Quantum key distribution using card, base station and trusted authority

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

Nordholt, Jane Elizabeth; Hughes, Richard John; Newell, Raymond Thorson

Techniques and tools for quantum key distribution ("QKD") between a quantum communication ("QC") card, base station and trusted authority are described herein. In example implementations, a QC card contains a miniaturized QC transmitter and couples with a base station. The base station provides a network connection with the trusted authority and can also provide electric power to the QC card. When coupled to the base station, after authentication by the trusted authority, the QC card acquires keys through QKD with a trusted authority. The keys can be used to set up secure communication, for authentication, for access control, or formore » other purposes. The QC card can be implemented as part of a smart phone or other mobile computing device, or the QC card can be used as a fillgun for distribution of the keys.« less

Quantum cascade light emitting diodes based on type-2 quantum wells

NASA Technical Reports Server (NTRS)

Lin, C. H.; Yang, R. Q.; Zhang, D.; Murry, S. J.; Pei, S. S.; Allerman, A. A.; Kurtz, S. R.

1997-01-01

The authors have demonstrated room-temperature CW operation of type-2 quantum cascade (QC) light emitting diodes at 4.2 (micro)m using InAs/InGaSb/InAlSb type-2 quantum wells. The type-2 QC configuration utilizes sequential multiple photon emissions in a staircase of coupled type-2 quantum wells. The device was grown by molecular beam epitaxy on a p-type GaSb substrate and was compared of 20 periods of active regions separated by digitally graded quantum well injection regions. The maximum average output power is about 250 (micro)W at 80 K, and 140 (micro)W at 300 K at a repetition rate of 1 kHz with a duty cycle of 50%.

Spectrally high performing quantum cascade lasers

NASA Astrophysics Data System (ADS)

Toor, Fatima

Quantum cascade (QC) lasers are versatile semiconductor light sources that can be engineered to emit light of almost any wavelength in the mid- to far-infrared (IR) and terahertz region from 3 to 300 mum [1-5]. Furthermore QC laser technology in the mid-IR range has great potential for applications in environmental, medical and industrial trace gas sensing [6-10] since several chemical vapors have strong rovibrational frequencies in this range and are uniquely identifiable by their absorption spectra through optical probing of absorption and transmission. Therefore, having a wide range of mid-IR wavelengths in a single QC laser source would greatly increase the specificity of QC laser-based spectroscopic systems, and also make them more compact and field deployable. This thesis presents work on several different approaches to multi-wavelength QC laser sources that take advantage of band-structure engineering and the uni-polar nature of QC lasers. Also, since for chemical sensing, lasers with narrow linewidth are needed, work is presented on a single mode distributed feedback (DFB) QC laser. First, a compact four-wavelength QC laser source, which is based on a 2-by-2 module design, with two waveguides having QC laser stacks for two different emission wavelengths each, one with 7.0 mum/11.2 mum, and the other with 8.7 mum/12.0 mum is presented. This is the first design of a four-wavelength QC laser source with widely different emission wavelengths that uses minimal optics and electronics. Second, since there are still several unknown factors that affect QC laser performance, results on a first ever study conducted to determine the effects of waveguide side-wall roughness on QC laser performance using the two-wavelength waveguides is presented. The results are consistent with Rayleigh scattering effects in the waveguides, with roughness effecting shorter wavelengths more than longer wavelengths. Third, a versatile time-multiplexed multi-wavelength QC laser system that

Countably QC-Approximating Posets

PubMed Central

Mao, Xuxin; Xu, Luoshan

2014-01-01

As a generalization of countably C-approximating posets, the concept of countably QC-approximating posets is introduced. With the countably QC-approximating property, some characterizations of generalized completely distributive lattices and generalized countably approximating posets are given. The main results are as follows: (1) a complete lattice is generalized completely distributive if and only if it is countably QC-approximating and weakly generalized countably approximating; (2) a poset L having countably directed joins is generalized countably approximating if and only if the lattice σ c(L)op of all σ-Scott-closed subsets of L is weakly generalized countably approximating. PMID:25165730

Examination of China's performance and thematic evolution in quantum cryptography research using quantitative and computational techniques.

