. The resulting bond order of the Sb2 dumbbells is 1, while the strength of the three-center bonds resembles a bond order of 1.5. The weak pressure dependence of the c/a ratio confirms the slightly different bonding picture in TiSb2 compared to that in CuAl2. Electrical transport measurements show the presence of free charge carriers, as well as a metal-like temperature dependence of the electrical resistivity.

Time-Resolved Quantum Cascade Laser Absorption Spectroscopy of Pulsed Plasma Assisted Chemical Vapor Deposition Processes Containing BCl3

NASA Astrophysics Data System (ADS)

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.

Influence of quantum effects on the parameters of a cold cathode with carbon nanotubes

NASA Astrophysics Data System (ADS)

Glukhova, O. E.; Kolesnikova, A. S.; Slepchenkov, M. M.

2016-01-01

We consider the effect of an external electric field on the parameters of a cold cathode on carbon nanotubes using the quantum-mechanical approach to the description of the interaction of the field with the atomic structure of nanoemitters. It is established for the first time that an increase in the length of the emitting edge of the tube in a field of 10-11 V/nm increases the field emission current of electrons by 3-10%. It is found that in a field of 11 V/nm and higher, atoms of the upper edge of a carbon nanotube are detached with the subsequent destruction of the atomic core.

Long wavelength emitting GaInN quantum wells on metamorphic GaInN buffer layers with enlarged in-plane lattice parameter

DOE Office of Scientific and Technical Information (OSTI.GOV)

Däubler, J., E-mail: juergen.daeubler@iaf.fraunhofer.de; Passow, T.; Aidam, R.

Metamorphic (i.e., linear composition graded) GaInN buffer layers with an increased in-plane lattice parameter, grown by plasma-assisted molecular beam epitaxy, were used as templates for metal organic vapor phase epitaxy (MOVPE) grown GaInN/GaInN quantum wells (QWs), emitting in the green to red spectral region. A composition pulling effect was observed allowing considerable higher growth temperatures for the QWs for a given In composition. The internal quantum efficiency (IQE) of the QWs was determined by temperature and excitation power density dependent photoluminescence (PL) spectroscopy. An increase in IQE by a factor of two was found for green emitting QWs grown onmore » metamorphic GaInN buffer compared to reference samples grown on standard GaN buffer layers. The ratio of room temperature to low temperature intensity PL of the red emitting QWs were found to be comparable to the PL efficiency of green emitting QWs, both grown on metamorphic GaInN buffers. The excitation density and well width dependence of the IQE indicate a reduction of the quantum confined Stark effect upon growth on GaInN buffer layers with increased in-plane lattice parameter.« less

The quantum measurement of time

NASA Technical Reports Server (NTRS)

Shepard, Scott R.

1994-01-01

Traditionally, in non-relativistic Quantum Mechanics, time is considered to be a parameter, rather than an observable quantity like space. In relativistic Quantum Field Theory, space and time are treated equally by reducing space to also be a parameter. Herein, after a brief review of other measurements, we describe a third possibility, which is to treat time as a directly observable quantity.

Electro-optical parameters of bond polarizability model for aluminosilicates.

PubMed

Smirnov, Konstantin S; Bougeard, Daniel; Tandon, Poonam

2006-04-06

Electro-optical parameters (EOPs) of bond polarizability model (BPM) for aluminosilicate structures were derived from quantum-chemical DFT calculations of molecular models. The tensor of molecular polarizability and the derivatives of the tensor with respect to the bond length are well reproduced with the BPM, and the EOPs obtained are in a fair agreement with available experimental data. The parameters derived were found to be transferable to larger molecules. This finding suggests that the procedure used can be applied to systems with partially ionic chemical bonds. The transferability of the parameters to periodic systems was tested in molecular dynamics simulation of the polarized Raman spectra of alpha-quartz. It appeared that the molecular Si-O bond EOPs failed to reproduce the intensity of peaks in the spectra. This limitation is due to large values of the longitudinal components of the bond polarizability and its derivative found in the molecular calculations as compared to those obtained from periodic DFT calculations of crystalline silica polymorphs by Umari et al. (Phys. Rev. B 2001, 63, 094305). It is supposed that the electric field of the solid is responsible for the difference of the parameters. Nevertheless, the EOPs obtained can be used as an initial set of parameters for calculations of polarizability related characteristics of relevant systems in the framework of BPM.

Relativistic Quantum Metrology: Exploiting relativity to improve quantum measurement technologies

PubMed Central

Ahmadi, Mehdi; Bruschi, David Edward; Sabín, Carlos; Adesso, Gerardo; Fuentes, Ivette

2014-01-01

We present a framework for relativistic quantum metrology that is useful for both Earth-based and space-based technologies. Quantum metrology has been so far successfully applied to design precision instruments such as clocks and sensors which outperform classical devices by exploiting quantum properties. There are advanced plans to implement these and other quantum technologies in space, for instance Space-QUEST and Space Optical Clock projects intend to implement quantum communications and quantum clocks at regimes where relativity starts to kick in. However, typical setups do not take into account the effects of relativity on quantum properties. To include and exploit these effects, we introduce techniques for the application of metrology to quantum field theory. Quantum field theory properly incorporates quantum theory and relativity, in particular, at regimes where space-based experiments take place. This framework allows for high precision estimation of parameters that appear in quantum field theory including proper times and accelerations. Indeed, the techniques can be applied to develop a novel generation of relativistic quantum technologies for gravimeters, clocks and sensors. As an example, we present a high precision device which in principle improves the state-of-the-art in quantum accelerometers by exploiting relativistic effects. PMID:24851858

Effects of correlated parameters and uncertainty in electronic-structure-based chemical kinetic modelling

NASA Astrophysics Data System (ADS)

Sutton, Jonathan E.; Guo, Wei; Katsoulakis, Markos A.; Vlachos, Dionisios G.

2016-04-01

Kinetic models based on first principles are becoming common place in heterogeneous catalysis because of their ability to interpret experimental data, identify the rate-controlling step, guide experiments and predict novel materials. To overcome the tremendous computational cost of estimating parameters of complex networks on metal catalysts, approximate quantum mechanical calculations are employed that render models potentially inaccurate. Here, by introducing correlative global sensitivity analysis and uncertainty quantification, we show that neglecting correlations in the energies of species and reactions can lead to an incorrect identification of influential parameters and key reaction intermediates and reactions. We rationalize why models often underpredict reaction rates and show that, despite the uncertainty being large, the method can, in conjunction with experimental data, identify influential missing reaction pathways and provide insights into the catalyst active site and the kinetic reliability of a model. The method is demonstrated in ethanol steam reforming for hydrogen production for fuel cells.

Chemically functionalized ZnS quantum dots as new optical nanosensor of herbicides

NASA Astrophysics Data System (ADS)

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.

Quantum control of isomerization by robust navigation in the energy spectrum

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murgida, G. E., E-mail: murgida@tandar.cnea.gov.ar; Arranz, F. J., E-mail: fj.arranz@upm.es; Borondo, F., E-mail: f.borondo@uam.es

2015-12-07

In this paper, we present a detailed study on the application of the quantum control technique of navigation in the energy spectrum to chemical isomerization processes, namely, CN–Li⇆ Li–CN. This technique is based on the controlled time variation of a Hamiltonian parameter, an external uniform electric field in our case. The main result of our work establishes that the navigation involved in the method is robust, in the sense that quite sizable deviations from a pre-established control parameter time profile can be introduced and still get good final results. This is specially relevant thinking of a experimental implementation of themore » method.« less

Microscopic origin of the fast blue-green luminescence of chemically synthesized non-oxidized silicon quantum dots.

PubMed

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.

A quantum chemical study of molecular properties and QSPR modeling of oximes, amidoximes and hydroxamic acids with nucleophilic activity against toxic organophosphorus agents

NASA Astrophysics Data System (ADS)

Alencar Filho, Edilson B.; Santos, Aline A.; Oliveira, Boaz G.

2017-04-01

The proposal of this work includes the use of quantum chemical methods and cheminformatics strategies in order to understand the structural profile and reactivity of α-nucleophiles compounds such as oximes, amidoximes and hydroxamic acids, related to hydrolysis rate of organophosphates. Theoretical conformational study of 41 compounds were carried out through the PM3 semiempirical Hamiltonian, followed by the geometry optimization at the B3LYP/6-31+G(d,p) level of theory, complemented by Polarized Continuum Model (PCM) to simulate the aqueous environment. In line with the experimental hypothesis about hydrolytic power, the strength of the Intramolecular Hydrogen Bonds (IHBs) at light of the Bader's Quantum Theory of Atoms in Molecules (QTAIM) is related to the preferential conformations of α-nucleophiles. A set of E-Dragon descriptors (1,666) were submitted to a variable selection through Ordered Predictor Selection (OPS) algorithm. Five descriptors, including atomic charges obtained from the Natural Bond Orbitals (NBO) protocol jointly with a fragment index associated to the presence/absence of IHBs, provided a Quantitative Structure-Property Relationship (QSPR) model via Multiple Linear Regression (MLR). This model showed good validation parameters (R2 = 0.80, Qloo2 = 0.67 and Qext2 = 0.81) and allowed the identification of significant physicochemical features on the molecular scaffold in order to design compounds potentially more active against organophosphorus poisoning.

Quantum coding with finite resources.

PubMed

Tomamichel, Marco; Berta, Mario; Renes, Joseph M

2016-05-09

The quantum capacity of a memoryless channel determines the maximal rate at which we can communicate reliably over asymptotically many uses of the channel. Here we illustrate that this asymptotic characterization is insufficient in practical scenarios where decoherence severely limits our ability to manipulate large quantum systems in the encoder and decoder. In practical settings, we should instead focus on the optimal trade-off between three parameters: the rate of the code, the size of the quantum devices at the encoder and decoder, and the fidelity of the transmission. We find approximate and exact characterizations of this trade-off for various channels of interest, including dephasing, depolarizing and erasure channels. In each case, the trade-off is parameterized by the capacity and a second channel parameter, the quantum channel dispersion. In the process, we develop several bounds that are valid for general quantum channels and can be computed for small instances.

Quantum junction solar cells.

PubMed

Tang, Jiang; Liu, Huan; Zhitomirsky, David; Hoogland, Sjoerd; Wang, Xihua; Furukawa, Melissa; Levina, Larissa; Sargent, Edward H

2012-09-12

Colloidal quantum dot solids combine convenient solution-processing with quantum size effect tuning, offering avenues to high-efficiency multijunction cells based on a single materials synthesis and processing platform. The highest-performing colloidal quantum dot rectifying devices reported to date have relied on a junction between a quantum-tuned absorber and a bulk material (e.g., TiO(2)); however, quantum tuning of the absorber then requires complete redesign of the bulk acceptor, compromising the benefits of facile quantum tuning. Here we report rectifying junctions constructed entirely using inherently band-aligned quantum-tuned materials. Realizing these quantum junction diodes relied upon the creation of an n-type quantum dot solid having a clean bandgap. We combine stable, chemically compatible, high-performance n-type and p-type materials to create the first quantum junction solar cells. We present a family of photovoltaic devices having widely tuned bandgaps of 0.6-1.6 eV that excel where conventional quantum-to-bulk devices fail to perform. Devices having optimal single-junction bandgaps exhibit certified AM1.5 solar power conversion efficiencies of 5.4%. Control over doping in quantum solids, and the successful integration of these materials to form stable quantum junctions, offers a powerful new degree of freedom to colloidal quantum dot optoelectronics.

Chemically differentiating ascorbate-mediated dissolution of quantum dots in cell culture media

NASA Astrophysics Data System (ADS)

Su, Cheng-Kuan; Sun, Yuh-Chang

2013-02-01

To investigate the dynamic dissolution of quantum dots (QDs) in cell culture media, in this study we constructed an online automatic analytical system comprising a sequential in-tube solid phase extraction (SPE) device and an inductively coupled plasma (ICP) mass spectrometer. By means of selectively extracting QDs and cadmium ions (Cd2+) onto the interior surface of the polytetrafluoroethylene (PTFE) tube, this novel SPE device could be used to determine the degree of QD dissolution through a simple adjustment of sample acidity. To the best of our knowledge, this study is the first to exploit PTFE tubing as a selective SPE adsorbent for the online chemical differentiation of QDs and Cd2+ ions with the goal of monitoring the phenomenon of QD dissolution in complicated biological matrices. We confirmed the analytical reliability of this system through comparison of the measured Cd-to-QD ratios to the expected values. When analyzing QDs and Cd2+ ions at picomolar levels, a temporal resolution of 8 min was required to load sufficient amounts of the analytes to meet the sensitivity requirements of the ICP mass spectrometer. To demonstrate the practicability of this developed method, we measured the dynamic variations in the Cd-to-QD705 ratio in the presence of ascorbate as a physiological stimulant to generate reactive oxygen species in cell culture media and trigger the dissolution of QDs; our results suggest that the ascorbate-induced QD dissolution was dependent on the time, treatment concentration, and nature of the biomolecule.To investigate the dynamic dissolution of quantum dots (QDs) in cell culture media, in this study we constructed an online automatic analytical system comprising a sequential in-tube solid phase extraction (SPE) device and an inductively coupled plasma (ICP) mass spectrometer. By means of selectively extracting QDs and cadmium ions (Cd2+) onto the interior surface of the polytetrafluoroethylene (PTFE) tube, this novel SPE device could be

The IINS/quantum chemical studies of 17α- and 21-hydroxy-derivatives of progesterone

NASA Astrophysics Data System (ADS)

Szyczewski, A.; Hołderna-Natkaniec, K.; Natkaniec, I.

2003-05-01

The inelastic incoherent neutron scattering and quantum chemical studies have been performed on 17 and 21 hydroxy progesterone and the assignment of internal modes have been proposed in the range up to 700 cm -1. The lattice branch of PDS reveals modes which could be attributed to torsions of rings A and D (cyclohexane and cyclopentane) of the pregnane skeleton. An assignment of the torsional vibrations of methyl groups in the range 150-300 cm -1 and the deformation and out-of plane vibrations of CCOH groups has been proposed. An analysis of the effect of hydrogen bonds on PDS spectra has been performed.

High fidelity quantum teleportation assistance with quantum neural network

NASA Astrophysics Data System (ADS)

Huang, Chunhui; Wu, Bichun

2014-09-01

In this paper, a high fidelity scheme of quantum teleportation based on quantum neural network (QNN) is proposed. The QNN is composed of multi-bit control-not gates. The quantum teleportation of a qubit state via two-qubit entangled channels is investigated by solving the master equation in Lindblad operators with a noisy environment. To ensure the security of quantum teleportation, the indirect training of QNN is employed. Only 10% of teleported information is extracted for the training of QNN parameters. Then the outputs are corrected by the other QNN at Bob's side. We build a random series of numbers ranged in [0, π] as inputs and simulate the properties of our teleportation scheme. The results show that the fidelity of quantum teleportation system is significantly improved to approach 1 by the error-correction of QNN. It illustrates that the distortion can be eliminated perfectly and the high fidelity of quantum teleportation could be implemented.

Abundance of Chemical Elements in RR Lyrae Variables and their Kinematic Parameters

NASA Astrophysics Data System (ADS)

Gozha, M. L.; Marsakov, V. A.; Koval', V. V.

2018-03-01

A catalog of the chemical and spatial-kinematic parameters of 415 RR Lyrae variables (Lyrids) in the galactic field is compiled. Spectroscopic determinations of the relative abundances of 13 chemical elements in 101 of the RR Lyrae variables are collected from 25 papers published between 1995 and 2017. The data from different sources are reduced to a single solar abundance scale. The mean weighted chemical abundances are calculated with coefficients inversely proportional to the reported errors. An analysis of the deviations in the published relative abundances in each star from the mean square values calculated from them reveals an absence of systematic biases among the results from the various articles. The rectangular coordinates of 407 of the RR Lyrae variables and the components of the three-dimensional (3D) velocities of 401 of the stars are calculated using data from several sources. The collected data on the abundances of chemical elements produced by various nuclear fusion processes for the RR Lyrae variables of the field, as well as the calculated 3D velocities, can be used for studying the evolution of the Galaxy.

Two-electrons quantum dot in plasmas under the external fields

NASA Astrophysics Data System (ADS)

Bahar, M. K.; Soylu, A.

2018-02-01

In this study, for the first time, the combined effects of the external electric field, magnetic field, and confinement frequency on energies of two-electron parabolic quantum dots in Debye and quantum plasmas modeled by more general exponential cosine screened Coulomb (MGECSC) potential are investigated by numerically solving the Schrödinger equation using the asymptotic iteration method. The MGECSC potential includes four different potential forms when considering different sets of the parameters in potential. Since the plasma is an important experimental argument for quantum dots, the influence of plasmas modeled by the MGECSC potential on quantum dots is probed. The confinement frequency of quantum dots and the external fields created significant quantum restrictions on quantum dot. In this study, as well as discussion of the functionalities of the quantum restrictions for experimental applications, the parameters are also compared with each other in terms of influence and behaviour. In this manner, the motivation points of this study are summarized as follows: Which parameter can be alternative to which parameter, in terms of experimental applications? Which parameters exhibit similar behaviour? What is the role of plasmas on the corresponding behaviours? In the light of these research studies, it can be said that obtained results and performed discussions would be important in experimental and theoretical research related to plasma physics and/or quantum dots.

Quantum Metropolis sampling.

PubMed

Temme, K; Osborne, T J; Vollbrecht, K G; Poulin, D; Verstraete, F

2011-03-03

The original motivation to build a quantum computer came from Feynman, who imagined a machine capable of simulating generic quantum mechanical systems--a task that is believed to be intractable for classical computers. Such a machine could have far-reaching applications in the simulation of many-body quantum physics in condensed-matter, chemical and high-energy systems. Part of Feynman's challenge was met by Lloyd, who showed how to approximately decompose the time evolution operator of interacting quantum particles into a short sequence of elementary gates, suitable for operation on a quantum computer. However, this left open the problem of how to simulate the equilibrium and static properties of quantum systems. This requires the preparation of ground and Gibbs states on a quantum computer. For classical systems, this problem is solved by the ubiquitous Metropolis algorithm, a method that has basically acquired a monopoly on the simulation of interacting particles. Here we demonstrate how to implement a quantum version of the Metropolis algorithm. This algorithm permits sampling directly from the eigenstates of the Hamiltonian, and thus evades the sign problem present in classical simulations. A small-scale implementation of this algorithm should be achievable with today's technology.

Quantitative structure-activation barrier relationship modeling for Diels-Alder ligations utilizing quantum chemical structural descriptors.

PubMed

Nandi, Sisir; Monesi, Alessandro; Drgan, Viktor; Merzel, Franci; Novič, Marjana

2013-10-30

In the present study, we show the correlation of quantum chemical structural descriptors with the activation barriers of the Diels-Alder ligations. A set of 72 non-catalysed Diels-Alder reactions were subjected to quantitative structure-activation barrier relationship (QSABR) under the framework of theoretical quantum chemical descriptors calculated solely from the structures of diene and dienophile reactants. Experimental activation barrier data were obtained from literature. Descriptors were computed using Hartree-Fock theory using 6-31G(d) basis set as implemented in Gaussian 09 software. Variable selection and model development were carried out by stepwise multiple linear regression methodology. Predictive performance of the quantitative structure-activation barrier relationship (QSABR) model was assessed by training and test set concept and by calculating leave-one-out cross-validated Q2 and predictive R2 values. The QSABR model can explain and predict 86.5% and 80% of the variances, respectively, in the activation energy barrier training data. Alternatively, a neural network model based on back propagation of errors was developed to assess the nonlinearity of the sought correlations between theoretical descriptors and experimental reaction barriers. A reasonable predictability for the activation barrier of the test set reactions was obtained, which enabled an exploration and interpretation of the significant variables responsible for Diels-Alder interaction between dienes and dienophiles. Thus, studies in the direction of QSABR modelling that provide efficient and fast prediction of activation barriers of the Diels-Alder reactions turn out to be a meaningful alternative to transition state theory based computation.

New 'phase' of quantum gravity.

PubMed

Wang, Charles H-T

2006-12-15

The emergence of loop quantum gravity over the past two decades has stimulated a great resurgence of interest in unifying general relativity and quantum mechanics. Among a number of appealing features of this approach is the intuitive picture of quantum geometry using spin networks and powerful mathematical tools from gauge field theory. However, the present form of loop quantum gravity suffers from a quantum ambiguity, owing to the presence of a free (Barbero-Immirzi) parameter. Following the recent progress on conformal decomposition of gravitational fields, we present a new phase space for general relativity. In addition to spin-gauge symmetry, the new phase space also incorporates conformal symmetry making the description parameter free. The Barbero-Immirzi ambiguity is shown to occur only if the conformal symmetry is gauge fixed prior to quantization. By withholding its full symmetries, the new phase space offers a promising platform for the future development of loop quantum gravity. This paper aims to provide an exposition, at a reduced technical level, of the above theoretical advances and their background developments. Further details are referred to cited references.

Single Nucleobase Identification Using Biophysical Signatures from Nanoelectronic Quantum Tunneling.

PubMed

Korshoj, Lee E; Afsari, Sepideh; Khan, Sajida; Chatterjee, Anushree; Nagpal, Prashant

2017-03-01

Nanoelectronic DNA sequencing can provide an important alternative to sequencing-by-synthesis by reducing sample preparation time, cost, and complexity as a high-throughput next-generation technique with accurate single-molecule identification. However, sample noise and signature overlap continue to prevent high-resolution and accurate sequencing results. Probing the molecular orbitals of chemically distinct DNA nucleobases offers a path for facile sequence identification, but molecular entropy (from nucleotide conformations) makes such identification difficult when relying only on the energies of lowest-unoccupied and highest-occupied molecular orbitals (LUMO and HOMO). Here, nine biophysical parameters are developed to better characterize molecular orbitals of individual nucleobases, intended for single-molecule DNA sequencing using quantum tunneling of charges. For this analysis, theoretical models for quantum tunneling are combined with transition voltage spectroscopy to obtain measurable parameters unique to the molecule within an electronic junction. Scanning tunneling spectroscopy is then used to measure these nine biophysical parameters for DNA nucleotides, and a modified machine learning algorithm identified nucleobases. The new parameters significantly improve base calling over merely using LUMO and HOMO frontier orbital energies. Furthermore, high accuracies for identifying DNA nucleobases were observed at different pH conditions. These results have significant implications for developing a robust and accurate high-throughput nanoelectronic DNA sequencing technique. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Chemical Abundances and Physical Parameters of H II Regions in the Magellanic Clouds

NASA Astrophysics Data System (ADS)

Reyes, R. E. C.

The chemical abundances and physical parameters of H II regions are important pa rameters to determine in order to understand how stars and galaxies evolve. The Magellanic Clouds offer us a unique oportunity to persue such studies in low metallicity galaxies. In this contribution we present the results of the photoionization modeling of 5 H II regions in each of the Large Magellanic Cloud (LMC) and Small Magellanic Cloud (SMC) sys tems. Optical data were collected from the literature, complemented by our own observa tions (Carlos Reyes et al. 1998), including UV spectra from the new IUE data ban k and infrared fluxes from the IRAS satellite. The chemical abundances of He, C, N, O, Ne, S, Ar and physical parameters like the densities, the ionized masses, the luminosities, the ionization temperatures , the filling factor and optical depth are determined. A comparison of the abundances of these HII regions with those of typical planetary nebulae and supergiants stars is also presented.

Toward the realization of a compact chemical sensor platform using quantum cascade lasers

NASA Astrophysics Data System (ADS)

Holthoff, Ellen L.; Marcus, Logan S.; Pellegrino, Paul M.

2015-05-01

The Army is investigating several spectroscopic techniques (e.g., infrared spectroscopy) that could allow for an adaptable sensor platform. Traditionally, chemical sensing platforms have been hampered by the opposing concerns of increasing sensor capability while maintaining a minimal package size. Current sensors, although reasonably sized, are geared to more classical chemical threats, and the ability to expand their capabilities to a broader range of emerging threats is uncertain. Recently, photoacoustic spectroscopy, employed in a sensor format, has shown enormous potential to address these ever-changing threats, while maintaining a compact sensor design. In order to realize the advantage of photoacoustic sensor miniaturization, light sources of comparable size are required. Recent research has employed quantum cascade lasers (QCLs) in combination with MEMS-scale photoacoustic cell designs. The continuous tuning capability of QCLs over a broad wavelength range in the mid-infrared spectral region greatly expands the number of compounds that can be identified. Results have demonstrated that utilizing a tunable QCL with a MEMS-scale photoacoustic cell produces favorable detection limits (ppb levels) for chemical targets (e.g., dimethyl methyl phosphonate (DMMP), vinyl acetate, 1,4-dioxane). Although our chemical sensing research has benefitted from the broad tuning capabilities of QCLs, the limitations of these sources must be considered. Current commercially available tunable systems are still expensive and obviously geared more toward laboratory operation, not fielding. Although the laser element itself is quite small, the packaging, power supply, and controller remain logistical burdens. Additionally, operational features such as continuous wave (CW) modulation and laser output powers while maintaining wide tunability are not yet ideal for a variety of sensing applications. In this paper, we will discuss our continuing evaluation of QCL technology as it matures

Quantum state engineering using one-dimensional discrete-time quantum walks

NASA Astrophysics Data System (ADS)

Innocenti, Luca; Majury, Helena; Giordani, Taira; Spagnolo, Nicolò; Sciarrino, Fabio; Paternostro, Mauro; Ferraro, Alessandro

2017-12-01

Quantum state preparation in high-dimensional systems is an essential requirement for many quantum-technology applications. The engineering of an arbitrary quantum state is, however, typically strongly dependent on the experimental platform chosen for implementation, and a general framework is still missing. Here we show that coined quantum walks on a line, which represent a framework general enough to encompass a variety of different platforms, can be used for quantum state engineering of arbitrary superpositions of the walker's sites. We achieve this goal by identifying a set of conditions that fully characterize the reachable states in the space comprising walker and coin and providing a method to efficiently compute the corresponding set of coin parameters. We assess the feasibility of our proposal by identifying a linear optics experiment based on photonic orbital angular momentum technology.

Quantum interpolation for high-resolution sensing.

PubMed

Ajoy, Ashok; Liu, Yi-Xiang; Saha, Kasturi; Marseglia, Luca; Jaskula, Jean-Christophe; Bissbort, Ulf; Cappellaro, Paola

2017-02-28

Recent advances in engineering and control of nanoscale quantum sensors have opened new paradigms in precision metrology. Unfortunately, hardware restrictions often limit the sensor performance. In nanoscale magnetic resonance probes, for instance, finite sampling times greatly limit the achievable sensitivity and spectral resolution. Here we introduce a technique for coherent quantum interpolation that can overcome these problems. Using a quantum sensor associated with the nitrogen vacancy center in diamond, we experimentally demonstrate that quantum interpolation can achieve spectroscopy of classical magnetic fields and individual quantum spins with orders of magnitude finer frequency resolution than conventionally possible. Not only is quantum interpolation an enabling technique to extract structural and chemical information from single biomolecules, but it can be directly applied to other quantum systems for superresolution quantum spectroscopy.

Quantum coding with finite resources

PubMed Central

Tomamichel, Marco; Berta, Mario; Renes, Joseph M.

2016-01-01

The quantum capacity of a memoryless channel determines the maximal rate at which we can communicate reliably over asymptotically many uses of the channel. Here we illustrate that this asymptotic characterization is insufficient in practical scenarios where decoherence severely limits our ability to manipulate large quantum systems in the encoder and decoder. In practical settings, we should instead focus on the optimal trade-off between three parameters: the rate of the code, the size of the quantum devices at the encoder and decoder, and the fidelity of the transmission. We find approximate and exact characterizations of this trade-off for various channels of interest, including dephasing, depolarizing and erasure channels. In each case, the trade-off is parameterized by the capacity and a second channel parameter, the quantum channel dispersion. In the process, we develop several bounds that are valid for general quantum channels and can be computed for small instances. PMID:27156995

Synthesis, inhibition effects and quantum chemical studies of a novel coumarin derivative on the corrosion of mild steel in a hydrochloric acid solution.

PubMed

Al-Azawi, Khalida F; Al-Baghdadi, Shaimaa B; Mohamed, Ayad Z; Al-Amiery, Ahmed A; Abed, Talib K; Mohammed, Salam A; Kadhum, Abdul Amir H; Mohamad, Abu Bakar

2016-01-01

The acid corrosion inhibition process of mild steel in 1 M HCl by 4-[(2-amino-1, 3, 4-thiadiazol-5-yl)methoxy]coumarin (ATC), has been investigated using weight loss technique and scanning electron microscopy (SEM). ATC was synthesized, and its chemical structure was elucidated and confirmed using spectroscopic techniques (infrared and nuclear magnetic resonance spectroscopy). The results indicated that inhibition efficiencies were enhanced with an increase in concentration of inhibitor and decreased with a rise in temperature. The adsorption equilibrium constant (K) and standard free energy of adsorption (ΔGads) were calculated. Quantum chemical parameters such as highest occupied molecular orbital energy, lowest unoccupied molecular orbital energy (EHOMO and ELUMO, respectively) and dipole moment (μ) were calculated and discussed. The results showed that the corrosion inhibition efficiency increased with an increase in both the EHOMO and μ values but with a decrease in the ELUMO value. Our research show that the synthesized macromolecule represents an excellent inhibitor for materials in acidic solutions. The efficiency of this macromolecule had maximum inhibition efficiency up to 96 % at 0.5 mM and diminishes with a higher temperature degree, which is revealing of chemical adsorption. An inhibitor molecule were absorbed by metal surface and follow Langmuir isotherms low and establishes an efficient macromolecule inhibitor having excellent inhibitive properties due to entity of S (sulfur) atom, N (nitrogen) atom and O (oxygen) atom.

Standoff detection of explosives and chemical agents using broadly tuned external-cavity quantum cascade lasers (EC-QCLs)

NASA Astrophysics Data System (ADS)

Takeuchi, Eric B.; Rayner, Timothy; Weida, Miles; Crivello, Salvatore; Day, Timothy

2007-10-01

Civilian soft targets such as transportation systems are being targeted by terrorists using IEDs and suicide bombers. Having the capability to remotely detect explosives, precursors and other chemicals would enable these assets to be protected with minimal interruption of the flow of commerce. Mid-IR laser technology offers the potential to detect explosives and other chemicals in real-time and from a safe standoff distance. While many of these agents possess "fingerprint" signatures in the mid-IR (i.e. in the 3-20 micron regime), their effective interrogation by a practical, field-deployable system has been limited by size, complexity, reliability and cost constraints of the base laser technology. Daylight Solutions has addressed these shortcomings by developing compact, portable, broadly tunable mid-IR laser sources based upon external-cavity quantum cascade technology. This technology is now being applied by Daylight in system level architectures for standoff and remote detection of explosives, precursors and chemical agents. Several of these architectures and predicted levels of performance will be presented.

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

NASA Astrophysics Data System (ADS)

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.

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

NASA Astrophysics Data System (ADS)

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.

Tsallis entropy and general polygamy of multiparty quantum entanglement in arbitrary dimensions

NASA Astrophysics Data System (ADS)

Kim, Jeong San

2016-12-01

We establish a unified view of the polygamy of multiparty quantum entanglement in arbitrary dimensions. Using quantum Tsallis-q entropy, we provide a one-parameter class of polygamy inequalities of multiparty quantum entanglement. This class of polygamy inequalities reduces to the known polygamy inequalities based on tangle and entanglement of assistance for a selective choice of the parameter q . We further provide one-parameter generalizations of various quantum correlations based on Tsallis-q entropy. By investigating the properties of the generalized quantum correlations, we provide a sufficient condition on which the Tsallis-q polygamy inequalities hold in multiparty quantum systems of arbitrary dimensions.

Quantum chemical study on the stability of honeybee queen pheromone against atmospheric factors.

PubMed

Shi, Rongwei; Liu, Fanglin

2016-06-01

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

A new multimedia contaminant fate model for China: how important are environmental parameters in influencing chemical persistence and long-range transport potential?

PubMed

Zhu, Ying; Price, Oliver R; Tao, Shu; Jones, Kevin C; Sweetman, Andy J

2014-08-01

We present a new multimedia chemical fate model (SESAMe) which was developed to assess chemical fate and behaviour across China. We apply the model to quantify the influence of environmental parameters on chemical overall persistence (POV) and long-range transport potential (LRTP) in China, which has extreme diversity in environmental conditions. Sobol sensitivity analysis was used to identify the relative importance of input parameters. Physicochemical properties were identified as more influential than environmental parameters on model output. Interactive effects of environmental parameters on POV and LRTP occur mainly in combination with chemical properties. Hypothetical chemicals and emission data were used to model POV and LRTP for neutral and acidic chemicals with different KOW/DOW, vapour pressure and pKa under different precipitation, wind speed, temperature and soil organic carbon contents (fOC). Generally for POV, precipitation was more influential than the other environmental parameters, whilst temperature and wind speed did not contribute significantly to POV variation; for LRTP, wind speed was more influential than the other environmental parameters, whilst the effects of other environmental parameters relied on specific chemical properties. fOC had a slight effect on POV and LRTP, and higher fOC always increased POV and decreased LRTP. Example case studies were performed on real test chemicals using SESAMe to explore the spatial variability of model output and how environmental properties affect POV and LRTP. Dibenzofuran released to multiple media had higher POV in northwest of Xinjiang, part of Gansu, northeast of Inner Mongolia, Heilongjiang and Jilin. Benzo[a]pyrene released to the air had higher LRTP in south Xinjiang and west Inner Mongolia, whilst acenaphthene had higher LRTP in Tibet and west Inner Mongolia. TCS released into water had higher LRTP in Yellow River and Yangtze River catchments. The initial case studies demonstrated that SESAMe

Quantum interpolation for high-resolution sensing

PubMed Central

Ajoy, Ashok; Liu, Yi-Xiang; Saha, Kasturi; Marseglia, Luca; Jaskula, Jean-Christophe; Bissbort, Ulf; Cappellaro, Paola

2017-01-01

Recent advances in engineering and control of nanoscale quantum sensors have opened new paradigms in precision metrology. Unfortunately, hardware restrictions often limit the sensor performance. In nanoscale magnetic resonance probes, for instance, finite sampling times greatly limit the achievable sensitivity and spectral resolution. Here we introduce a technique for coherent quantum interpolation that can overcome these problems. Using a quantum sensor associated with the nitrogen vacancy center in diamond, we experimentally demonstrate that quantum interpolation can achieve spectroscopy of classical magnetic fields and individual quantum spins with orders of magnitude finer frequency resolution than conventionally possible. Not only is quantum interpolation an enabling technique to extract structural and chemical information from single biomolecules, but it can be directly applied to other quantum systems for superresolution quantum spectroscopy. PMID:28196889

Experimental and Quantum-Chemical Study of Electronically Excited States of Protolytic Isovanillin Species

NASA Astrophysics Data System (ADS)

Vusovich, O. V.; Tchaikovskaya, O. N.; Sokolova, I. V.; Vasil'eva, N. Yu.

2014-05-01

Methods of electronic spectroscopy and quantum chemistry are used to compare protolytic vanillin and isovanillin species. Three protolytic species: anion, cation, and neutral are distinguished in the ground state of the examined molecules. Vanillin and isovanillin in the ground state in water possess identical spectral characteristics: line positions and intensities in the absorption spectra coincide. Minima of the electrostatic potential demonstrate that the deepest isomer minimum is observed on the carbonyl oxygen atom. However, investigations of the fluorescence spectra show that the radiative properties of isomers differ. An analysis of results of quantum-chemical calculations demonstrate that the long-wavelength ππ* transition in the vanillin absorption spectra is formed due to electron charge transfer from the phenol part of the molecule to oxygen atoms of the methoxy and carbonyl groups, and in the isovanillin absorption spectra, it is formed only on the oxygen atom of the methoxy group. The presence of hydroxyl and carbonyl groups in the structure of the examined molecules leads to the fact that isovanillin in the ground S0 state, the same as vanillin, possesses acidic properties, whereas in the excited S1 state, they possess basic properties. A comparison of the рKа values of aqueous solutions demonstrates that vanillin possesses stronger acidic and basic properties in comparison with isovanillin.

Thermodynamic properties for applications in chemical industry via classical force fields.

PubMed

Guevara-Carrion, Gabriela; Hasse, Hans; Vrabec, Jadran

2012-01-01

Thermodynamic properties of fluids are of key importance for the chemical industry. Presently, the fluid property models used in process design and optimization are mostly equations of state or G (E) models, which are parameterized using experimental data. Molecular modeling and simulation based on classical force fields is a promising alternative route, which in many cases reasonably complements the well established methods. This chapter gives an introduction to the state-of-the-art in this field regarding molecular models, simulation methods, and tools. Attention is given to the way modeling and simulation on the scale of molecular force fields interact with other scales, which is mainly by parameter inheritance. Parameters for molecular force fields are determined both bottom-up from quantum chemistry and top-down from experimental data. Commonly used functional forms for describing the intra- and intermolecular interactions are presented. Several approaches for ab initio to empirical force field parameterization are discussed. Some transferable force field families, which are frequently used in chemical engineering applications, are described. Furthermore, some examples of force fields that were parameterized for specific molecules are given. Molecular dynamics and Monte Carlo methods for the calculation of transport properties and vapor-liquid equilibria are introduced. Two case studies are presented. First, using liquid ammonia as an example, the capabilities of semi-empirical force fields, parameterized on the basis of quantum chemical information and experimental data, are discussed with respect to thermodynamic properties that are relevant for the chemical industry. Second, the ability of molecular simulation methods to describe accurately vapor-liquid equilibrium properties of binary mixtures containing CO(2) is shown.

Quantum probability ranking principle for ligand-based virtual screening.

PubMed

Al-Dabbagh, Mohammed Mumtaz; Salim, Naomie; Himmat, Mubarak; Ahmed, Ali; Saeed, Faisal

2017-04-01

Chemical libraries contain thousands of compounds that need screening, which increases the need for computational methods that can rank or prioritize compounds. The tools of virtual screening are widely exploited to enhance the cost effectiveness of lead drug discovery programs by ranking chemical compounds databases in decreasing probability of biological activity based upon probability ranking principle (PRP). In this paper, we developed a novel ranking approach for molecular compounds inspired by quantum mechanics, called quantum probability ranking principle (QPRP). The QPRP ranking criteria would make an attempt to draw an analogy between the physical experiment and molecular structure ranking process for 2D fingerprints in ligand based virtual screening (LBVS). The development of QPRP criteria in LBVS has employed the concepts of quantum at three different levels, firstly at representation level, this model makes an effort to develop a new framework of molecular representation by connecting the molecular compounds with mathematical quantum space. Secondly, estimate the similarity between chemical libraries and references based on quantum-based similarity searching method. Finally, rank the molecules using QPRP approach. Simulated virtual screening experiments with MDL drug data report (MDDR) data sets showed that QPRP outperformed the classical ranking principle (PRP) for molecular chemical compounds.

Quantum probability ranking principle for ligand-based virtual screening

NASA Astrophysics Data System (ADS)

Al-Dabbagh, Mohammed Mumtaz; Salim, Naomie; Himmat, Mubarak; Ahmed, Ali; Saeed, Faisal

2017-04-01

Chemical libraries contain thousands of compounds that need screening, which increases the need for computational methods that can rank or prioritize compounds. The tools of virtual screening are widely exploited to enhance the cost effectiveness of lead drug discovery programs by ranking chemical compounds databases in decreasing probability of biological activity based upon probability ranking principle (PRP). In this paper, we developed a novel ranking approach for molecular compounds inspired by quantum mechanics, called quantum probability ranking principle (QPRP). The QPRP ranking criteria would make an attempt to draw an analogy between the physical experiment and molecular structure ranking process for 2D fingerprints in ligand based virtual screening (LBVS). The development of QPRP criteria in LBVS has employed the concepts of quantum at three different levels, firstly at representation level, this model makes an effort to develop a new framework of molecular representation by connecting the molecular compounds with mathematical quantum space. Secondly, estimate the similarity between chemical libraries and references based on quantum-based similarity searching method. Finally, rank the molecules using QPRP approach. Simulated virtual screening experiments with MDL drug data report (MDDR) data sets showed that QPRP outperformed the classical ranking principle (PRP) for molecular chemical compounds.

Simulation of a broadband nano-biosensor based on an onion-like quantum dot-quantum well structure

DOE Office of Scientific and Technical Information (OSTI.GOV)

Absalan, H; SalmanOgli, A; Rostami, R

The fluorescence resonance energy transfer is studied between modified quantum-dots and quantum-wells used as a donor and an acceptor. Because of the unique properties of quantum dots, including diverse surface modification flexibility, bio-compatibility, high quantum yields and wide absorption, their use as nano-biosensors and bio-markers used in diagnosis of cancer is suggested. The fluorescence resonance energy transfer is simulated in a quantum dot-quantum well system, where the energy can flow from donor to acceptor. If the energy transfer can be either turned on or off by a specific interaction, such as interaction with any dyes, a molecular binding event ormore » a cleavage reaction, a sensor can be designed (under assumption that the healthy cells have a known effect or unyielding effect on output parameters while cancerous cells, due to their pandemic optical properties, can impact the fluorescence resonance energy transfer parameters). The developed nano-biosensor can operate in a wide range of wavelengths (310 - 760 nm). (laser applications in biology and medicine)« less

Intermolecular CH···O/N H-bonds in the biologically important pairs of natural nucleobases: a thorough quantum-chemical study.

PubMed

Brovarets', Ol'ha O; Yurenko, Yevgen P; Hovorun, Dmytro M

2014-01-01

This study aims to cast light on the physico-chemical nature and energetic of the non-conventional CH···O/N H-bonds in the biologically important natural nucleobase pairs using a comprehensive quantum-chemical approach. As a whole, the 36 biologically important pairs, involving canonical and rare tautomers of nucleobases, were studied by means of all available up-to-date state-of-the-art quantum-chemical techniques along with quantum theory "Atoms in molecules" (QTAIM), Natural Bond Orbital (NBO) analysis, Grunenberg's compliance constants theory, geometrical and vibrational analyses to identify the CH···O/N interactions, reveal their physico-chemical nature and estimate their strengths as well as contribution to the overall base-pairs stability. It was shown that all the 38 CH···O/N contacts (25 CH···O and 13 CH···N H-bonds) completely satisfy all classical geometrical, electron-topological, in particular Bader's and "two-molecule" Koch and Popelier's, and vibrational criteria of H-bonding. The positive values of Grunenberg's compliance constants prove that the CH···O/N contacts in nucleobase pairs are stabilizing interactions unlike electrostatic repulsion and anti-H-bonds. NBO analysis indicates the electron density transfer from the lone electron pair of the acceptor atom (O/N) to the antibonding orbital corresponding to the donor group σ(∗)(CH). Moreover, significant increase in the frequency of the out-of-plane deformation modes γ (CH) under the formation of the CH···O (by 17.2÷81.3/10.8÷84.7 cm(-1)) and CH···N (by 32.7÷85.9/9.0÷77.9 cm(-1)) H-bonds at the density functional theory (DFT)/second-order Møller-Plesset (MP2) levels of theory, respectively, and concomitant changes of their intensities can be considered as reliable indicators of H-bonding. The strengths of the CH···O/N interactions, evaluated by means of Espinosa-Molins-Lecomte formula, lie within the range 0.45÷3.89/0.62÷4.10 kcal/mol for the CH�

Quantum-correlated two-photon transitions to excitons in semiconductor quantum wells.

PubMed

Salazar, L J; Guzmán, D A; Rodríguez, F J; Quiroga, L

2012-02-13

The dependence of the excitonic two-photon absorption on the quantum correlations (entanglement) of exciting biphotons by a semiconductor quantum well is studied. We show that entangled photon absorption can display very unusual features depending on space-time-polarization biphoton parameters and absorber density of states for both bound exciton states as well as for unbound electron-hole pairs. We report on the connection between biphoton entanglement, as quantified by the Schmidt number, and absorption by a semiconductor quantum well. Comparison between frequency-anti-correlated, unentangled and frequency-correlated biphoton absorption is addressed. We found that exciton oscillator strengths are highly increased when photons arrive almost simultaneously in an entangled state. Two-photon-absorption becomes a highly sensitive probe of photon quantum correlations when narrow semiconductor quantum wells are used as two-photon absorbers.

Scaling of the local quantum uncertainty at quantum phase transitions

NASA Astrophysics Data System (ADS)

Coulamy, I. B.; Warnes, J. H.; Sarandy, M. S.; Saguia, A.

2016-04-01

We investigate the local quantum uncertainty (LQU) between a block of L qubits and one single qubit in a composite system of n qubits driven through a quantum phase transition (QPT). A first-order QPT is analytically considered through a Hamiltonian implementation of the quantum search. In the case of second-order QPTs, we consider the transverse-field Ising chain via a numerical analysis through density matrix renormalization group. For both cases, we compute the LQU for finite-sizes as a function of L and of the coupling parameter, analyzing its pronounced behavior at the QPT.

Investigations of quantum heuristics for optimization

NASA Astrophysics Data System (ADS)

Rieffel, Eleanor; Hadfield, Stuart; Jiang, Zhang; Mandra, Salvatore; Venturelli, Davide; Wang, Zhihui

We explore the design of quantum heuristics for optimization, focusing on the quantum approximate optimization algorithm, a metaheuristic developed by Farhi, Goldstone, and Gutmann. We develop specific instantiations of the of quantum approximate optimization algorithm for a variety of challenging combinatorial optimization problems. Through theoretical analyses and numeric investigations of select problems, we provide insight into parameter setting and Hamiltonian design for quantum approximate optimization algorithms and related quantum heuristics, and into their implementation on hardware realizable in the near term.

Quantum chemistry in environmental pesticide risk assessment.

PubMed

Villaverde, Juan J; López-Goti, Carmen; Alcamí, Manuel; Lamsabhi, Al Mokhtar; Alonso-Prados, José L; Sandín-España, Pilar

2017-11-01

The scientific community and regulatory bodies worldwide, currently promote the development of non-experimental tests that produce reliable data for pesticide risk assessment. The use of standard quantum chemistry methods could allow the development of tools to perform a first screening of compounds to be considered for the experimental studies, improving the risk assessment. This fact results in a better distribution of resources and in better planning, allowing a more exhaustive study of the pesticides and their metabolic products. The current paper explores the potential of quantum chemistry in modelling toxicity and environmental behaviour of pesticides and their by-products by using electronic descriptors obtained computationally. Quantum chemistry has potential to estimate the physico-chemical properties of pesticides, including certain chemical reaction mechanisms and their degradation pathways, allowing modelling of the environmental behaviour of both pesticides and their by-products. In this sense, theoretical methods can contribute to performing a more focused risk assessment of pesticides used in the market, and may lead to higher quality and safer agricultural products. © 2017 Society of Chemical Industry. © 2017 Society of Chemical Industry.

Observation of the Quantum Anomalous Hall Insulator to Anderson Insulator Quantum Phase Transition and its Scaling Behavior.

PubMed

Chang, Cui-Zu; Zhao, Weiwei; Li, Jian; Jain, J K; Liu, Chaoxing; Moodera, Jagadeesh S; Chan, Moses H W

2016-09-16

Fundamental insight into the nature of the quantum phase transition from a superconductor to an insulator in two dimensions, or from one plateau to the next or to an insulator in the quantum Hall effect, has been revealed through the study of its scaling behavior. Here, we report on the experimental observation of a quantum phase transition from a quantum-anomalous-Hall insulator to an Anderson insulator in a magnetic topological insulator by tuning the chemical potential. Our experiment demonstrates the existence of scaling behavior from which we extract the critical exponent for this quantum phase transition. We expect that our work will motivate much further investigation of many properties of quantum phase transition in this new context.

Low temperature regulated growth of PbS quantum dots by wet chemical method

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kumar, Hitanshu, E-mail: hitanshuminhas@gmail.com; Barman, P. B.; Singh, Ragini Raj

2015-08-28

Narrow size distribution with regulated synthesis of lead sulfide (PbS) quantum dots (QDs) was achieved through wet chemical method. Different concentrations of 2-mercaptoethanol (capping agent) were used for tailoring the QDs size. Transmission electron microscopy and X-ray diffraction studies revealed that the QDs have mean diameters between 6 to 15 nm. The optical absorption spectra were compared to the predictions of a theoretical model for the electronic structure. The theory agrees well with experiment for QDs larger than 7 nm, but for smaller dots there is some deviation from the theoretical predictions. Consequently, the produced particles are having monodispersity, good water solubility,more » stability and may be good arguments to be biologically compatible due to the use of 2-mercaptoethanol.« less

Integrating machine learning to achieve an automatic parameter prediction for practical continuous-variable quantum key distribution

NASA Astrophysics Data System (ADS)

Liu, Weiqi; Huang, Peng; Peng, Jinye; Fan, Jianping; Zeng, Guihua

2018-02-01

For supporting practical quantum key distribution (QKD), it is critical to stabilize the physical parameters of signals, e.g., the intensity, phase, and polarization of the laser signals, so that such QKD systems can achieve better performance and practical security. In this paper, an approach is developed by integrating a support vector regression (SVR) model to optimize the performance and practical security of the QKD system. First, a SVR model is learned to precisely predict the time-along evolutions of the physical parameters of signals. Second, such predicted time-along evolutions are employed as feedback to control the QKD system for achieving the optimal performance and practical security. Finally, our proposed approach is exemplified by using the intensity evolution of laser light and a local oscillator pulse in the Gaussian modulated coherent state QKD system. Our experimental results have demonstrated three significant benefits of our SVR-based approach: (1) it can allow the QKD system to achieve optimal performance and practical security, (2) it does not require any additional resources and any real-time monitoring module to support automatic prediction of the time-along evolutions of the physical parameters of signals, and (3) it is applicable to any measurable physical parameter of signals in the practical QKD system.

Universal non-adiabatic holonomic quantum computation in decoherence-free subspaces with quantum dots inside a cavity

NASA Astrophysics Data System (ADS)

Liu, Jun; Dong, Ping; Zhou, Jian; Cao, Zhuo-Liang

2017-05-01

A scheme for implementing the non-adiabatic holonomic quantum computation in decoherence-free subspaces is proposed with the interactions between a microcavity and quantum dots. A universal set of quantum gates can be constructed on the encoded logical qubits with high fidelities. The current scheme can suppress both local and collective noises, which is very important for achieving universal quantum computation. Discussions about the gate fidelities with the experimental parameters show that our schemes can be implemented in current experimental technology. Therefore, our scenario offers a method for universal and robust solid-state quantum computation.

Controllable Synthesis of Highly Luminescent Boron Nitride Quantum Dots.

PubMed

Li, Hongling; Tay, Roland Yingjie; Tsang, Siu Hon; Zhen, Xu; Teo, Edwin Hang Tong

2015-12-22

Boron nitride quantum dots (BNQDs), as a new member of heavy metal-free quantum dots, have aroused great interest in fundamental research and practical application due to their unique physical/chemical properties. However, it is still a challenge to controllably synthesize high-quality BNQDs with high quantum yield (QY), uniform size and strong fluorescent. In this work, BNQDs have been successfully fabricated by the liquid exfoliation and the subsequent solvothermal process with respect to its facileness and easy large scale up. Importantly, BNQDs with high-quality can be controllably obtained by adjusting the synthetic parameters involved in the solvothermal process including filling factor, synthesis temperature, and duration time. Encouragingly, the as-prepared BNQDs possess strong blue luminescence with QY as high as 19.5%, which can be attributed to the synergetic effect of size, surface chemistry and edge defects. In addition, this strategy presented here provides a new reference for the controllable synthesis of other heavy metal-free QDs. Furthermore, the as-prepared BNQDs are non-toxic to cells and exhibit nanosecond-scaled lifetimes, suggesting they have great potential biological and optoelectronic applications. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A quantum–quantum Metropolis algorithm

PubMed Central

Yung, Man-Hong; Aspuru-Guzik, Alán

2012-01-01

The classical Metropolis sampling method is a cornerstone of many statistical modeling applications that range from physics, chemistry, and biology to economics. This method is particularly suitable for sampling the thermal distributions of classical systems. The challenge of extending this method to the simulation of arbitrary quantum systems is that, in general, eigenstates of quantum Hamiltonians cannot be obtained efficiently with a classical computer. However, this challenge can be overcome by quantum computers. Here, we present a quantum algorithm which fully generalizes the classical Metropolis algorithm to the quantum domain. The meaning of quantum generalization is twofold: The proposed algorithm is not only applicable to both classical and quantum systems, but also offers a quantum speedup relative to the classical counterpart. Furthermore, unlike the classical method of quantum Monte Carlo, this quantum algorithm does not suffer from the negative-sign problem associated with fermionic systems. Applications of this algorithm include the study of low-temperature properties of quantum systems, such as the Hubbard model, and preparing the thermal states of sizable molecules to simulate, for example, chemical reactions at an arbitrary temperature. PMID:22215584

The geometric field (gravity) as an electro-chemical potential in a Ginzburg-Landau theory of superconductivity

NASA Astrophysics Data System (ADS)

Atanasov, Victor

2017-07-01

We extend the superconductor's free energy to include an interaction of the order parameter with the curvature of space-time. This interaction leads to geometry dependent coherence length and Ginzburg-Landau parameter which suggests that the curvature of space-time can change the superconductor's type. The curvature of space-time doesn't affect the ideal diamagnetism of the superconductor but acts as chemical potential. In a particular circumstance, the geometric field becomes order-parameter dependent, therefore the superconductor's order parameter dynamics affects the curvature of space-time and electrical or internal quantum mechanical energy can be channelled into the curvature of space-time. Experimental consequences are discussed.

Quantum chemical modeling of new derivatives of (E,E)-azomethines: Synthesis, spectroscopic (FT-IR, UV/Vis, polarization) and thermophysical investigations

NASA Astrophysics Data System (ADS)

Shahab, Siyamak; Sheikhi, Masoome; Filippovich, Liudmila; Anatol'evich, Dikusar Evgenij; Yahyaei, Hooriye

2017-06-01

In the present work, the molecular structures of three new azomethine dyes: N-benzylidene-4-((E)-phenyldiazenyl)aniline (PAZB-1), 2-methoxy-4-(((4-((E)- phenyldiazenyl)phenyl)imino)methyl)phenol (PAZB-2) and 2-methoxy-5-((E)-((4-((E)- phenyldiazenyl)phenyl)imino)methyl)phenol (PAZB-8) have been predicted and investigated using Density Functional Theory (DFT) in dimethylformamide (DMF). The geometries of the azomethine dyes were optimized by PBE0/6-31 + G* level of theory. The electronic spectra of these azomethine dyes in a DMF solution was carried out by TDPBE0/6-31 + G* method. After quantum-chemical calculations three new azomethine dyes for optoelectronic applications were synthesized. FT-IR spectra of the title compounds are recorded and discussed. The computed absorption spectral data of the azomethine dyes are in good agreement with the experimental data, thus allowing an assignment of the UV/Vis spectra. On the basis of polyvinyl alcohol (PVA) and the new synthesized azomethine dyes polarizing films for Visible region of spectrum were developed. The main optical parameters of polarizing PVA-films (Transmittance, Polarization Efficiency and Dichroic Ratio) have been measured and discussed. Anisotropy of thermal conductivity of the PVA-films has been studied.

ESR, spectroscopic, and quantum-chemical studies on the electronic structures of complexes formed by Cu(I) with radicals (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gritsan, N.P.; Usov, O.M.; Shokhirev, N.V.

1986-07-01

The optical and ESR spectra have been examined for complexes of Cu(I) with various radicals, which contain various numbers of Cl/sup -/ ions in the central-atom coordination sphere. The spin-Hamiltonian parameters have been determined for all these radical complexes, and the observed ESR spectra have been compared with those calculated with allowance for second-order effects. The observed values for the isotropic and anisotropic components of the HFI constant from the central ion have been used to estimate the contributions from the 4s and 3d/sup 2//sub z/ orbitals of the copper ion to the unpaired-electron MO. Quantum-chemical calculations have been performedmore » by the INDO method on the electronic structures and geometries of complexes formed by CH/sub 2/OH with Cu(I) for various Cl/sup -/ contents in the coordination sphere. The radical is coordinated by the ..pi.. orbital on the carbon atom, and the stabilities of the radical complexes decrease as the number of Cl/sup -/ ions in the coordination sphere increases. A geometry close to planar for the CuCl/sub 4//sup 3 -/ fragment in a complex containing four Cl/sup -/ ions.« less

Toward structural dynamics: protein motions viewed by chemical shift modulations and direct detection of C'N multiple-quantum relaxation.

PubMed

Mori, Mirko; Kateb, Fatiha; Bodenhausen, Geoffrey; Piccioli, Mario; Abergel, Daniel

2010-03-17

Multiple quantum relaxation in proteins reveals unexpected relationships between correlated or anti-correlated conformational backbone dynamics in alpha-helices or beta-sheets. The contributions of conformational exchange to the relaxation rates of C'N coherences (i.e., double- and zero-quantum coherences involving backbone carbonyl (13)C' and neighboring amide (15)N nuclei) depend on the kinetics of slow exchange processes, as well as on the populations of the conformations and chemical shift differences of (13)C' and (15)N nuclei. The relaxation rates of C'N coherences, which reflect concerted fluctuations due to slow chemical shift modulations (CSMs), were determined by direct (13)C detection in diamagnetic and paramagnetic proteins. In well-folded proteins such as lanthanide-substituted calbindin (CaLnCb), copper,zinc superoxide dismutase (Cu,Zn SOD), and matrix metalloproteinase (MMP12), slow conformational exchange occurs along the entire backbone. Our observations demonstrate that relaxation rates of C'N coherences arising from slow backbone dynamics have positive signs (characteristic of correlated fluctuations) in beta-sheets and negative signs (characteristic of anti-correlated fluctuations) in alpha-helices. This extends the prospects of structure-dynamics relationships to slow time scales that are relevant for protein function and enzymatic activity.

A quantum optical transistor with a single quantum dot in a photonic crystal nanocavity.

PubMed

Li, Jin-Jin; Zhu, Ka-Di

2011-02-04

Laser and strong coupling can coexist in a single quantum dot (QD) coupled to a photonic crystal nanocavity. This provides an important clue towards the realization of a quantum optical transistor. Using experimentally realistic parameters, in this work, theoretical analysis shows that such a quantum optical transistor can be switched on or off by turning on or off the pump laser, which corresponds to attenuation or amplification of the probe laser, respectively. Furthermore, based on this quantum optical transistor, an all-optical measurement of the vacuum Rabi splitting is also presented. The idea of associating a quantum optical transistor with this coupled QD-nanocavity system may achieve images of light controlling light in all-optical logic circuits and quantum computers.

Transverse fields to tune an Ising-nematic quantum phase transition [Transverse fields to tune an Ising-nematic quantum critical transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Maharaj, Akash V.; Rosenberg, Elliott W.; Hristov, Alexander T.

Here, the paradigmatic example of a continuous quantum phase transition is the transverse field Ising ferromagnet. In contrast to classical critical systems, whose properties depend only on symmetry and the dimension of space, the nature of a quantum phase transition also depends on the dynamics. In the transverse field Ising model, the order parameter is not conserved, and increasing the transverse field enhances quantum fluctuations until they become strong enough to restore the symmetry of the ground state. Ising pseudospins can represent the order parameter of any system with a twofold degenerate broken-symmetry phase, including electronic nematic order associated withmore » spontaneous point-group symmetry breaking. Here, we show for the representative example of orbital-nematic ordering of a non-Kramers doublet that an orthogonal strain or a perpendicular magnetic field plays the role of the transverse field, thereby providing a practical route for tuning appropriate materials to a quantum critical point. While the transverse fields are conjugate to seemingly unrelated order parameters, their nontrivial commutation relations with the nematic order parameter, which can be represented by a Berry-phase term in an effective field theory, intrinsically intertwine the different order parameters.« less

Transverse fields to tune an Ising-nematic quantum phase transition [Transverse fields to tune an Ising-nematic quantum critical transition

DOE PAGES

Maharaj, Akash V.; Rosenberg, Elliott W.; Hristov, Alexander T.; ...

2017-12-05

Here, the paradigmatic example of a continuous quantum phase transition is the transverse field Ising ferromagnet. In contrast to classical critical systems, whose properties depend only on symmetry and the dimension of space, the nature of a quantum phase transition also depends on the dynamics. In the transverse field Ising model, the order parameter is not conserved, and increasing the transverse field enhances quantum fluctuations until they become strong enough to restore the symmetry of the ground state. Ising pseudospins can represent the order parameter of any system with a twofold degenerate broken-symmetry phase, including electronic nematic order associated withmore » spontaneous point-group symmetry breaking. Here, we show for the representative example of orbital-nematic ordering of a non-Kramers doublet that an orthogonal strain or a perpendicular magnetic field plays the role of the transverse field, thereby providing a practical route for tuning appropriate materials to a quantum critical point. While the transverse fields are conjugate to seemingly unrelated order parameters, their nontrivial commutation relations with the nematic order parameter, which can be represented by a Berry-phase term in an effective field theory, intrinsically intertwine the different order parameters.« less

On subgame perfect equilibria in quantum Stackelberg duopoly

NASA Astrophysics Data System (ADS)

Frąckiewicz, Piotr; Pykacz, Jarosław

2018-02-01

Our purpose is to study the Stackelberg duopoly with the use of the Li-Du-Massar quantum duopoly scheme. The result of Lo and Kiang has shown that the correlation of players's quantities caused by the quantum entanglement enlarges the first-mover advantage in the quantum Stackelberg duopoly. However, the interval of entanglement parameters for which this result is valid is bounded from above. It has been an open question what the equilibrium result is over the upper bound, in particular when the entanglement parameter goes to infinity. Our work provides complete analysis of subgame perfect equilibria of the game for all the values of the entanglement parameter.

The polarization response in InAs quantum dots: theoretical correlation between composition and electronic properties.

PubMed

Usman, Muhammad; Tasco, Vittorianna; Todaro, Maria Teresa; De Giorgi, Milena; O'Reilly, Eoin P; Klimeck, Gerhard; Passaseo, Adriana

2012-04-27

III-V growth and surface conditions strongly influence the physical structure and resulting optical properties of self-assembled quantum dots (QDs). Beyond the design of a desired active optical wavelength, the polarization response of QDs is of particular interest for optical communications and quantum information science. Previous theoretical studies based on a pure InAs QD model failed to reproduce experimentally observed polarization properties. In this work, multi-million atom simulations are performed in an effort to understand the correlation between chemical composition and polarization properties of QDs. A systematic analysis of QD structural parameters leads us to propose a two-layer composition model, mimicking In segregation and In-Ga intermixing effects. This model, consistent with mostly accepted compositional findings, allows us to accurately fit the experimental PL spectra. The detailed study of QD morphology parameters presented here serves as a tool for using growth dynamics to engineer the strain field inside and around the QD structures, allowing tuning of the polarization response.

Determinism Beneath Composite Quantum Systems

NASA Astrophysics Data System (ADS)

Blasone, Massimo; Vitiello, Giuseppe; Jizba, Petr; Scardigli, Fabio

This paper aims at the development of 't Hooft's quantization proposal to describe composite quantum mechanical systems. In particular, we show how 't Hooft's method can be utilized to obtain from two classical Bateman oscillators a composite quantum system corresponding to a quantum isotonic oscillator. For a suitable range of parameters, the composite system can be also interpreted as a particle in an effective magnetic field interacting through a spin-orbital interaction term. In the limit of a large separation from the interaction region we can identify the irreducible subsystems with two independent quantum oscillators.

Quantum synchronization of quantum van der Pol oscillators with trapped ions.

PubMed

Lee, Tony E; Sadeghpour, H R

2013-12-06

The van der Pol oscillator is the prototypical self-sustained oscillator and has been used to model nonlinear behavior in biological and other classical processes. We investigate how quantum fluctuations affect phase locking of one or many van der Pol oscillators. We find that phase locking is much more robust in the quantum model than in the equivalent classical model. Trapped-ion experiments are ideally suited to simulate van der Pol oscillators in the quantum regime via sideband heating and cooling of motional modes. We provide realistic experimental parameters for 171Yb+ achievable with current technology.

Efficient quantum state transfer in an engineered chain of quantum bits

NASA Astrophysics Data System (ADS)

Sandberg, Martin; Knill, Emanuel; Kapit, Eliot; Vissers, Michael R.; Pappas, David P.

2016-03-01

We present a method of performing quantum state transfer in a chain of superconducting quantum bits. Our protocol is based on engineering the energy levels of the qubits in the chain and tuning them all simultaneously with an external flux bias. The system is designed to allow sequential adiabatic state transfers, resulting in on-demand quantum state transfer from one end of the chain to the other. Numerical simulations of the master equation using realistic parameters for capacitive nearest-neighbor coupling, energy relaxation, and dephasing show that fast, high-fidelity state transfer should be feasible using this method.

Optimized multiple quantum MAS lineshape simulations in solid state NMR

NASA Astrophysics Data System (ADS)

Brouwer, William J.; Davis, Michael C.; Mueller, Karl T.

2009-10-01

The majority of nuclei available for study in solid state Nuclear Magnetic Resonance have half-integer spin I>1/2, with corresponding electric quadrupole moment. As such, they may couple with a surrounding electric field gradient. This effect introduces anisotropic line broadening to spectra, arising from distinct chemical species within polycrystalline solids. In Multiple Quantum Magic Angle Spinning (MQMAS) experiments, a second frequency dimension is created, devoid of quadrupolar anisotropy. As a result, the center of gravity of peaks in the high resolution dimension is a function of isotropic second order quadrupole and chemical shift alone. However, for complex materials, these parameters take on a stochastic nature due in turn to structural and chemical disorder. Lineshapes may still overlap in the isotropic dimension, complicating the task of assignment and interpretation. A distributed computational approach is presented here which permits simulation of the two-dimensional MQMAS spectrum, generated by random variates from model distributions of isotropic chemical and quadrupole shifts. Owing to the non-convex nature of the residual sum of squares (RSS) function between experimental and simulated spectra, simulated annealing is used to optimize the simulation parameters. In this manner, local chemical environments for disordered materials may be characterized, and via a re-sampling approach, error estimates for parameters produced. Program summaryProgram title: mqmasOPT Catalogue identifier: AEEC_v1_0 Program summary URL:http://cpc.cs.qub.ac.uk/summaries/AEEC_v1_0.html Program obtainable from: CPC Program Library, Queen's University, Belfast, N. Ireland Licensing provisions: Standard CPC licence, http://cpc.cs.qub.ac.uk/licence/licence.html No. of lines in distributed program, including test data, etc.: 3650 No. of bytes in distributed program, including test data, etc.: 73 853 Distribution format: tar.gz Programming language: C, OCTAVE Computer: UNIX

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

NASA Astrophysics Data System (ADS)

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.

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

PubMed Central

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

2016-01-01

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. PMID:27991584

The quantum phase-transitions of water

NASA Astrophysics Data System (ADS)

Fillaux, François

2017-08-01

It is shown that hexagonal ices and steam are macroscopically quantum condensates, with continuous spacetime-translation symmetry, whereas liquid water is a quantum fluid with broken time-translation symmetry. Fusion and vaporization are quantum phase-transitions. The heat capacities, the latent heats, the phase-transition temperatures, the critical temperature, the molar volume expansion of ice relative to water, as well as neutron scattering data and dielectric measurements are explained. The phase-transition mechanisms along with the key role of quantum interferences and that of Hartley-Shannon's entropy are enlightened. The notions of chemical bond and force-field are questioned.

Filamentation instability in a quantum magnetized plasma

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bret, A.; and Instituto de Investigaciones Energeticas y Aplicaciones Industriales, Campus Universitario de Ciudad Real, 13071 Ciudad Real

2008-02-15

The filamentation instability occurring when a nonrelativistic electron beam passes through a quantum magnetized plasma is investigated by means of a cold quantum magnetohydrodynamic model. It is proved that the instability can be completely suppressed by quantum effects if and only if a finite magnetic field is present. A dimensionless parameter is identified that measures the strength of quantum effects. Strong quantum effects allow for a much smaller magnetic field to suppress the instability than in the classical regime.

Elucidating reaction mechanisms on quantum computers.

PubMed

Reiher, Markus; Wiebe, Nathan; Svore, Krysta M; Wecker, Dave; Troyer, Matthias

2017-07-18

With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.

Elucidating reaction mechanisms on quantum computers

PubMed Central

Reiher, Markus; Wiebe, Nathan; Svore, Krysta M.; Wecker, Dave; Troyer, Matthias

2017-01-01

With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources. PMID:28674011

Elucidating reaction mechanisms on quantum computers

NASA Astrophysics Data System (ADS)

Reiher, Markus; Wiebe, Nathan; Svore, Krysta M.; Wecker, Dave; Troyer, Matthias

2017-07-01

With rapid recent advances in quantum technology, we are close to the threshold of quantum devices whose computational powers can exceed those of classical supercomputers. Here, we show that a quantum computer can be used to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical computer simulations used to probe these reaction mechanisms, to significantly increase their accuracy and enable hitherto intractable simulations. Our resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. Our results demonstrate that quantum computers will be able to tackle important problems in chemistry without requiring exorbitant resources.

Elucidating Reaction Mechanisms on Quantum Computers

NASA Astrophysics Data System (ADS)

Wiebe, Nathan; Reiher, Markus; Svore, Krysta; Wecker, Dave; Troyer, Matthias

We show how a quantum computer can be employed to elucidate reaction mechanisms in complex chemical systems, using the open problem of biological nitrogen fixation in nitrogenase as an example. We discuss how quantum computers can augment classical-computer simulations for such problems, to significantly increase their accuracy and enable hitherto intractable simulations. Detailed resource estimates show that, even when taking into account the substantial overhead of quantum error correction, and the need to compile into discrete gate sets, the necessary computations can be performed in reasonable time on small quantum computers. This demonstrates that quantum computers will realistically be able to tackle important problems in chemistry that are both scientifically and economically significant.

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

PubMed

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.

Ab initio quantum chemical calculation of electron transfer matrix elements for large molecules

NASA Astrophysics Data System (ADS)

Zhang, Linda Yu; Friesner, Richard A.; Murphy, Robert B.

1997-07-01

Using a diabatic state formalism and pseudospectral numerical methods, we have developed an efficient ab initio quantum chemical approach to the calculation of electron transfer matrix elements for large molecules. The theory is developed at the Hartree-Fock level and validated by comparison with results in the literature for small systems. As an example of the power of the method, we calculate the electronic coupling between two bacteriochlorophyll molecules in various intermolecular geometries. Only a single self-consistent field (SCF) calculation on each of the monomers is needed to generate coupling matrix elements for all of the molecular pairs. The largest calculations performed, utilizing 1778 basis functions, required ˜14 h on an IBM 390 workstation. This is considerably less cpu time than would be necessitated with a supermolecule adiabatic state calculation and a conventional electronic structure code.

Characterizing quantum phase transition by teleportation

NASA Astrophysics Data System (ADS)

Wu, Meng-He; Ling, Yi; Shu, Fu-Wen; Gan, Wen-Cong

2018-04-01

In this paper we provide a novel way to explore the relation between quantum teleportation and quantum phase transition. We construct a quantum channel with a mixed state which is made from one dimensional quantum Ising chain with infinite length, and then consider the teleportation with the use of entangled Werner states as input qubits. The fidelity as a figure of merit to measure how well the quantum state is transferred is studied numerically. Remarkably we find the first-order derivative of the fidelity with respect to the parameter in quantum Ising chain exhibits a logarithmic divergence at the quantum critical point. The implications of this phenomenon and possible applications are also briefly discussed.

Quantum speed limits in open system dynamics.

PubMed

del Campo, A; Egusquiza, I L; Plenio, M B; Huelga, S F

2013-02-01

Bounds to the speed of evolution of a quantum system are of fundamental interest in quantum metrology, quantum chemical dynamics, and quantum computation. We derive a time-energy uncertainty relation for open quantum systems undergoing a general, completely positive, and trace preserving evolution which provides a bound to the quantum speed limit. When the evolution is of the Lindblad form, the bound is analogous to the Mandelstam-Tamm relation which applies in the unitary case, with the role of the Hamiltonian being played by the adjoint of the generator of the dynamical semigroup. The utility of the new bound is exemplified in different scenarios, ranging from the estimation of the passage time to the determination of precision limits for quantum metrology in the presence of dephasing noise.

Energy-consistent small-core pseudopotentials for 3d-transition metals adapted to quantum Monte Carlo calculations.

PubMed

Burkatzki, M; Filippi, Claudia; Dolg, M

2008-10-28

We extend our recently published set of energy-consistent scalar-relativistic Hartree-Fock pseudopotentials by the 3d-transition metal elements, scandium through zinc. The pseudopotentials do not exhibit a singularity at the nucleus and are therefore suitable for quantum Monte Carlo (QMC) calculations. The pseudopotentials and the accompanying basis sets (VnZ with n=T,Q) are given in standard Gaussian representation and their parameter sets are presented. Coupled cluster, configuration interaction, and QMC studies are carried out for the scandium and titanium atoms and their oxides, demonstrating the good performance of the pseudopotentials. Even though the choice of pseudopotential form is motivated by QMC, these pseudopotentials can also be employed in other quantum chemical approaches.

Quantum State Tomography via Linear Regression Estimation

PubMed Central

Qi, Bo; Hou, Zhibo; Li, Li; Dong, Daoyi; Xiang, Guoyong; Guo, Guangcan

2013-01-01

A simple yet efficient state reconstruction algorithm of linear regression estimation (LRE) is presented for quantum state tomography. In this method, quantum state reconstruction is converted into a parameter estimation problem of a linear regression model and the least-squares method is employed to estimate the unknown parameters. An asymptotic mean squared error (MSE) upper bound for all possible states to be estimated is given analytically, which depends explicitly upon the involved measurement bases. This analytical MSE upper bound can guide one to choose optimal measurement sets. The computational complexity of LRE is O(d4) where d is the dimension of the quantum state. Numerical examples show that LRE is much faster than maximum-likelihood estimation for quantum state tomography. PMID:24336519

Dirac Cellular Automaton from Split-step Quantum Walk

PubMed Central

Mallick, Arindam; Chandrashekar, C. M.

2016-01-01

Simulations of one quantum system by an other has an implication in realization of quantum machine that can imitate any quantum system and solve problems that are not accessible to classical computers. One of the approach to engineer quantum simulations is to discretize the space-time degree of freedom in quantum dynamics and define the quantum cellular automata (QCA), a local unitary update rule on a lattice. Different models of QCA are constructed using set of conditions which are not unique and are not always in implementable configuration on any other system. Dirac Cellular Automata (DCA) is one such model constructed for Dirac Hamiltonian (DH) in free quantum field theory. Here, starting from a split-step discrete-time quantum walk (QW) which is uniquely defined for experimental implementation, we recover the DCA along with all the fine oscillations in position space and bridge the missing connection between DH-DCA-QW. We will present the contribution of the parameters resulting in the fine oscillations on the Zitterbewegung frequency and entanglement. The tuneability of the evolution parameters demonstrated in experimental implementation of QW will establish it as an efficient tool to design quantum simulator and approach quantum field theory from principles of quantum information theory. PMID:27184159

Physical re-examination of parameters on a molecular collisions-based diffusion model for diffusivity prediction in polymers.

PubMed

Ohashi, Hidenori; Tamaki, Takanori; Yamaguchi, Takeo

2011-12-29

Molecular collisions, which are the microscopic origin of molecular diffusive motion, are affected by both the molecular surface area and the distance between molecules. Their product can be regarded as the free space around a penetrant molecule defined as the "shell-like free volume" and can be taken as a characteristic of molecular collisions. On the basis of this notion, a new diffusion theory has been developed. The model can predict molecular diffusivity in polymeric systems using only well-defined single-component parameters of molecular volume, molecular surface area, free volume, and pre-exponential factors. By consideration of the physical description of the model, the actual body moved and which neighbor molecules are collided with are the volume and the surface area of the penetrant molecular core. In the present study, a semiempirical quantum chemical calculation was used to calculate both of these parameters. The model and the newly developed parameters offer fairly good predictive ability. © 2011 American Chemical Society

On the bathochromic shift of the absorption by astaxanthin in crustacyanin: a quantum chemical study

NASA Astrophysics Data System (ADS)

Durbeej, Bo; Eriksson, Leif A.

2003-06-01

The structural origin of the bathochromic shift assumed by the electronic absorption spectrum of protein-bound astaxanthin, the carotenoid that upon binding to crustacyanin is responsible for the blue colouration of lobster shell, is investigated by means of quantum chemical methods. The calculations suggest that the bathochromic shift is largely due to one of the astaxanthin C4 keto groups being hydrogen-bonded to a histidine residue of the surrounding protein, and that the effect of this histidine is directly dependent on its protonation state. Out of the different methodologies (CIS, TD-DFT, and ZINDO/S) employed to calculate wavelengths of maximum absorption, the best agreement with experimental data is obtained using the semiempirical ZINDO/S method.

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

NASA Astrophysics Data System (ADS)

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.

Non-commutative geometry of the h-deformed quantum plane

NASA Astrophysics Data System (ADS)

Cho, S.; Madore, J.; Park, K. S.

1998-03-01

The h-deformed quantum plane is a counterpart of the q-deformed one in the set of quantum planes which are covariant under those quantum deformations of GL(2) which admit a central determinant. We have investigated the non-commutative geometry of the h-deformed quantum plane. There is a two-parameter family of torsion-free linear connections, a one-parameter sub-family of which are compatible with a skew-symmetric non-degenerate bilinear map. The skew-symmetric map resembles a symplectic 2-form and induces a metric. It is also shown that the extended h-deformed quantum plane is a non-commutative version of the Poincaré half-plane, a surface of constant negative Gaussian

Adiabatic quantum computation along quasienergies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tanaka, Atushi; Nemoto, Kae; National Institute of Informatics, 2-1-2 Hitotsubashi, Chiyoda ku, Tokyo 101-8430

2010-02-15

The parametric deformations of quasienergies and eigenvectors of unitary operators are applied to the design of quantum adiabatic algorithms. The conventional, standard adiabatic quantum computation proceeds along eigenenergies of parameter-dependent Hamiltonians. By contrast, discrete adiabatic computation utilizes adiabatic passage along the quasienergies of parameter-dependent unitary operators. For example, such computation can be realized by a concatenation of parameterized quantum circuits, with an adiabatic though inevitably discrete change of the parameter. A design principle of adiabatic passage along quasienergy was recently proposed: Cheon's quasienergy and eigenspace anholonomies on unitary operators is available to realize anholonomic adiabatic algorithms [A. Tanaka and M.more » Miyamoto, Phys. Rev. Lett. 98, 160407 (2007)], which compose a nontrivial family of discrete adiabatic algorithms. It is straightforward to port a standard adiabatic algorithm to an anholonomic adiabatic one, except an introduction of a parameter |v>, which is available to adjust the gaps of the quasienergies to control the running time steps. In Grover's database search problem, the costs to prepare |v> for the qualitatively different (i.e., power or exponential) running time steps are shown to be qualitatively different.« less

QIPS: quantum information and quantum physics in space

NASA Astrophysics Data System (ADS)

Schmitt-Manderbach, Tobias; Scheidl, Thomas; Ursin, Rupert; Tiefenbacher, Felix; Weier, Henning; Fürst, Martin; Jennewein, T.; Perdigues, J.; Sodnik, Z.; Rarity, J.; Zeilinger, Anton; Weinfurter, Harald

2017-11-01

The aim of the QIPS project (financed by ESA) is to explore quantum phenomena and to demonstrate quantum communication over long distances. Based on the current state-of-the-art a first study investigating the feasibility of space based quantum communication has to establish goals for mid-term and long-term missions, but also has to test the feasibility of key issues in a long distance ground-to-ground experiment. We have therefore designed a proof-of-concept demonstration for establishing single photon links over a distance of 144 km between the Canary Islands of La Palma and Tenerife to evaluate main limitations for future space experiments. Here we report on the progress of this project and present first measurements of crucial parameters of the optical free space link.

Determination of band structure parameters and the quasi-particle gap of CdSe quantum dots by cyclic voltammetry.

PubMed

Inamdar, Shaukatali N; Ingole, Pravin P; Haram, Santosh K

2008-12-01

Band structure parameters such as the conduction band edge, the valence band edge and the quasi-particle gap of diffusing CdSe quantum dots (Q-dots) of various sizes were determined using cyclic voltammetry. These parameters are strongly dependent on the size of the Q-dots. The results obtained from voltammetric measurements are compared to spectroscopic and theoretical data. The fit obtained to the reported calculations based on the semi-empirical pseudopotential method (SEPM)-especially in the strong size-confinement region, is the best reported so far, according to our knowledge. For the smallest CdSe Q-dots, the difference between the quasi-particle gap and the optical band gap gives the electron-hole Coulombic interaction energy (J(e1,h1)). Interband states seen in the photoluminescence spectra were verified with cyclic voltammetry measurements.

Quantum to classical transition in the Hořava-Lifshitz quantum cosmology

NASA Astrophysics Data System (ADS)

Bernardini, A. E.; Leal, P.; Bertolami, O.

2018-02-01

A quasi-Gaussian quantum superposition of Hořava-Lifshitz (HL) stationary states is built in order to describe the transition of the quantum cosmological problem to the related classical dynamics. The obtained HL phase-space superposed Wigner function and its associated Wigner currents describe the conditions for the matching between classical and quantum phase-space trajectories. The matching quantum superposition parameter is associated to the total energy of the classical trajectory which, at the same time, drives the engendered Wigner function to the classical stationary regime. Through the analysis of the Wigner flows, the quantum fluctuations that distort the classical regime can be quantified as a measure of (non)classicality. Finally, the modifications to the Wigner currents due to the inclusion of perturbative potentials are computed in the HL quantum cosmological context. In particular, the inclusion of a cosmological constant provides complementary information that allows for connecting the age of the Universe with the overall stiff matter density profile.

The Interplay of Quantum Confinement and Hydrogenation in Amorphous Silicon Quantum Dots.

PubMed

Askari, Sadegh; Svrcek, Vladmir; Maguire, Paul; Mariotti, Davide

2015-12-22

Hydrogenation in amorphous silicon quantum dots (QDs) has a dramatic impact on the corresponding optical properties and band energy structure, leading to a quantum-confined composite material with unique characteristics. The synthesis of a-Si:H QDs is demonstrated with an atmospheric-pressure plasma process, which allows for accurate control of a highly chemically reactive non-equilibrium environment with temperatures well below the crystallization temperature of Si QDs. © 2015 The Authors. Published by WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Some new reaction pathways for the formation of cytosine in interstellar space - A quantum chemical study

NASA Astrophysics Data System (ADS)

Gupta, V. P.; Tandon, Poonam; Mishra, Priti

2013-03-01

The detection of nucleic acid bases in carbonaceous meteorites suggests that their formation and survival is possible outside of the Earth. Small N-heterocycles, including pyrimidine, purines and nucleobases, have been extensively sought in the interstellar medium. It has been suggested theoretically that reactions between some interstellar molecules may lead to the formation of cytosine, uracil and thymine though these processes involve significantly high potential barriers. We attempted therefore to use quantum chemical techniques to explore if cytosine can possibly form in the interstellar space by radical-radical and radical-molecule interaction schemes, both in the gas phase and in the grains, through barrier-less or low barrier pathways. Results of DFT calculations for the formation of cytosine starting from some of the simple molecules and radicals detected in the interstellar space are being reported. Global and local descriptors such as molecular hardness, softness and electrophilicity, and condensed Fukui functions and local philicity indices were used to understand the mechanistic aspects of chemical reaction. The presence and nature of weak bonds in the molecules and transition states formed during the reaction process have been ascertained using Bader's quantum theory of atoms in molecules (QTAIMs). Two exothermic reaction pathways starting from propynylidyne (CCCH) and cyanoacetylene (HCCCN), respectively, have been identified. While the first reaction path is found to be totally exothermic, it involves a barrier of 12.5 kcal/mol in the gas phase against the lowest value of about 32 kcal/mol reported in the literature. The second path is both exothermic and barrier-less. The later has, therefore, a greater probability of occurrence in the cold interstellar clouds (10-50 K).

Centrality dependence of chemical freeze-out parameters from net-proton and net-charge fluctuations using a hadron resonance gas model

NASA Astrophysics Data System (ADS)

Adak, Rama Prasad; Das, Supriya; Ghosh, Sanjay K.; Ray, Rajarshi; Samanta, Subhasis

2017-07-01

We estimate chemical freeze-out parameters in Hadron Resonance Gas (HRG) and Excluded Volume HRG (EVHRG) models by fitting the experimental information of net-proton and net-charge fluctuations measured in Au + Au collisions by the STAR Collaboration at the BNL Relativistic Heavy Ion Collider (RHIC). We observe that chemical freeze-out parameters obtained from lower and higher order fluctuations are almost the same for √{sNN}>27 GeV, but tend to deviate from each other at lower √{sNN}. Moreover, these separations increase with decrease of √{sNN}, and for a fixed √{sNN} increase towards central collisions. Furthermore, we observe an approximate scaling behavior of (μB/T ) /(μB/T)central with (Npart) /(Npart)central for the parameters estimated from lower order fluctuations for 11.5 ≤√{sNN}≤200 GeV. Scaling is violated for the parameters estimated from higher order fluctuations for √{sNN}=11.5 and 19.6 GeV. It is observed that the chemical freeze-out parameter, which can describe σ2/M of net protons very well in all energies and centralities, cannot describe the s σ equally well, and vice versa.

Confinement control mechanism for two-electron Hulthen quantum dots in plasmas

NASA Astrophysics Data System (ADS)

Bahar, M. K.; Soylu, A.

2018-05-01

In this study, for the first time, the energies of two-electron Hulthen quantum dots (TEHQdots) embedded in Debye and quantum plasmas modeled by the more general exponential cosine screened Coulomb (MGECSC) potential under the combined influence of electric and magnetic fields are investigated by numerically solving the Schrödinger equation using the asymptotic iteration method. To do this, the four different forms of the MGECSC potential, which set through the different cases of the potential parameters, are taken into consideration. We propose that plasma environments form considerable quantum mechanical effects for quantum dots and other atomic systems and that plasmas are important experimental arguments. In this study, by considering the quantum dot parameters, the external field parameters, and the plasma screening parameters, a control mechanism of the confinement on energies of TEHQdots and the frequency of the radiation emitted by TEHQdots as a result of any excitation is discussed. In this mechanism, the behaviors, similarities, the functionalities of the control parameters, and the influences of plasmas on these quantities are explored.

Realizing a partial general quantum cloning machine with superconducting quantum-interference devices in a cavity QED

NASA Astrophysics Data System (ADS)

Fang, Bao-Long; Yang, Zhen; Ye, Liu

2009-05-01

We propose a scheme for implementing a partial general quantum cloning machine with superconducting quantum-interference devices coupled to a nonresonant cavity. By regulating the time parameters, our system can perform optimal symmetric (asymmetric) universal quantum cloning, optimal symmetric (asymmetric) phase-covariant cloning, and optimal symmetric economical phase-covariant cloning. In the scheme the cavity is only virtually excited, thus, the cavity decay is suppressed during the cloning operations.

Sound propagation in liquid foams: Unraveling the balance between physical and chemical parameters.

PubMed

Pierre, Juliette; Giraudet, Brice; Chasle, Patrick; Dollet, Benjamin; Saint-Jalmes, Arnaud

2015-04-01

We present experimental results on the propagation of an ultrasonic wave (40 kHz) in liquid foams, as a function of the foam physical and chemical parameters. We have first implemented an original setup, using transducers in a transmission configuration. The foam coarsening was used to vary the bubble size (remaining in the submillimeter range), and we have made foams with various chemical formulations, to investigate the role of the chemicals at the bubble interfaces or in bulk. The results are compared with recently published theoretical works, and good agreements are found. In particular, for all the foams, we have evidenced two asymptotic limits, at small and large bubble size, connected by a nontrivial resonant behavior, associated to an effective negative density. These qualitative features are robust whatever the chemical formulation; we discuss the observed differences between the samples, in relation to the interfacial and bulk viscoelasticity. These results demonstrate the rich and complex acoustic behavior of foams. While the bubble size remain here always smaller than the sound wavelength, it turns out that one must go well beyond mean-field modeling to describe the foam acoustic properties.

Sound propagation in liquid foams: Unraveling the balance between physical and chemical parameters

NASA Astrophysics Data System (ADS)

Pierre, Juliette; Giraudet, Brice; Chasle, Patrick; Dollet, Benjamin; Saint-Jalmes, Arnaud

2015-04-01

We present experimental results on the propagation of an ultrasonic wave (40 kHz) in liquid foams, as a function of the foam physical and chemical parameters. We have first implemented an original setup, using transducers in a transmission configuration. The foam coarsening was used to vary the bubble size (remaining in the submillimeter range), and we have made foams with various chemical formulations, to investigate the role of the chemicals at the bubble interfaces or in bulk. The results are compared with recently published theoretical works, and good agreements are found. In particular, for all the foams, we have evidenced two asymptotic limits, at small and large bubble size, connected by a nontrivial resonant behavior, associated to an effective negative density. These qualitative features are robust whatever the chemical formulation; we discuss the observed differences between the samples, in relation to the interfacial and bulk viscoelasticity. These results demonstrate the rich and complex acoustic behavior of foams. While the bubble size remain here always smaller than the sound wavelength, it turns out that one must go well beyond mean-field modeling to describe the foam acoustic properties.

Coprocessors for quantum devices

NASA Astrophysics Data System (ADS)

Kay, Alastair

2018-03-01

Quantum devices, from simple fixed-function tools to the ultimate goal of a universal quantum computer, will require high-quality, frequent repetition of a small set of core operations, such as the preparation of entangled states. These tasks are perfectly suited to realization by a coprocessor or supplementary instruction set, as is common practice in modern CPUs. In this paper, we present two quintessentially quantum coprocessor functions: production of a Greenberger-Horne-Zeilinger state and implementation of optimal universal (asymmetric) quantum cloning. Both are based on the evolution of a fixed Hamiltonian. We introduce a technique for deriving the parameters of these Hamiltonians based on the numerical integration of Toda-like flows.

Simulated quantum computation of molecular energies.

PubMed

Aspuru-Guzik, Alán; Dutoi, Anthony D; Love, Peter J; Head-Gordon, Martin

2005-09-09

The calculation time for the energy of atoms and molecules scales exponentially with system size on a classical computer but polynomially using quantum algorithms. We demonstrate that such algorithms can be applied to problems of chemical interest using modest numbers of quantum bits. Calculations of the water and lithium hydride molecular ground-state energies have been carried out on a quantum computer simulator using a recursive phase-estimation algorithm. The recursive algorithm reduces the number of quantum bits required for the readout register from about 20 to 4. Mappings of the molecular wave function to the quantum bits are described. An adiabatic method for the preparation of a good approximate ground-state wave function is described and demonstrated for a stretched hydrogen molecule. The number of quantum bits required scales linearly with the number of basis functions, and the number of gates required grows polynomially with the number of quantum bits.

Ferritin-Templated Quantum-Dots for Quantum Logic Gates

NASA Technical Reports Server (NTRS)

Choi, Sang H.; Kim, Jae-Woo; Chu, Sang-Hyon; Park, Yeonjoon; King, Glen C.; Lillehei, Peter T.; Kim, Seon-Jeong; Elliott, James R.

2005-01-01

Quantum logic gates (QLGs) or other logic systems are based on quantum-dots (QD) with a stringent requirement of size uniformity. The QD are widely known building units for QLGs. The size control of QD is a critical issue in quantum-dot fabrication. The work presented here offers a new method to develop quantum-dots using a bio-template, called ferritin, that ensures QD production in uniform size of nano-scale proportion. The bio-template for uniform yield of QD is based on a ferritin protein that allows reconstitution of core material through the reduction and chelation processes. One of the biggest challenges for developing QLG is the requirement of ordered and uniform size of QD for arrays on a substrate with nanometer precision. The QD development by bio-template includes the electrochemical/chemical reconsitution of ferritins with different core materials, such as iron, cobalt, manganese, platinum, and nickel. The other bio-template method used in our laboratory is dendrimers, precisely defined chemical structures. With ferritin-templated QD, we fabricated the heptagonshaped patterned array via direct nano manipulation of the ferritin molecules with a tip of atomic force microscope (AFM). We also designed various nanofabrication methods of QD arrays using a wide range manipulation techniques. The precise control of the ferritin-templated QD for a patterned arrangement are offered by various methods, such as a site-specific immobilization of thiolated ferritins through local oxidation using the AFM tip, ferritin arrays induced by gold nanoparticle manipulation, thiolated ferritin positioning by shaving method, etc. In the signal measurements, the current-voltage curve is obtained by measuring the current through the ferritin, between the tip and the substrate for potential sweeping or at constant potential. The measured resistance near zero bias was 1.8 teraohm for single holoferritin and 5.7 teraohm for single apoferritin, respectively.

Parameter-free driven Liouville-von Neumann approach for time-dependent electronic transport simulations in open quantum systems

DOE PAGES

Zelovich, Tamar; Hansen, Thorsten; Liu, Zhen-Fei; ...

2017-03-02

A parameter-free version of the recently developed driven Liouville-von Neumann equation [T. Zelovich et al., J. Chem. Theory Comput. 10(8), 2927-2941 (2014)] for electronic transport calculations in molecular junctions is presented. The single driving rate, appearing as a fitting parameter in the original methodology, is replaced by a set of state-dependent broadening factors applied to the different single-particle lead levels. These broadening factors are extracted explicitly from the self-energy of the corresponding electronic reservoir and are fully transferable to any junction incorporating the same lead model. Furthermore, the performance of the method is demonstrated via tight-binding and extended Hückel calculationsmore » of simple junction models. Our analytic considerations and numerical results indicate that the developed methodology constitutes a rigorous framework for the design of "black-box" algorithms to simulate electron dynamics in open quantum systems out of equilibrium.« less

Parameter-free driven Liouville-von Neumann approach for time-dependent electronic transport simulations in open quantum systems

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zelovich, Tamar; Hansen, Thorsten; Liu, Zhen-Fei

A parameter-free version of the recently developed driven Liouville-von Neumann equation [T. Zelovich et al., J. Chem. Theory Comput. 10(8), 2927-2941 (2014)] for electronic transport calculations in molecular junctions is presented. The single driving rate, appearing as a fitting parameter in the original methodology, is replaced by a set of state-dependent broadening factors applied to the different single-particle lead levels. These broadening factors are extracted explicitly from the self-energy of the corresponding electronic reservoir and are fully transferable to any junction incorporating the same lead model. Furthermore, the performance of the method is demonstrated via tight-binding and extended Hückel calculationsmore » of simple junction models. Our analytic considerations and numerical results indicate that the developed methodology constitutes a rigorous framework for the design of "black-box" algorithms to simulate electron dynamics in open quantum systems out of equilibrium.« less

Quantum dot nanoparticle conjugation, characterization, and applications in neuroscience

NASA Astrophysics Data System (ADS)

Pathak, Smita

Quantum dot are semiconducting nanoparticles that have been used for decades in a variety of applications such as solar cells, LEDs and medical imaging. Their use in the last area, however, has been extremely limited despite their potential as revolutionary new biological labeling tools. Quantum dots are much brighter and more stable than conventional fluorophores, making them optimal for high resolution imaging and long term studies. Prior work in this area involves synthesizing and chemically conjugating quantum dots to molecules of interest in-house. However this method is both time consuming and prone to human error. Additionally, non-specific binding and nanoparticle aggregation currently prevent researchers from utilizing this system to its fullest capacity. Another critical issue that has not been addressed is determining the number of ligands bound to nanoparticles, which is crucial for proper interpretation of results. In this work, methods to label fixed cells using two types of chemically modified quantum dots are studied. Reproducible non-specific artifact labeling is consistently demonstrated if antibody-quantum dot conditions are less than optimal. In order to explain this, antibodies bound to quantum dots were characterized and quantified. While other groups have qualitatively characterized antibody functionalized quantum dots using TEM, AFM, UV spectroscopy and gel electrophoresis, and in some cases have reported calculated estimates of the putative number of total antibodies bound to quantum dots, no quantitative experimental results had been reported prior to this work. The chemical functionalization and characterization of quantum dot nanocrystals achieved in this work elucidates binding mechanisms of ligands to nanoparticles and allows researchers to not only translate our tools to studies in their own areas of interest but also derive quantitative results from these studies. This research brings ease of use and increased reliability to

Array of nanoparticles coupling with quantum-dot: Lattice plasmon quantum features

NASA Astrophysics Data System (ADS)

Salmanogli, Ahmad; Gecim, H. Selcuk

2018-06-01

In this study, we analyze the interaction of lattice plasmon with quantum-dot in order to mainly examine the quantum features of the lattice plasmon containing the photonic/plasmonic properties. Despite optical properties of the localized plasmon, the lattice plasmon severely depends on the array geometry, which may influence its quantum features such as uncertainty and the second-order correlation function. To investigate this interaction, we consider a closed system containing an array of the plasmonic nanoparticles and quantum-dot. We analyze this system with full quantum theory by which the array electric far field is quantized and the strength coupling of the quantum-dot array is analytically calculated. Moreover, the system's dynamics are evaluated and studied via the Heisenberg-Langevin equations to attain the system optical modes. We also analytically examine the Purcell factor, which shows the effect of the lattice plasmon on the quantum-dot spontaneous emission. Finally, the lattice plasmon uncertainty and its time evolution of the second-order correlation function at different spatial points are examined. These parameters are dramatically affected by the retarded field effect of the array nanoparticles. We found a severe quantum fluctuation at points where the lattice plasmon occurs, suggesting that the lattice plasmon photons are correlated.

Convexity of quantum χ2-divergence.

PubMed

Hansen, Frank

2011-06-21

The general quantum χ(2)-divergence has recently been introduced by Temme et al. [Temme K, Kastoryano M, Ruskai M, Wolf M, Verstrate F (2010) J Math Phys 51:122201] and applied to quantum channels (quantum Markov processes). The quantum χ(2)-divergence is not unique, as opposed to the classical χ(2)-divergence, but depends on the choice of quantum statistics. It was noticed that the elements in a particular one-parameter family of quantum χ(2)-divergences are convex functions in the density matrices (ρ,σ), thus mirroring the convexity of the classical χ(2)(p,q)-divergence in probability distributions (p,q). We prove that any quantum χ(2)-divergence is a convex function in its two arguments.

On Macroscopic Quantum Phenomena in Biomolecules and Cells: From Levinthal to Hopfield

PubMed Central

Raković, Dejan; Dugić, Miroljub; Jeknić-Dugić, Jasmina; Plavšić, Milenko; Jaćimovski, Stevo; Šetrajčić, Jovan

2014-01-01

In the context of the macroscopic quantum phenomena of the second kind, we hereby seek for a solution-in-principle of the long standing problem of the polymer folding, which was considered by Levinthal as (semi)classically intractable. To illuminate it, we applied quantum-chemical and quantum decoherence approaches to conformational transitions. Our analyses imply the existence of novel macroscopic quantum biomolecular phenomena, with biomolecular chain folding in an open environment considered as a subtle interplay between energy and conformation eigenstates of this biomolecule, governed by quantum-chemical and quantum decoherence laws. On the other hand, within an open biological cell, a system of all identical (noninteracting and dynamically noncoupled) biomolecular proteins might be considered as corresponding spatial quantum ensemble of these identical biomolecular processors, providing spatially distributed quantum solution to a single corresponding biomolecular chain folding, whose density of conformational states might be represented as Hopfield-like quantum-holographic associative neural network too (providing an equivalent global quantum-informational alternative to standard molecular-biology local biochemical approach in biomolecules and cells and higher hierarchical levels of organism, as well). PMID:25028662

Continuous quantum measurement and the quantum to classical transition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bhattacharya, Tanmoy; Habib, Salman; Jacobs, Kurt

2003-04-01

While ultimately they are described by quantum mechanics, macroscopic mechanical systems are nevertheless observed to follow the trajectories predicted by classical mechanics. Hence, in the regime defining macroscopic physics, the trajectories of the correct classical motion must emerge from quantum mechanics, a process referred to as the quantum to classical transition. Extending previous work [Bhattacharya, Habib, and Jacobs, Phys. Rev. Lett. 85, 4852 (2000)], here we elucidate this transition in some detail, showing that once the measurement processes that affect all macroscopic systems are taken into account, quantum mechanics indeed predicts the emergence of classical motion. We derive inequalities thatmore » describe the parameter regime in which classical motion is obtained, and provide numerical examples. We also demonstrate two further important properties of the classical limit: first, that multiple observers all agree on the motion of an object, and second, that classical statistical inference may be used to correctly track the classical motion.« less

Geometric diffusion of quantum trajectories

PubMed Central

Yang, Fan; Liu, Ren-Bao

2015-01-01

A quantum object can acquire a geometric phase (such as Berry phases and Aharonov–Bohm phases) when evolving along a path in a parameter space with non-trivial gauge structures. Inherent to quantum evolutions of wavepackets, quantum diffusion occurs along quantum trajectories. Here we show that quantum diffusion can also be geometric as characterized by the imaginary part of a geometric phase. The geometric quantum diffusion results from interference between different instantaneous eigenstate pathways which have different geometric phases during the adiabatic evolution. As a specific example, we study the quantum trajectories of optically excited electron-hole pairs in time-reversal symmetric insulators, driven by an elliptically polarized terahertz field. The imaginary geometric phase manifests itself as elliptical polarization in the terahertz sideband generation. The geometric quantum diffusion adds a new dimension to geometric phases and may have applications in many fields of physics, e.g., transport in topological insulators and novel electro-optical effects. PMID:26178745

Quantum optical effective-medium theory and transformation quantum optics for metamaterials

NASA Astrophysics Data System (ADS)

Wubs, Martijn; Amooghorban, Ehsan; Zhang, Jingjing; Mortensen, N. Asger

2016-09-01

While typically designed to manipulate classical light, metamaterials have many potential applications for quantum optics as well. We argue why a quantum optical effective-medium theory is needed. We present such a theory for layered metamaterials that is valid for light propagation in all spatial directions, thereby generalizing earlier work for one-dimensional propagation. In contrast to classical effective-medium theory there is an additional effective parameter that describes quantum noise. Our results for metamaterials are based on a rather general Lagrangian theory for the quantum electrodynamics of media with both loss and gain. In the second part of this paper, we present a new application of transformation optics whereby local spontaneous-emission rates of quantum emitters can be designed. This follows from an analysis how electromagnetic Green functions trans- form under coordinate transformations. Spontaneous-emission rates can be either enhanced or suppressed using invisibility cloaks or gradient index lenses. Furthermore, the anisotropic material profile of the cloak enables the directional control of spontaneous emission.

EPR parameters of L-α-alanine radicals in aqueous solution: a first-principles study

NASA Astrophysics Data System (ADS)

Janbazi, Mehdi; T. Azar, Yavar; Ziaie, Farhood

2018-07-01

EPR (electron paramagnetic resonance) response for a wide range of possible alanine radicals has been analysed employing quantum chemical methods. The strong correlation between geometry and EPR parameter structure of these radicals has been shown in this research work. Significant solvent effect on EPR parameters has been shown employing both explicit and implicit solvent models. In a relatively good agreement with the experiment, stable conformation of these radicals in acidic and basic conditions was determined, and a new conformation was suggested based on possible proton transfer in the intermediate pH range. The employed methodology along with experimental results may be used for the characterisation of different radiation-induced amino acid radicals.

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

NASA Technical Reports Server (NTRS)

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.

Quantum Optics Initiative

DTIC Science & Technology

2007-06-30

the choice for the specificity parameter (S), which is the area around the 51(±3) cm 1 frequency in the Fourier plane (right in Fig...1). The HOMO is believed to be entirely of phthalocyanine character in Alu symmetry of the D4h group [6]. The full-width-at- half - maximum (FWHM) of...quantum Lyapunov exponents or by examining the corresponding Poincare sections in this limit. Since the Bohmian formulation of quantum theory is based

PREDICTION OF CHEMICAL REACTIVITY PARAMETERS AND PHYSICAL PROPERTIES OF ORGANIC COMPOUNDS FROM MOLECULAR STRUCTURE USING SPARC

EPA Science Inventory

The computer program SPARC (SPARC Performs Automated Reasoning in Chemistry) has been under development for several years to estimate physical properties and chemical reactivity parameters of organic compounds strictly from molecular structure. SPARC uses computational algorithms...

Quantum Yield Heterogeneity among Single Nonblinking Quantum Dots Revealed by Atomic Structure-Quantum Optics Correlation

DOE PAGES

Orfield, Noah J.; McBride, James R.; Wang, Feng; ...

2016-02-05

Physical variations in colloidal nanostructures give rise to heterogeneity in expressed optical behavior. This correlation between nanoscale structure and function demands interrogation of both atomic structure and photophysics at the level of single nanostructures to be fully understood. In this paper, by conducting detailed analyses of fine atomic structure, chemical composition, and time-resolved single-photon photoluminescence data for the same individual nanocrystals, we reveal inhomogeneity in the quantum yields of single nonblinking “giant” CdSe/CdS core/shell quantum dots (g-QDs). We find that each g-QD possesses distinctive single exciton and biexciton quantum yields that result mainly from variations in the degree of charging,more » rather than from volume or structure inhomogeneity. We further establish that there is a very limited nonemissive “dark” fraction (<2%) among the studied g-QDs and present direct evidence that the g-QD core must lack inorganic passivation for the g-QD to be “dark”. Finally and therefore, in contrast to conventional QDs, ensemble photoluminescence quantum yield is principally defined by charging processes rather than the existence of dark g-QDs.« less

Bohm's Quantum Potential and the Visualization of Molecular Structure

NASA Technical Reports Server (NTRS)

Levit, Creon; Chancellor, Marisa K. (Technical Monitor)

1997-01-01

David Bohm's ontological interpretation of quantum theory can shed light on otherwise counter-intuitive quantum mechanical phenomena including chemical bonding. In the field of quantum chemistry, Richard Bader has shown that the topology of the Laplacian of the electronic charge density characterizes many features of molecular structure and reactivity. Visual and computational examination suggests that the Laplacian of Bader and the quantum potential of Bohm are morphologically equivalent. It appears that Bohmian mechanics and the quantum potential can make chemistry as clear as they makes physics.

Statistical moments of quantum-walk dynamics reveal topological quantum transitions.

PubMed

Cardano, Filippo; Maffei, Maria; Massa, Francesco; Piccirillo, Bruno; de Lisio, Corrado; De Filippis, Giulio; Cataudella, Vittorio; Santamato, Enrico; Marrucci, Lorenzo

2016-04-22

Many phenomena in solid-state physics can be understood in terms of their topological properties. Recently, controlled protocols of quantum walk (QW) are proving to be effective simulators of such phenomena. Here we report the realization of a photonic QW showing both the trivial and the non-trivial topologies associated with chiral symmetry in one-dimensional (1D) periodic systems. We find that the probability distribution moments of the walker position after many steps can be used as direct indicators of the topological quantum transition: while varying a control parameter that defines the system phase, these moments exhibit a slope discontinuity at the transition point. Numerical simulations strongly support the conjecture that these features are general of 1D topological systems. Extending this approach to higher dimensions, different topological classes, and other typologies of quantum phases may offer general instruments for investigating and experimentally detecting quantum transitions in such complex systems.

Combined friction force microscopy and quantum chemical investigation of the tribotronic response at the propylammonium nitrate-graphite interface.

PubMed

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.

Determination and correction of persistent biases in quantum annealers

PubMed Central

Perdomo-Ortiz, Alejandro; O’Gorman, Bryan; Fluegemann, Joseph; Biswas, Rupak; Smelyanskiy, Vadim N.

2016-01-01

Calibration of quantum computers is essential to the effective utilisation of their quantum resources. Specifically, the performance of quantum annealers is likely to be significantly impaired by noise in their programmable parameters, effectively misspecification of the computational problem to be solved, often resulting in spurious suboptimal solutions. We developed a strategy to determine and correct persistent, systematic biases between the actual values of the programmable parameters and their user-specified values. We applied the recalibration strategy to two D-Wave Two quantum annealers, one at NASA Ames Research Center in Moffett Field, California, and another at D-Wave Systems in Burnaby, Canada. We show that the recalibration procedure not only reduces the magnitudes of the biases in the programmable parameters but also enhances the performance of the device on a set of random benchmark instances. PMID:26783120

Quantum games on evolving random networks

NASA Astrophysics Data System (ADS)

Pawela, Łukasz

2016-09-01

We study the advantages of quantum strategies in evolutionary social dilemmas on evolving random networks. We focus our study on the two-player games: prisoner's dilemma, snowdrift and stag-hunt games. The obtained result show the benefits of quantum strategies for the prisoner's dilemma game. For the other two games, we obtain regions of parameters where the quantum strategies dominate, as well as regions where the classical strategies coexist.

Effects of quantum confinement and shape on band gap of core/shell quantum dots and nanowires

NASA Astrophysics Data System (ADS)

Gao, Faming

2011-05-01

A quantum confinement model for nanocrystals developed is extended to study for the optical gap shifts in core/shell quantum dots and nanowires. The chemical bond properties and gap shifts in the InP/ZnS, CdSe/CdS, CdSe/ZnS, and CdTe/ZnS core/shell quantum dots are calculated in detail. The calculated band gaps are in excellent agreement with experimental values. The effects of structural taping and twinning on quantum confinement of InP and Si nanowires are elucidated. It is found theoretically that a competition between the positive Kubo energy-gap shift and the negative surface energy shift plays the crucial role in the optical gaps of these nanosystems.

Error Sensitivity to Environmental Noise in Quantum Circuits for Chemical State Preparation.

PubMed

Sawaya, Nicolas P D; Smelyanskiy, Mikhail; McClean, Jarrod R; Aspuru-Guzik, Alán

2016-07-12

Calculating molecular energies is likely to be one of the first useful applications to achieve quantum supremacy, performing faster on a quantum than a classical computer. However, if future quantum devices are to produce accurate calculations, errors due to environmental noise and algorithmic approximations need to be characterized and reduced. In this study, we use the high performance qHiPSTER software to investigate the effects of environmental noise on the preparation of quantum chemistry states. We simulated 18 16-qubit quantum circuits under environmental noise, each corresponding to a unitary coupled cluster state preparation of a different molecule or molecular configuration. Additionally, we analyze the nature of simple gate errors in noise-free circuits of up to 40 qubits. We find that, in most cases, the Jordan-Wigner (JW) encoding produces smaller errors under a noisy environment as compared to the Bravyi-Kitaev (BK) encoding. For the JW encoding, pure dephasing noise is shown to produce substantially smaller errors than pure relaxation noise of the same magnitude. We report error trends in both molecular energy and electron particle number within a unitary coupled cluster state preparation scheme, against changes in nuclear charge, bond length, number of electrons, noise types, and noise magnitude. These trends may prove to be useful in making algorithmic and hardware-related choices for quantum simulation of molecular energies.

Chloramine demand estimation using surrogate chemical and microbiological parameters.

PubMed

Moradi, Sina; Liu, Sanly; Chow, Christopher W K; van Leeuwen, John; Cook, David; Drikas, Mary; Amal, Rose

2017-07-01

A model is developed to enable estimation of chloramine demand in full scale drinking water supplies based on chemical and microbiological factors that affect chloramine decay rate via nonlinear regression analysis method. The model is based on organic character (specific ultraviolet absorbance (SUVA)) of the water samples and a laboratory measure of the microbiological (F m ) decay of chloramine. The applicability of the model for estimation of chloramine residual (and hence chloramine demand) was tested on several waters from different water treatment plants in Australia through statistical test analysis between the experimental and predicted data. Results showed that the model was able to simulate and estimate chloramine demand at various times in real drinking water systems. To elucidate the loss of chloramine over the wide variation of water quality used in this study, the model incorporates both the fast and slow chloramine decay pathways. The significance of estimated fast and slow decay rate constants as the kinetic parameters of the model for three water sources in Australia was discussed. It was found that with the same water source, the kinetic parameters remain the same. This modelling approach has the potential to be used by water treatment operators as a decision support tool in order to manage chloramine disinfection. Copyright © 2017. Published by Elsevier B.V.

Accidental degeneracies in nonlinear quantum deformed systems

NASA Astrophysics Data System (ADS)

Aleixo, A. N. F.; Balantekin, A. B.

2011-09-01

We construct a multi-parameter nonlinear deformed algebra for quantum confined systems that includes many other deformed models as particular cases. We demonstrate that such systems exhibit the property of accidental pairwise energy level degeneracies. We also study, as a special case of our multi-parameter deformation formalism, the extension of the Tamm-Dancoff cutoff deformed oscillator and the occurrence of accidental pairwise degeneracy in the energy levels of the deformed system. As an application, we discuss the case of a trigonometric Rosen-Morse potential, which is successfully used in models for quantum confined systems, ranging from electrons in quantum dots to quarks in hadrons.

[Optimization of the parameters of microcirculatory structural adaptation model based on improved quantum-behaved particle swarm optimization algorithm].

PubMed

Pan, Qing; Yao, Jialiang; Wang, Ruofan; Cao, Ping; Ning, Gangmin; Fang, Luping

2017-08-01

The vessels in the microcirculation keep adjusting their structure to meet the functional requirements of the different tissues. A previously developed theoretical model can reproduce the process of vascular structural adaptation to help the study of the microcirculatory physiology. However, until now, such model lacks the appropriate methods for its parameter settings with subsequent limitation of further applications. This study proposed an improved quantum-behaved particle swarm optimization (QPSO) algorithm for setting the parameter values in this model. The optimization was performed on a real mesenteric microvascular network of rat. The results showed that the improved QPSO was superior to the standard particle swarm optimization, the standard QPSO and the previously reported Downhill algorithm. We conclude that the improved QPSO leads to a better agreement between mathematical simulation and animal experiment, rendering the model more reliable in future physiological studies.

Quantum-Like Bayesian Networks for Modeling Decision Making

PubMed Central

Moreira, Catarina; Wichert, Andreas

2016-01-01

In this work, we explore an alternative quantum structure to perform quantum probabilistic inferences to accommodate the paradoxical findings of the Sure Thing Principle. We propose a Quantum-Like Bayesian Network, which consists in replacing classical probabilities by quantum probability amplitudes. However, since this approach suffers from the problem of exponential growth of quantum parameters, we also propose a similarity heuristic that automatically fits quantum parameters through vector similarities. This makes the proposed model general and predictive in contrast to the current state of the art models, which cannot be generalized for more complex decision scenarios and that only provide an explanatory nature for the observed paradoxes. In the end, the model that we propose consists in a nonparametric method for estimating inference effects from a statistical point of view. It is a statistical model that is simpler than the previous quantum dynamic and quantum-like models proposed in the literature. We tested the proposed network with several empirical data from the literature, mainly from the Prisoner's Dilemma game and the Two Stage Gambling game. The results obtained show that the proposed quantum Bayesian Network is a general method that can accommodate violations of the laws of classical probability theory and make accurate predictions regarding human decision-making in these scenarios. PMID:26858669

Estimation of Physical Properties and Chemical Reactivity Parameters of Organic Compounds for Environmental Modeling by SPARC

EPA Science Inventory

Mathematical models for predicting the transport and fate of pollutants in the environment require reactivity parameter values that is value of the physical and chemical constants that govern reactivity. Although empirical structure activity relationships have been developed th...

Preface: Special Topic on Nuclear Quantum Effects

NASA Astrophysics Data System (ADS)

Tuckerman, Mark; Ceperley, David

2018-03-01

Although the observable universe strictly obeys the laws of quantum mechanics, in many instances, a classical description that either ignores quantum effects entirely or accounts for them at a very crude level is sufficient to describe a wide variety of phenomena. However, when this approximation breaks down, as is often the case for processes involving light nuclei, a full quantum treatment becomes indispensable. This Special Topic in The Journal of Chemical Physics showcases recent advances in our understanding of nuclear quantum effects in condensed phases as well as novel algorithmic developments and applications that have enhanced the capability to study these effects.

Preface: Special Topic on Nuclear Quantum Effects.

PubMed

Tuckerman, Mark; Ceperley, David

2018-03-14

Although the observable universe strictly obeys the laws of quantum mechanics, in many instances, a classical description that either ignores quantum effects entirely or accounts for them at a very crude level is sufficient to describe a wide variety of phenomena. However, when this approximation breaks down, as is often the case for processes involving light nuclei, a full quantum treatment becomes indispensable. This Special Topic in The Journal of Chemical Physics showcases recent advances in our understanding of nuclear quantum effects in condensed phases as well as novel algorithmic developments and applications that have enhanced the capability to study these effects.

Clinical Potential of Quantum Dots

PubMed Central

Iga, Arthur M.; Robertson, John H. P.; Winslet, Marc C.; Seifalian, Alexander M.

2007-01-01

Advances in nanotechnology have led to the development of novel fluorescent probes called quantum dots. Quantum dots have revolutionalized the processes of tagging molecules within research settings and are improving sentinel lymph node mapping and identification in vivo studies. As the unique physical and chemical properties of these fluorescent probes are being unraveled, new potential methods of early cancer detection, rapid spread and therapeutic management, that is, photodynamic therapy are being explored. Encouraging results of optical and real time identification of sentinel lymph nodes and lymph flow using quantum dots in vivo models are emerging. Quantum dots have also superseded many of the limitations of organic fluorophores and are a promising alternative as a research tool. In this review, we examine the promising clinical potential of quantum dots, their hindrances for clinical use and the current progress in abrogating their inherent toxicity. PMID:18317518

Interaction of surface hydroxyls with adsorbed molecules. A quantum-chemical study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Geerlings, P.; Tariel, N.; Botrel, A.

1984-11-08

A study has been conducted to explain the interaction mechanisms of (bridging and terminal) surface hydroxyl groups with molecules, using ab initio, EHT, and CNDO/2-FA quantum-chemical calculations. Bond strength variations and charge shifts were found to be in complete agreement with Gutmann's rules, and provide a basis for the understanding of the Bronsted acid properties of zeolites and amorphous silica-alumina. A quantitative measure of the interaction strength is possible by referring to the experimentally determined donor number (Gutmann) following many molecules, but care should be taken for those molecules for which the donor strength was determined by indirect methods. Onlymore » a few exceptions to Gutmann's rules should exist, e.g., in those cases where the atom interacting with the proton is not the most electronegative of the donor molecule (such as for CO). Individual bonds in a given complex are more susceptible to perturbations (changes in composition and interactions with adsorbing molecules) if the coordination number increases. These rules are in agreement with the observations and apply to all reactions (inter- or intramolecular) involving a change in coordination. 52 references, 6 figures, 4 tables.« less

Structural properties of templated Ge quantum dot arrays: impact of growth and pre-pattern parameters

NASA Astrophysics Data System (ADS)

Tempeler, J.; Danylyuk, S.; Brose, S.; Loosen, P.; Juschkin, L.

2018-07-01

In this study we analyze the impact of process and growth parameters on the structural properties of germanium (Ge) quantum dot (QD) arrays. The arrays were deposited by molecular-beam epitaxy on pre-patterned silicon (Si) substrates. Periodic arrays of pits with diameters between 120 and 20 nm and pitches ranging from 200 nm down to 40 nm were etched into the substrate prior to growth. The structural perfection of the two-dimensional QD arrays was evaluated based on SEM images. The impact of two processing steps on the directed self-assembly of Ge QD arrays is investigated. First, a thin Si buffer layer grown on a pre-patterned substrate reshapes the pre-pattern pits and determines the nucleation and initial shape of the QDs. Subsequently, the deposition parameters of the Ge define the overall shape and uniformity of the QDs. In particular, the growth temperature and the deposition rate are relevant and need to be optimized according to the design of the pre-pattern. Applying this knowledge, we are able to fabricate regular arrays of pyramid shaped QDs with dot densities up to 7.2 × 1010 cm‑2.

Structural properties of templated Ge quantum dot arrays: impact of growth and pre-pattern parameters.

PubMed

Tempeler, J; Danylyuk, S; Brose, S; Loosen, P; Juschkin, L

2018-07-06

In this study we analyze the impact of process and growth parameters on the structural properties of germanium (Ge) quantum dot (QD) arrays. The arrays were deposited by molecular-beam epitaxy on pre-patterned silicon (Si) substrates. Periodic arrays of pits with diameters between 120 and 20 nm and pitches ranging from 200 nm down to 40 nm were etched into the substrate prior to growth. The structural perfection of the two-dimensional QD arrays was evaluated based on SEM images. The impact of two processing steps on the directed self-assembly of Ge QD arrays is investigated. First, a thin Si buffer layer grown on a pre-patterned substrate reshapes the pre-pattern pits and determines the nucleation and initial shape of the QDs. Subsequently, the deposition parameters of the Ge define the overall shape and uniformity of the QDs. In particular, the growth temperature and the deposition rate are relevant and need to be optimized according to the design of the pre-pattern. Applying this knowledge, we are able to fabricate regular arrays of pyramid shaped QDs with dot densities up to 7.2 × 10 10 cm -2 .

Conceptual versus Algorithmic Learning in High School Chemistry: The Case of Basic Quantum Chemical Concepts--Part 1. Statistical Analysis of a Quantitative Study

ERIC Educational Resources Information Center

Papaphotis, Georgios; Tsaparlis, Georgios

2008-01-01

Part 1 of the findings are presented of a quantitative study (n = 125) on basic quantum chemical concepts taught in the twelfth grade (age 17-18 years) in Greece. A paper-and-pencil test of fourteen questions was used. The study compared performance in five questions that tested recall of knowledge or application of algorithmic procedures (type-A…

Quantum Games under Decoherence

NASA Astrophysics Data System (ADS)

Huang, Zhiming; Qiu, Daowen

2016-02-01

Quantum systems are easily influenced by ambient environments. Decoherence is generated by system interaction with external environment. In this paper, we analyse the effects of decoherence on quantum games with Eisert-Wilkens-Lewenstein (EWL) (Eisert et al., Phys. Rev. Lett. 83(15), 3077 1999) and Marinatto-Weber (MW) (Marinatto and Weber, Phys. Lett. A 272, 291 2000) schemes. Firstly, referring to the analytical approach that was introduced by Eisert et al. (Phys. Rev. Lett. 83(15), 3077 1999), we analyse the effects of decoherence on quantum Chicken game by considering different traditional noisy channels. We investigate the Nash equilibria and changes of payoff in specific two-parameter strategy set for maximally entangled initial states. We find that the Nash equilibria are different in different noisy channels. Since Unruh effect produces a decoherence-like effect and can be perceived as a quantum noise channel (Omkar et al., arXiv: 1408.1477v1), with the same two parameter strategy set, we investigate the influences of decoherence generated by the Unruh effect on three-player quantum Prisoners' Dilemma, the non-zero sum symmetric multiplayer quantum game both for unentangled and entangled initial states. We discuss the effect of the acceleration of noninertial frames on the the game's properties such as payoffs, symmetry, Nash equilibrium, Pareto optimal, dominant strategy, etc. Finally, we study the decoherent influences of correlated noise and Unruh effect on quantum Stackelberg duopoly for entangled and unentangled initial states with the depolarizing channel. Our investigations show that under the influence of correlated depolarizing channel and acceleration in noninertial frame, some critical points exist for an unentangled initial state at which firms get equal payoffs and the game becomes a follower advantage game. It is shown that the game is always a leader advantage game for a maximally entangled initial state and there appear some points at which

Controlling the Properties of Matter with Quantum Dots

DOE Office of Scientific and Technical Information (OSTI.GOV)

Klimov, Victor

2017-03-22

Solar cells and photodetectors could soon be made from new types of materials based on semiconductor quantum dots, thanks to new insights based on ultrafast measurements capturing real-time photoconversion processes. Photoconversion is a process wherein the energy of a photon, or quantum of light, is converted into other forms of energy, for example, chemical or electrical. Semiconductor quantum dots are chemically synthesized crystalline nanoparticles that have been studied for more than three decades in the context of various photoconversion schemes including photovoltaics (generation of photo-electricity) and photo-catalysis (generation of “solar fuels”). The appeal of quantum dots comes from the unmatchedmore » tunability of their physical properties, which can be adjusted by controlling the size, shape and composition of the dots. At Los Alamos, the research connects to the institutional mission of solving national security challenges through scientific excellence, in this case focusing on novel physical principles for highly efficient photoconversion, charge manipulation in exploratory device structures and novel nanomaterials.« less

Superconducting Qubits as Mechanical Quantum Engines

NASA Astrophysics Data System (ADS)

Sachtleben, Kewin; Mazon, Kahio T.; Rego, Luis G. C.

2017-09-01

We propose the equivalence of superconducting qubits with a pistonlike mechanical quantum engine. The work reports a study on the nature of the nonequilibrium work exchanged with the quantum-nonadiabatic working medium, which is modeled as a multilevel coupled quantum well system subject to an external control parameter. The quantum dynamics is solved for arbitrary control protocols. It is shown that the work output has two components: one that depends instantaneously on the level populations and another that is due to the quantum coherences built in the system. The nonadiabatic coherent dynamics of the quantum engine gives rise to a resistance (friction) force that decreases the work output. We consider the functional equivalence of such a device and a rf-SQUID flux qubit.

Quantum Simulation of the Quantum Rabi Model in a Trapped Ion

NASA Astrophysics Data System (ADS)

Lv, Dingshun; An, Shuoming; Liu, Zhenyu; Zhang, Jing-Ning; Pedernales, Julen S.; Lamata, Lucas; Solano, Enrique; Kim, Kihwan

2018-04-01

The quantum Rabi model, involving a two-level system and a bosonic field mode, is arguably the simplest and most fundamental model describing quantum light-matter interactions. Historically, due to the restricted parameter regimes of natural light-matter processes, the richness of this model has been elusive in the lab. Here, we experimentally realize a quantum simulation of the quantum Rabi model in a single trapped ion, where the coupling strength between the simulated light mode and atom can be tuned at will. The versatility of the demonstrated quantum simulator enables us to experimentally explore the quantum Rabi model in detail, including a wide range of otherwise unaccessible phenomena, as those happening in the ultrastrong and deep strong-coupling regimes. In this sense, we are able to adiabatically generate the ground state of the quantum Rabi model in the deep strong-coupling regime, where we are able to detect the nontrivial entanglement between the bosonic field mode and the two-level system. Moreover, we observe the breakdown of the rotating-wave approximation when the coupling strength is increased, and the generation of phonon wave packets that bounce back and forth when the coupling reaches the deep strong-coupling regime. Finally, we also measure the energy spectrum of the quantum Rabi model in the ultrastrong-coupling regime.

On-chip quantum interference of a superconducting microsphere

NASA Astrophysics Data System (ADS)

Pino, H.; Prat-Camps, J.; Sinha, K.; Prasanna Venkatesh, B.; Romero-Isart, O.

2018-04-01

We propose and analyze an all-magnetic scheme to perform a Young’s double slit experiment with a micron-sized superconducting sphere of mass ≳ {10}13 amu. We show that its center of mass could be prepared in a spatial quantum superposition state with an extent of the order of half a micrometer. The scheme is based on magnetically levitating the sphere above a superconducting chip and letting it skate through a static magnetic potential landscape where it interacts for short intervals with quantum circuits. In this way, a protocol for fast quantum interferometry using quantum magnetomechanics is passively implemented. Such a table-top earth-based quantum experiment would operate in a parameter regime where gravitational energy scales become relevant. In particular, we show that the faint parameter-free gravitationally-induced decoherence collapse model, proposed by Diósi and Penrose, could be unambiguously falsified.

Semiempirical Quantum Mechanical Methods for Noncovalent Interactions for Chemical and Biochemical Applications

PubMed Central

2016-01-01

Semiempirical (SE) methods can be derived from either Hartree–Fock or density functional theory by applying systematic approximations, leading to efficient computational schemes that are several orders of magnitude faster than ab initio calculations. Such numerical efficiency, in combination with modern computational facilities and linear scaling algorithms, allows application of SE methods to very large molecular systems with extensive conformational sampling. To reliably model the structure, dynamics, and reactivity of biological and other soft matter systems, however, good accuracy for the description of noncovalent interactions is required. In this review, we analyze popular SE approaches in terms of their ability to model noncovalent interactions, especially in the context of describing biomolecules, water solution, and organic materials. We discuss the most significant errors and proposed correction schemes, and we review their performance using standard test sets of molecular systems for quantum chemical methods and several recent applications. The general goal is to highlight both the value and limitations of SE methods and stimulate further developments that allow them to effectively complement ab initio methods in the analysis of complex molecular systems. PMID:27074247

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

PubMed

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.

Statistical moments of quantum-walk dynamics reveal topological quantum transitions

PubMed Central

Cardano, Filippo; Maffei, Maria; Massa, Francesco; Piccirillo, Bruno; de Lisio, Corrado; De Filippis, Giulio; Cataudella, Vittorio; Santamato, Enrico; Marrucci, Lorenzo

2016-01-01

Many phenomena in solid-state physics can be understood in terms of their topological properties. Recently, controlled protocols of quantum walk (QW) are proving to be effective simulators of such phenomena. Here we report the realization of a photonic QW showing both the trivial and the non-trivial topologies associated with chiral symmetry in one-dimensional (1D) periodic systems. We find that the probability distribution moments of the walker position after many steps can be used as direct indicators of the topological quantum transition: while varying a control parameter that defines the system phase, these moments exhibit a slope discontinuity at the transition point. Numerical simulations strongly support the conjecture that these features are general of 1D topological systems. Extending this approach to higher dimensions, different topological classes, and other typologies of quantum phases may offer general instruments for investigating and experimentally detecting quantum transitions in such complex systems. PMID:27102945

Quantum chemical determination of Young's modulus of lignin. Calculations on a beta-O-4' model compound.

PubMed

Elder, Thomas

2007-11-01

The calculation of Young's modulus of lignin has been examined by subjecting a dimeric model compound to strain, coupled with the determination of energy and stress. The computational results, derived from quantum chemical calculations, are in agreement with available experimental results. Changes in geometry indicate that modifications in dihedral angles occur in response to linear strain. At larger levels of strain, bond rupture is evidenced by abrupt changes in energy, structure, and charge. Based on the current calculations, the bond scission may be occurring through a homolytic reaction between aliphatic carbon atoms. These results may have implications in the reactivity of lignin especially when subjected to processing methods that place large mechanical forces on the structure.

Electromechanical quantum simulators

NASA Astrophysics Data System (ADS)

Tacchino, F.; Chiesa, A.; LaHaye, M. D.; Carretta, S.; Gerace, D.

2018-06-01

Digital quantum simulators are among the most appealing applications of a quantum computer. Here we propose a universal, scalable, and integrated quantum computing platform based on tunable nonlinear electromechanical nano-oscillators. It is shown that very high operational fidelities for single- and two-qubits gates can be achieved in a minimal architecture, where qubits are encoded in the anharmonic vibrational modes of mechanical nanoresonators, whose effective coupling is mediated by virtual fluctuations of an intermediate superconducting artificial atom. An effective scheme to induce large single-phonon nonlinearities in nanoelectromechanical devices is explicitly discussed, thus opening the route to experimental investigation in this direction. Finally, we explicitly show the very high fidelities that can be reached for the digital quantum simulation of model Hamiltonians, by using realistic experimental parameters in state-of-the-art devices, and considering the transverse field Ising model as a paradigmatic example.

Multiparameter Estimation in Networked Quantum Sensors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Proctor, Timothy J.; Knott, Paul A.; Dunningham, Jacob A.

We introduce a general model for a network of quantum sensors, and we use this model to consider the question: When can entanglement between the sensors, and/or global measurements, enhance the precision with which the network can measure a set of unknown parameters? We rigorously answer this question by presenting precise theorems proving that for a broad class of problems there is, at most, a very limited intrinsic advantage to using entangled states or global measurements. Moreover, for many estimation problems separable states and local measurements are optimal, and can achieve the ultimate quantum limit on the estimation uncertainty. Thismore » immediately implies that there are broad conditions under which simultaneous estimation of multiple parameters cannot outperform individual, independent estimations. Our results apply to any situation in which spatially localized sensors are unitarily encoded with independent parameters, such as when estimating multiple linear or non-linear optical phase shifts in quantum imaging, or when mapping out the spatial profile of an unknown magnetic field. We conclude by showing that entangling the sensors can enhance the estimation precision when the parameters of interest are global properties of the entire network.« less

Multiparameter Estimation in Networked Quantum Sensors

NASA Astrophysics Data System (ADS)

Proctor, Timothy J.; Knott, Paul A.; Dunningham, Jacob A.

2018-02-01

We introduce a general model for a network of quantum sensors, and we use this model to consider the following question: When can entanglement between the sensors, and/or global measurements, enhance the precision with which the network can measure a set of unknown parameters? We rigorously answer this question by presenting precise theorems proving that for a broad class of problems there is, at most, a very limited intrinsic advantage to using entangled states or global measurements. Moreover, for many estimation problems separable states and local measurements are optimal, and can achieve the ultimate quantum limit on the estimation uncertainty. This immediately implies that there are broad conditions under which simultaneous estimation of multiple parameters cannot outperform individual, independent estimations. Our results apply to any situation in which spatially localized sensors are unitarily encoded with independent parameters, such as when estimating multiple linear or nonlinear optical phase shifts in quantum imaging, or when mapping out the spatial profile of an unknown magnetic field. We conclude by showing that entangling the sensors can enhance the estimation precision when the parameters of interest are global properties of the entire network.

Multiparameter Estimation in Networked Quantum Sensors

DOE PAGES

Proctor, Timothy J.; Knott, Paul A.; Dunningham, Jacob A.

2018-02-21

We introduce a general model for a network of quantum sensors, and we use this model to consider the question: When can entanglement between the sensors, and/or global measurements, enhance the precision with which the network can measure a set of unknown parameters? We rigorously answer this question by presenting precise theorems proving that for a broad class of problems there is, at most, a very limited intrinsic advantage to using entangled states or global measurements. Moreover, for many estimation problems separable states and local measurements are optimal, and can achieve the ultimate quantum limit on the estimation uncertainty. Thismore » immediately implies that there are broad conditions under which simultaneous estimation of multiple parameters cannot outperform individual, independent estimations. Our results apply to any situation in which spatially localized sensors are unitarily encoded with independent parameters, such as when estimating multiple linear or non-linear optical phase shifts in quantum imaging, or when mapping out the spatial profile of an unknown magnetic field. We conclude by showing that entangling the sensors can enhance the estimation precision when the parameters of interest are global properties of the entire network.« less

A new chalcone structure of (E)-1-(4-Bromophenyl)-3-(napthalen-2-yl)prop-2-en-1-one: Synthesis, structural characterizations, quantum chemical investigations and biological evaluations.

PubMed

Thanigaimani, Kaliyaperumal; Arshad, Suhana; Khalib, Nuridayanti Che; Razak, Ibrahim Abdul; Arunagiri, C; Subashini, A; Sulaiman, Shaida Fariza; Hashim, Nurul Shafiqah; Ooi, Kheng Leong

2015-01-01

The structure of (E)-1-(4-Bromophenyl)-3-(napthalen-2-yl)prop-2-en-1-one (C19H13BrO) crystallized in the triclinic system of P-1 space group. The unit cell dimensions are: a=5.8944 (9)Å, b=7.8190 (12)Å, c=16.320 (2)Å, α=102.4364 (19)°, β=95.943 (2)°, γ=96.274 (2)° and Z=2. The physical properties of this compound was determined by the spectroscopic methods (FTIR and (1)H and (13)C NMR). Quantum chemical investigations have been employed to investigate the structural and spectral properties. The molecular structure, vibrational assignments, (1)H and (13)C NMR chemical shift values, non-linear optical (NLO) effect, HOMO-LUMO analysis and natural bonding orbital (NBO) analysis were calculated using HF and DFT/B3LYP methods with 6-311++G(d,p) basis set in the ground state. The results show that the theoretical calculation of the geometrical parameters, vibrational frequencies and chemical shifts are comparable with the experimental data. The crystal structure is influenced and stabilized by weak C-H⋯π interactions connecting the molecules into infinite supramolecular one dimensional ladder-like arrangement. Additionally, this compound is evaluated for their antibacterial activities against gram positive and gram negative strains using a micro dilution procedure and shows activities against a panel of microorganisms. Copyright © 2015 Elsevier B.V. All rights reserved.

Are Cloned Quantum States Macroscopic?

NASA Astrophysics Data System (ADS)

Fröwis, F.; Dür, W.

2012-10-01

We study quantum states produced by optimal phase covariant quantum cloners. We argue that cloned quantum superpositions are not macroscopic superpositions in the spirit of Schrödinger’s cat, despite their large particle number. This is indicated by calculating several measures for macroscopic superpositions from the literature, as well as by investigating the distinguishability of the two superposed cloned states. The latter rapidly diminishes when considering imperfect detectors or noisy states and does not increase with the system size. In contrast, we find that cloned quantum states themselves are macroscopic, in the sense of both proposed measures and their usefulness in quantum metrology with an optimal scaling in system size. We investigate the applicability of cloned states for parameter estimation in the presence of different kinds of noise.

Quantum chemical investigations of AlN-doped C60 for use as a nano-biosensor in detection of mispairing between DNA bases.

PubMed

Siddiqui, Shamoon Ahmad; Bouarissa, Nadir; Rasheed, Tabish; Al-Hajry, A

2014-12-01

Quantum chemical calculations were carried out to study the electronic structure and stability of adenine-thymine and the rare tautomer of adenine-thymine base pairs along with their Cu 2+ complexes and their interactions with AlN-modified fullerene (C58AlN) using Density Functional Theory (B3LYP method). Since, these two forms of base pairs and their Cu 2+ complexes have almost similar electronic structures, their chemical differentiation is an extremely difficult task. In this investigation, we have observed that AlN-doped C 60 could be used as a potentially viable nanoscale sensor to detect these two base pairs as well as their Cu2+ complexes.

Use of external cavity quantum cascade laser compliance voltage in real-time trace gas sensing of multiple chemicals

NASA Astrophysics Data System (ADS)

Phillips, Mark C.; Taubman, Matthew S.; Kriesel, Jason

2015-01-01

We describe a prototype trace gas sensor designed for real-time detection of multiple chemicals. The sensor uses an external cavity quantum cascade laser (ECQCL) swept over its tuning range of 940-1075 cm-1 (9.30-10.7 μm) at a 10 Hz repetition rate. The sensor was designed for operation in multiple modes, including gas sensing within a multi-pass Heriott cell and intracavity absorption sensing using the ECQCL compliance voltage. In addition, the ECQCL compliance voltage was used to reduce effects of long-term drifts in the ECQCL output power. The sensor was characterized for noise, drift, and detection of chemicals including ammonia, methanol, ethanol, isopropanol, Freon- 134a, Freon-152a, and diisopropyl methylphosphonate (DIMP). We also present use of the sensor for mobile detection of ammonia downwind of cattle facilities, in which concentrations were recorded at 1-s intervals.

Quantum Chemistry, 5th Edition by Ira N. Levine

NASA Astrophysics Data System (ADS)

Hinde, Robert J.

2000-12-01

Of course, there is no one- or two-week shortcut by which nonspecialists can master enough quantum mechanics to become informed users of quantum chemical techniques. Nevertheless, a text that integrated the fundamentals of quantum theory with a rigorous introduction to quantum chemistry could help instructors design a class that would benefit both these nonspecialists and graduate students in physical chemistry. Could such a class overcome the (undeserved) stigma associated with the physical chemistry curriculum? That remains to be seen.

Slow-roll approximation in loop quantum cosmology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Luc, Joanna; Mielczarek, Jakub, E-mail: joanna.luc@uj.edu.pl, E-mail: jakub.mielczarek@uj.edu.pl

The slow-roll approximation is an analytical approach to study dynamical properties of the inflationary universe. In this article, systematic construction of the slow-roll expansion for effective loop quantum cosmology is presented. The analysis is performed up to the fourth order in both slow-roll parameters and the parameter controlling the strength of deviation from the classical case. The expansion is performed for three types of the slow-roll parameters: Hubble slow-roll parameters, Hubble flow parameters and potential slow-roll parameters. An accuracy of the approximation is verified by comparison with the numerical phase space trajectories for the case with a massive potential term.more » The results obtained in this article may be helpful in the search for the subtle quantum gravitational effects with use of the cosmological data.« less

Non-Markovianity hinders Quantum Darwinism.

PubMed

Galve, Fernando; Zambrini, Roberta; Maniscalco, Sabrina

2016-01-20

We investigate Quantum Darwinism and the emergence of a classical world from the quantum one in connection with the spectral properties of the environment. We use a microscopic model of quantum environment in which, by changing a simple system parameter, we can modify the information back flow from environment into the system, and therefore its non-Markovian character. We show that the presence of memory effects hinders the emergence of classical objective reality, linking these two apparently unrelated concepts via a unique dynamical feature related to decoherence factors.

Non-Markovianity hinders Quantum Darwinism

NASA Astrophysics Data System (ADS)

Galve, Fernando; Zambrini, Roberta; Maniscalco, Sabrina

2016-01-01

We investigate Quantum Darwinism and the emergence of a classical world from the quantum one in connection with the spectral properties of the environment. We use a microscopic model of quantum environment in which, by changing a simple system parameter, we can modify the information back flow from environment into the system, and therefore its non-Markovian character. We show that the presence of memory effects hinders the emergence of classical objective reality, linking these two apparently unrelated concepts via a unique dynamical feature related to decoherence factors.

Non-Markovianity hinders Quantum Darwinism

PubMed Central

Galve, Fernando; Zambrini, Roberta; Maniscalco, Sabrina

2016-01-01

We investigate Quantum Darwinism and the emergence of a classical world from the quantum one in connection with the spectral properties of the environment. We use a microscopic model of quantum environment in which, by changing a simple system parameter, we can modify the information back flow from environment into the system, and therefore its non-Markovian character. We show that the presence of memory effects hinders the emergence of classical objective reality, linking these two apparently unrelated concepts via a unique dynamical feature related to decoherence factors. PMID:26786857

In situ electron-beam polymerization stabilized quantum dot micelles.

PubMed

Travert-Branger, Nathalie; Dubois, Fabien; Renault, Jean-Philippe; Pin, Serge; Mahler, Benoit; Gravel, Edmond; Dubertret, Benoit; Doris, Eric

2011-04-19

A polymerizable amphiphile polymer containing PEG was synthesized and used to encapsulate quantum dots in micelles. The quantum dot micelles were then polymerized using a "clean" electron beam process that did not require any post-irradiation purification. Fluorescence spectroscopy revealed that the polymerized micelles provided an organic coating that preserved the quantum dot fluorescence better than nonpolymerized micelles, even under harsh conditions. © 2011 American Chemical Society

The fluorescence intensities ratio is not a reliable parameter for evaluation of protein unfolding transitions.

PubMed

Žoldák, Gabriel; Jancura, Daniel; Sedlák, Erik

2017-06-01

Monitoring the fluorescence of proteins, particularly the fluorescence of intrinsic tryptophan residues, is a popular method often used in the analysis of unfolding transitions (induced by temperature, chemical denaturant, and pH) in proteins. The tryptophan fluorescence provides several suitable parameters, such as steady-state fluorescence intensity, apparent quantum yield, mean fluorescence lifetime, position of emission maximum that are often utilized for the observation of the conformational/unfolding transitions of proteins. In addition, the fluorescence intensities ratio at different wavelengths (usually at 330 nm and 350 nm) is becoming an increasingly popular parameter for the evaluation of thermal transitions. We show that, under certain conditions, the use of this parameter for the analysis of unfolding transitions leads to the incorrect determination of thermodynamic parameters characterizing unfolding transitions in proteins (e.g., melting temperature) and, hence, can compromise the hit identification during high-throughput drug screening campaigns. © 2017 The Protein Society.

Conformation of the azo bond and its influence on the molecular and crystal structures, IR and Raman spectra, and electron properties of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine - Quantum chemical DFT calculations.

PubMed

Michalski, J; Bryndal, I; Lorenc, J; Hermanowicz, K; Janczak, J; Hanuza, J

2018-02-15

The crystal and molecular structures of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine have been determined by X-ray diffraction and quantum chemical DFT calculations. The crystal is monoclinic, space group Cc (No. 9) with Z=4 with the unit cell parameters: a=12.083(7), b=12.881(6), c=8.134(3) Å and β=97.09(5)°. The azo-bridge appears in the trans conformation in which C2-N2-N2'-C1' torsion angle takes a value -178.6(3)°, whereas the dihedral angle between the planes of the phenyl and pyridine rings is 3.5(2)°. The IR and Raman spectra measured in the temperature range 80-350K and quantum chemical calculations with the use of B3LYP/6-311G(2d,2p) approach confirmed the trans configuration of the azo-bridge as the most stable energetically and allowed determination of the energy other virtual structures. The observed effects were used in the discussion of vibrational dynamics of the studied compound. The energy gap between cis and trans conformers equals to 1.054eV (0.03873 Hartree). The electron absorption and emission spectra have been measured and analyzed on the basis of DFT calculations. The life time of the excited state is 12μs and the Stokes shift is close to 5470cm -1 . Copyright © 2017 Elsevier B.V. All rights reserved.

Conformation of the azo bond and its influence on the molecular and crystal structures, IR and Raman spectra, and electron properties of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine - Quantum chemical DFT calculations

NASA Astrophysics Data System (ADS)

Michalski, J.; Bryndal, I.; Lorenc, J.; Hermanowicz, K.; Janczak, J.; Hanuza, J.

2018-02-01

The crystal and molecular structures of 6-methyl-3,5-dinitro-2-[(E)-phenyldiazenyl]pyridine have been determined by X-ray diffraction and quantum chemical DFT calculations. The crystal is monoclinic, space group Cc (No. 9) with Z = 4 with the unit cell parameters: a = 12.083(7), b = 12.881(6), c = 8.134(3) Å and β = 97.09(5)°. The azo-bridge appears in the trans conformation in which C2-N2-N2‧-C1‧ torsion angle takes a value - 178.6(3)°, whereas the dihedral angle between the planes of the phenyl and pyridine rings is 3.5(2)°. The IR and Raman spectra measured in the temperature range 80-350 K and quantum chemical calculations with the use of B3LYP/6-311G(2d,2p) approach confirmed the trans configuration of the azo-bridge as the most stable energetically and allowed determination of the energy other virtual structures. The observed effects were used in the discussion of vibrational dynamics of the studied compound. The energy gap between cis and trans conformers equals to 1.054 eV (0.03873 Hartree). The electron absorption and emission spectra have been measured and analyzed on the basis of DFT calculations. The life time of the excited state is 12 μs and the Stokes shift is close to 5470 cm- 1.

Experimental determination of the carboxylate oxygen electric-field-gradient and chemical shielding tensors in L-alanine and L-phenylalanine

NASA Astrophysics Data System (ADS)

Yamada, Kazuhiko; Asanuma, Miwako; Honda, Hisashi; Nemoto, Takahiro; Yamazaki, Toshio; Hirota, Hiroshi

2007-10-01

We report a solid-state 17O NMR study of the 17O electric-field-gradient (EFG) and chemical shielding (CS) tensors for each carboxylate group in polycrystalline L-alanine and L-phenylalanine. The magic angle spinning (MAS) and stationary 17O NMR spectra of these compounds were obtained at 9.4, 14.1, and 16.4 T. Analyzes of these 17O NMR spectra yielded reliable experimental NMR parameters including 17O CS tensor components, 17O quadrupole coupling parameters, and the relative orientations between the 17O CS and EFG tensors. The extensive quantum chemical calculations at both the restricted Hartree-Fock and density-functional theories were carried out with various basis sets to evaluate the quality of quantum chemical calculations for the 17O NMR tensors in L-alanine. For 17O CS tensors, the calculations at the B3LYP/D95 ∗∗ level could reasonably reproduce 17O CS tensors, but they still showed some discrepancies in the δ11 components by approximately 36 ppm. For 17O EFG calculations, it was advantageous to use calibrated Q value to give acceptable CQ values. The calculated results also demonstrated that not only complete intermolecular hydrogen-bonding networks to target oxygen in L-alanine, but also intermolecular interactions around the NH3+ group were significant to reproduce the 17O NMR tensors.

Old Wine in New Bottles: Quantum Theory in Historical Perspective.

ERIC Educational Resources Information Center

Bent, Henry A.

1984-01-01

Discusses similarities between chemistry and three central concepts of quantum physics: (1) stationary states; (2) wave functions; and (3) complementarity. Based on these and other similarities, it is indicated that quantum physics is a chemical physics. (JN)

Nonlinear absorption in AlGaAs/GaAs multiple quantum well structures grown by metalorganic chemical vapor deposition

NASA Technical Reports Server (NTRS)

Lee, H. C.; Hariz, A.; Dapkus, P. D.; Kost, A.; Kawase, M.

1987-01-01

This paper reports the study of growth conditions for achieving the sharp exciton resonances and low-intensity saturation of these resonances in AlGaAs-GaAs multiple quantum well structures grown by metalorganic chemical vapor deposition. Low growth temperature is necessary to observe this sharp resonance feature at room temperature. The optimal growth conditions are a tradeoff between the high temperatures required for high quality AlGaAs and low temperatures required for high-purity GaAs. A strong optical saturation of the excitonic absorption has been observed. A saturation density as low as 250 W/sq cm is reported.

Zinc sulfide quantum dots for photocatalytic and sensing applications

NASA Astrophysics Data System (ADS)

Sergeev, Alexander A.; Leonov, Andrei A.; Zhuikova, Elena I.; Postnova, Irina V.; Voznesenskiy, Sergey S.

2017-09-01

Herein, we report the photocatalytic and sensing applications of pure and Mn-doped ZnS quantum dots. The quantum dots were prepared by a chemical precipitation in an aqueous solution in the presence of glutathione as a stabilizing agent. The synthesized quantum dots were used as effective photocatalyst for the degradation of methylene blue dye. Interestingly, fully degradation of methylene blue dye was achieved in 5 min using pure ZnS quantum dots. Further, the synthesized quantum dots were used as efficient sensing element for methane fluorescent sensor. Interfering studies confirmed that the developed sensor possesses very good sensitivity and selectivity towards methane.

The energy-level crossing behavior and quantum Fisher information in a quantum well with spin-orbit coupling.

PubMed

Wang, Z H; Zheng, Q; Wang, Xiaoguang; Li, Yong

2016-03-02

We study the energy-level crossing behavior in a two-dimensional quantum well with the Rashba and Dresselhaus spin-orbit couplings (SOCs). By mapping the SOC Hamiltonian onto an anisotropic Rabi model, we obtain the approximate ground state and its quantum Fisher information (QFI) via performing a unitary transformation. We find that the energy-level crossing can occur in the quantum well system within the available parameters rather than in cavity and circuit quantum eletrodynamics systems. Furthermore, the influence of two kinds of SOCs on the QFI is investigated and an intuitive explanation from the viewpoint of the stationary perturbation theory is given.

The energy-level crossing behavior and quantum Fisher information in a quantum well with spin-orbit coupling

NASA Astrophysics Data System (ADS)

Wang, Z. H.; Zheng, Q.; Wang, Xiaoguang; Li, Yong

2016-03-01

We study the energy-level crossing behavior in a two-dimensional quantum well with the Rashba and Dresselhaus spin-orbit couplings (SOCs). By mapping the SOC Hamiltonian onto an anisotropic Rabi model, we obtain the approximate ground state and its quantum Fisher information (QFI) via performing a unitary transformation. We find that the energy-level crossing can occur in the quantum well system within the available parameters rather than in cavity and circuit quantum eletrodynamics systems. Furthermore, the influence of two kinds of SOCs on the QFI is investigated and an intuitive explanation from the viewpoint of the stationary perturbation theory is given.

Quantum-Sequencing: Biophysics of quantum tunneling through nucleic acids

NASA Astrophysics Data System (ADS)

Casamada Ribot, Josep; Chatterjee, Anushree; Nagpal, Prashant

2014-03-01

Tunneling microscopy and spectroscopy has extensively been used in physical surface sciences to study quantum tunneling to measure electronic local density of states of nanomaterials and to characterize adsorbed species. Quantum-Sequencing (Q-Seq) is a new method based on tunneling microscopy for electronic sequencing of single molecule of nucleic acids. A major goal of third-generation sequencing technologies is to develop a fast, reliable, enzyme-free single-molecule sequencing method. Here, we present the unique ``electronic fingerprints'' for all nucleotides on DNA and RNA using Q-Seq along their intrinsic biophysical parameters. We have analyzed tunneling spectra for the nucleotides at different pH conditions and analyzed the HOMO, LUMO and energy gap for all of them. In addition we show a number of biophysical parameters to further characterize all nucleobases (electron and hole transition voltage and energy barriers). These results highlight the robustness of Q-Seq as a technique for next-generation sequencing.

Quantum crystallography: A perspective.

PubMed

Massa, Lou; Matta, Chérif F

2018-06-30

Extraction of the complete quantum mechanics from X-ray scattering data is the ultimate goal of quantum crystallography. This article delivers a perspective for that possibility. It is desirable to have a method for the conversion of X-ray diffraction data into an electron density that reflects the antisymmetry of an N-electron wave function. A formalism for this was developed early on for the determination of a constrained idempotent one-body density matrix. The formalism ensures pure-state N-representability in the single determinant sense. Applications to crystals show that quantum mechanical density matrices of large molecules can be extracted from X-ray scattering data by implementing a fragmentation method termed the kernel energy method (KEM). It is shown how KEM can be used within the context of quantum crystallography to derive quantum mechanical properties of biological molecules (with low data-to-parameters ratio). © 2017 Wiley Periodicals, Inc. © 2017 Wiley Periodicals, Inc.

Path Integrals for Electronic Densities, Reactivity Indices, and Localization Functions in Quantum Systems

PubMed Central

Putz, Mihai V.

2009-01-01

The density matrix theory, the ancestor of density functional theory, provides the immediate framework for Path Integral (PI) development, allowing the canonical density be extended for the many-electronic systems through the density functional closure relationship. Yet, the use of path integral formalism for electronic density prescription presents several advantages: assures the inner quantum mechanical description of the system by parameterized paths; averages the quantum fluctuations; behaves as the propagator for time-space evolution of quantum information; resembles Schrödinger equation; allows quantum statistical description of the system through partition function computing. In this framework, four levels of path integral formalism were presented: the Feynman quantum mechanical, the semiclassical, the Feynman-Kleinert effective classical, and the Fokker-Planck non-equilibrium ones. In each case the density matrix or/and the canonical density were rigorously defined and presented. The practical specializations for quantum free and harmonic motions, for statistical high and low temperature limits, the smearing justification for the Bohr’s quantum stability postulate with the paradigmatic Hydrogen atomic excursion, along the quantum chemical calculation of semiclassical electronegativity and hardness, of chemical action and Mulliken electronegativity, as well as by the Markovian generalizations of Becke-Edgecombe electronic focalization functions – all advocate for the reliability of assuming PI formalism of quantum mechanics as a versatile one, suited for analytically and/or computationally modeling of a variety of fundamental physical and chemical reactivity concepts characterizing the (density driving) many-electronic systems. PMID:20087467

Path integrals for electronic densities, reactivity indices, and localization functions in quantum systems.

PubMed

Putz, Mihai V

2009-11-10

The density matrix theory, the ancestor of density functional theory, provides the immediate framework for Path Integral (PI) development, allowing the canonical density be extended for the many-electronic systems through the density functional closure relationship. Yet, the use of path integral formalism for electronic density prescription presents several advantages: assures the inner quantum mechanical description of the system by parameterized paths; averages the quantum fluctuations; behaves as the propagator for time-space evolution of quantum information; resembles Schrödinger equation; allows quantum statistical description of the system through partition function computing. In this framework, four levels of path integral formalism were presented: the Feynman quantum mechanical, the semiclassical, the Feynman-Kleinert effective classical, and the Fokker-Planck non-equilibrium ones. In each case the density matrix or/and the canonical density were rigorously defined and presented. The practical specializations for quantum free and harmonic motions, for statistical high and low temperature limits, the smearing justification for the Bohr's quantum stability postulate with the paradigmatic Hydrogen atomic excursion, along the quantum chemical calculation of semiclassical electronegativity and hardness, of chemical action and Mulliken electronegativity, as well as by the Markovian generalizations of Becke-Edgecombe electronic focalization functions - all advocate for the reliability of assuming PI formalism of quantum mechanics as a versatile one, suited for analytically and/or computationally modeling of a variety of fundamental physical and chemical reactivity concepts characterizing the (density driving) many-electronic systems.

Prospect of quantum anomalous Hall and quantum spin Hall effect in doped kagome lattice Mott insulators.

PubMed

Guterding, Daniel; Jeschke, Harald O; Valentí, Roser

2016-05-17

Electronic states with non-trivial topology host a number of novel phenomena with potential for revolutionizing information technology. The quantum anomalous Hall effect provides spin-polarized dissipation-free transport of electrons, while the quantum spin Hall effect in combination with superconductivity has been proposed as the basis for realizing decoherence-free quantum computing. We introduce a new strategy for realizing these effects, namely by hole and electron doping kagome lattice Mott insulators through, for instance, chemical substitution. As an example, we apply this new approach to the natural mineral herbertsmithite. We prove the feasibility of the proposed modifications by performing ab-initio density functional theory calculations and demonstrate the occurrence of the predicted effects using realistic models. Our results herald a new family of quantum anomalous Hall and quantum spin Hall insulators at affordable energy/temperature scales based on kagome lattices of transition metal ions.

Remote explosive and chemical agent detection using broadly tunable mid-infrared external cavity quantum cascade lasers

NASA Astrophysics Data System (ADS)

Rayner, Timothy; Weida, Miles; Pushkarsky, Michael; Day, Timothy

2007-04-01

Terrorists both with IEDs and suicide bombers are targeting civilian infrastructures such as transportation systems. Although explosive detection technologies exist and are used effectively in aviation, these technologies do not lend themselves well to protecting open architecture soft targets, as they are focused on a checkpoint form factor that limits throughput. However, remote detection of explosives and other chemicals would enable these kinds of targets to be protected without interrupting the flow of commerce. Tunable mid-IR laser technology offers the opportunity to detect explosives and other chemicals remotely and quickly. Most chemical compounds, including explosives, have their fundamental vibrational modes in the mid-infrared region (3 to 15μm). There are a variety of techniques that focus on examining interactions that have proven effective in the laboratory but could never work in the field due to complexity, size, reliability and cost. Daylight Solutions has solved these problems by integrating quantum cascade gain media into external tunable cavities. This has resulted in miniaturized, broadly tunable mid-IR laser sources. The laser sources have a capability to tune to +/- 5% of their center wavelength, which means they can sweep through an entire absorption spectrum to ensure very good detection and false alarm performance compared with fixed wavelength devices. These devices are also highly portable, operate at room temperature, and generate 10's to 100's of mW in optical power, in pulsed and continuous wave configurations. Daylight Solutions is in the process of developing a variety of standoff explosive and chemical weapon detection systems using this technology.

Possible ergodic-nonergodic regions in the quantum Sherrington-Kirkpatrick spin glass model and quantum annealing

NASA Astrophysics Data System (ADS)

Mukherjee, Sudip; Rajak, Atanu; Chakrabarti, Bikas K.

2018-02-01

We explore the behavior of the order parameter distribution of the quantum Sherrington-Kirkpatrick model in the spin glass phase using Monte Carlo technique for the effective Suzuki-Trotter Hamiltonian at finite temperatures and that at zero temperature obtained using the exact diagonalization method. Our numerical results indicate the existence of a low- but finite-temperature quantum-fluctuation-dominated ergodic region along with the classical fluctuation-dominated high-temperature nonergodic region in the spin glass phase of the model. In the ergodic region, the order parameter distribution gets narrower around the most probable value of the order parameter as the system size increases. In the other region, the Parisi order distribution function has nonvanishing value everywhere in the thermodynamic limit, indicating nonergodicity. We also show that the average annealing time for convergence (to a low-energy level of the model, within a small error range) becomes system size independent for annealing down through the (quantum-fluctuation-dominated) ergodic region. It becomes strongly system size dependent for annealing through the nonergodic region. Possible finite-size scaling-type behavior for the extent of the ergodic region is also addressed.

Statistics of the Work done in a Quantum Quench

NASA Astrophysics Data System (ADS)

Silva, Alessandro

2009-03-01

The quantum quench, i.e. a rapid change in time of a control parameter of a quantum system, is the simplest paradigm of non-equilibrium process, completely analogous to a standard thermodynamic transformation. The dynamics following a quantum quench is particularly interesting in strongly correlated quantum systems, most prominently when the quench in performed across a quantum critical point. In this talk I will present a way to characterize the physics of quantum quenches by looking at the statistics of a basic thermodynamic variable: the work done on the system by changing its parameters [1]. I will first elucidate the relation between the probability distribution of the work, quantum Jarzynski equalities, and the Loschmidt echo, a quantity that emerges usually in the context of dephasing. Using this connection, I will then characterize the statistics of the work done on a Quantum Ising chain by quenching locally or globally the transverse field. I will then show that for global quenches the presence of a quantum critical point results in singularities of the moments of the distribution, while, for local quenches starting at criticality, the probability distribution itself displays an interesting edge singularity. The results of a similar analysis for other systems will be discussed. [4pt] [1] A. Silva, Phys. Rev. Lett. 101, 120603 (2008).

Transverse fields to tune an Ising-nematic quantum phase transition

NASA Astrophysics Data System (ADS)

Maharaj, Akash V.; Rosenberg, Elliott W.; Hristov, Alexander T.; Berg, Erez; Fernandes, Rafael M.; Fisher, Ian R.; Kivelson, Steven A.

2017-12-01

The paradigmatic example of a continuous quantum phase transition is the transverse field Ising ferromagnet. In contrast to classical critical systems, whose properties depend only on symmetry and the dimension of space, the nature of a quantum phase transition also depends on the dynamics. In the transverse field Ising model, the order parameter is not conserved, and increasing the transverse field enhances quantum fluctuations until they become strong enough to restore the symmetry of the ground state. Ising pseudospins can represent the order parameter of any system with a twofold degenerate broken-symmetry phase, including electronic nematic order associated with spontaneous point-group symmetry breaking. Here, we show for the representative example of orbital-nematic ordering of a non-Kramers doublet that an orthogonal strain or a perpendicular magnetic field plays the role of the transverse field, thereby providing a practical route for tuning appropriate materials to a quantum critical point. While the transverse fields are conjugate to seemingly unrelated order parameters, their nontrivial commutation relations with the nematic order parameter, which can be represented by a Berry-phase term in an effective field theory, intrinsically intertwine the different order parameters.

Graph-theoretic quantum system modelling for neuronal microtubules as hierarchical clustered quantum Hopfield networks

NASA Astrophysics Data System (ADS)

Srivastava, D. P.; Sahni, V.; Satsangi, P. S.

2014-08-01

Graph-theoretic quantum system modelling (GTQSM) is facilitated by considering the fundamental unit of quantum computation and information, viz. a quantum bit or qubit as a basic building block. Unit directional vectors "ket 0" and "ket 1" constitute two distinct fundamental quantum across variable orthonormal basis vectors, for the Hilbert space, specifying the direction of propagation of information, or computation data, while complementary fundamental quantum through, or flow rate, variables specify probability parameters, or amplitudes, as surrogates for scalar quantum information measure (von Neumann entropy). This paper applies GTQSM in continuum of protein heterodimer tubulin molecules of self-assembling polymers, viz. microtubules in the brain as a holistic system of interacting components representing hierarchical clustered quantum Hopfield network, hQHN, of networks. The quantum input/output ports of the constituent elemental interaction components, or processes, of tunnelling interactions and Coulombic bidirectional interactions are in cascade and parallel interconnections with each other, while the classical output ports of all elemental components are interconnected in parallel to accumulate micro-energy functions generated in the system as Hamiltonian, or Lyapunov, energy function. The paper presents an insight, otherwise difficult to gain, for the complex system of systems represented by clustered quantum Hopfield network, hQHN, through the application of GTQSM construct.

Ab initio quantum chemistry: methodology and applications.

PubMed

Friesner, Richard A

2005-05-10

This Perspective provides an overview of state-of-the-art ab initio quantum chemical methodology and applications. The methods that are discussed include coupled cluster theory, localized second-order Moller-Plesset perturbation theory, multireference perturbation approaches, and density functional theory. The accuracy of each approach for key chemical properties is summarized, and the computational performance is analyzed, emphasizing significant advances in algorithms and implementation over the past decade. Incorporation of a condensed-phase environment by means of mixed quantum mechanical/molecular mechanics or self-consistent reaction field techniques, is presented. A wide range of illustrative applications, focusing on materials science and biology, are discussed briefly.

Atmospheric pollution history at Linfen (China) uncovered by magnetic and chemical parameters of sediments from a water reservoir.

PubMed

Ma, Mingming; Hu, Shouyun; Cao, Liwan; Appel, Erwin; Wang, Longsheng

2015-09-01

We studied magnetic and chemical parameters of sediments from sediments of a water reservoir at Linfen (China) in order to quantitatively reconstruct the atmospheric pollution history in this region. The results show that the main magnetic phases are magnetite and maghemite originating from the surrounding catchment and from anthropogenic activities, and there is a significant positive relationship between magnetic concentration parameters and heavy metals concentrations, indicating that magnetic proxies can be used to monitor the anthropogenic pollution. In order to uncover the atmospheric pollution history, we combined the known events of environmental improvement with variations of magnetic susceptibility (χ) and heavy metals along the cores to obtain a detailed chronological framework. In addition, air comprehensive pollution index (ACPI) was reconstructed from regression equation among magnetic and chemical parameters as well as atmospheric monitoring data. Based on these results, the atmospheric pollution history was successfully reconstructed. Copyright © 2015 Elsevier Ltd. All rights reserved.

Error assessment in molecular dynamics trajectories using computed NMR chemical shifts.

PubMed

Koes, David R; Vries, John K

2017-01-01

Accurate chemical shifts for the atoms in molecular mechanics (MD) trajectories can be obtained from quantum mechanical (QM) calculations that depend solely on the coordinates of the atoms in the localized regions surrounding atoms of interest. If these coordinates are correct and the sample size is adequate, the ensemble average of these chemical shifts should be equal to the chemical shifts obtained from NMR spectroscopy. If this is not the case, the coordinates must be incorrect. We have utilized this fact to quantify the errors associated with the backbone atoms in MD simulations of proteins. A library of regional conformers containing 169,499 members was constructed from 6 model proteins. The chemical shifts associated with the backbone atoms in each of these conformers was obtained from QM calculations using density functional theory at the B3LYP level with a 6-311+G(2d,p) basis set. Chemical shifts were assigned to each backbone atom in each MD simulation frame using a template matching approach. The ensemble average of these chemical shifts was compared to chemical shifts from NMR spectroscopy. A large systematic error was identified that affected the 1 H atoms of the peptide bonds involved in hydrogen bonding with water molecules or peptide backbone atoms. This error was highly sensitive to changes in electrostatic parameters. Smaller errors affecting the 13 C a and 15 N atoms were also detected. We believe these errors could be useful as metrics for comparing the force-fields and parameter sets used in MD simulation because they are directly tied to errors in atomic coordinates.

Quantum Hamiltonian identification from measurement time traces.

PubMed

Zhang, Jun; Sarovar, Mohan

2014-08-22

Precise identification of parameters governing quantum processes is a critical task for quantum information and communication technologies. In this Letter, we consider a setting where system evolution is determined by a parametrized Hamiltonian, and the task is to estimate these parameters from temporal records of a restricted set of system observables (time traces). Based on the notion of system realization from linear systems theory, we develop a constructive algorithm that provides estimates of the unknown parameters directly from these time traces. We illustrate the algorithm and its robustness to measurement noise by applying it to a one-dimensional spin chain model with variable couplings.

Quantum Jeffreys prior for displaced squeezed thermal states

NASA Astrophysics Data System (ADS)

Kwek, L. C.; Oh, C. H.; Wang, Xiang-Bin

1999-09-01

It is known that, by extending the equivalence of the Fisher information matrix to its quantum version, the Bures metric, the quantum Jeffreys prior can be determined from the volume element of the Bures metric. We compute the Bures metric for the displaced squeezed thermal state and analyse the quantum Jeffreys prior and its marginal probability distributions. To normalize the marginal probability density function, it is necessary to provide a range of values of the squeezing parameter or the inverse temperature. We find that if the range of the squeezing parameter is kept narrow, there are significant differences in the marginal probability density functions in terms of the squeezing parameters for the displaced and undisplaced situations. However, these differences disappear as the range increases. Furthermore, marginal probability density functions against temperature are very different in the two cases.

Quantum Effects in Biology