PubMed

Olijnyk, Nicholas V

2018-01-01

This study performed two phases of analysis to shed light on the performance and thematic evolution of China's quantum cryptography (QC) research. First, large-scale research publication metadata derived from QC research published from 2001-2017 was used to examine the research performance of China relative to that of global peers using established quantitative and qualitative measures. Second, this study identified the thematic evolution of China's QC research using co-word cluster network analysis, a computational science mapping technique. The results from the first phase indicate that over the past 17 years, China's performance has evolved dramatically, placing it in a leading position. Among the most significant findings is the exponential rate at which all of China's performance indicators (i.e., Publication Frequency, citation score, H-index) are growing. China's H-index (a normalized indicator) has surpassed all other countries' over the last several years. The second phase of analysis shows how China's main research focus has shifted among several QC themes, including quantum-key-distribution, photon-optical communication, network protocols, and quantum entanglement with an emphasis on applied research. Several themes were observed across time periods (e.g., photons, quantum-key-distribution, secret-messages, quantum-optics, quantum-signatures); some themes disappeared over time (e.g., computer-networks, attack-strategies, bell-state, polarization-state), while others emerged more recently (e.g., quantum-entanglement, decoy-state, unitary-operation). Findings from the first phase of analysis provide empirical evidence that China has emerged as the global driving force in QC. Considering China is the premier driving force in global QC research, findings from the second phase of analysis provide an understanding of China's QC research themes, which can provide clarity into how QC technologies might take shape. QC and science and technology policy researchers

Development of QC Procedures for Ocean Data Obtained by National Research Projects of Korea

NASA Astrophysics Data System (ADS)

Kim, S. D.; Park, H. M.

2017-12-01

To establish data management system for ocean data obtained by national research projects of Ministry of Oceans and Fisheries of Korea, KIOST conducted standardization and development of QC procedures. After reviewing and analyzing the existing international and domestic ocean-data standards and QC procedures, the draft version of standards and QC procedures were prepared. The proposed standards and QC procedures were reviewed and revised by experts in the field of oceanography and academic societies several times. A technical report on the standards of 25 data items and 12 QC procedures for physical, chemical, biological and geological data items. The QC procedure for temperature and salinity data was set up by referring the manuals published by GTSPP, ARGO and IOOS QARTOD. It consists of 16 QC tests applicable for vertical profile data and time series data obtained in real-time mode and delay mode. Three regional range tests to inspect annual, seasonal and monthly variations were included in the procedure. Three programs were developed to calculate and provide upper limit and lower limit of temperature and salinity at depth from 0 to 1550m. TS data of World Ocean Database, ARGO, GTSPP and in-house data of KIOST were analysed statistically to calculate regional limit of Northwest Pacific area. Based on statistical analysis, the programs calculate regional ranges using mean and standard deviation at 3 kind of grid systems (3° grid, 1° grid and 0.5° grid) and provide recommendation. The QC procedures for 12 data items were set up during 1st phase of national program for data management (2012-2015) and are being applied to national research projects practically at 2nd phase (2016-2019). The QC procedures will be revised by reviewing the result of QC application when the 2nd phase of data management programs is completed.

Lens Coupled Quantum Cascade Laser

NASA Technical Reports Server (NTRS)

Lee, Alan Wei Min (Inventor); Hu, Qing (Inventor)

2013-01-01

Terahertz quantum cascade (QC) devices are disclosed that can operate, e.g., in a range of about 1 THz to about 10 THz. In some embodiments, QC lasers are disclosed in which an optical element (e.g., a lens) is coupled to an output facet of the laser's active region to enhance coupling of the lasing radiation from the active region to an external environment. In other embodiments, terahertz amplifier and tunable terahertz QC lasers are disclosed.

Examination of China’s performance and thematic evolution in quantum cryptography research using quantitative and computational techniques

PubMed Central

2018-01-01

This study performed two phases of analysis to shed light on the performance and thematic evolution of China’s quantum cryptography (QC) research. First, large-scale research publication metadata derived from QC research published from 2001–2017 was used to examine the research performance of China relative to that of global peers using established quantitative and qualitative measures. Second, this study identified the thematic evolution of China’s QC research using co-word cluster network analysis, a computational science mapping technique. The results from the first phase indicate that over the past 17 years, China’s performance has evolved dramatically, placing it in a leading position. Among the most significant findings is the exponential rate at which all of China’s performance indicators (i.e., Publication Frequency, citation score, H-index) are growing. China’s H-index (a normalized indicator) has surpassed all other countries’ over the last several years. The second phase of analysis shows how China’s main research focus has shifted among several QC themes, including quantum-key-distribution, photon-optical communication, network protocols, and quantum entanglement with an emphasis on applied research. Several themes were observed across time periods (e.g., photons, quantum-key-distribution, secret-messages, quantum-optics, quantum-signatures); some themes disappeared over time (e.g., computer-networks, attack-strategies, bell-state, polarization-state), while others emerged more recently (e.g., quantum-entanglement, decoy-state, unitary-operation). Findings from the first phase of analysis provide empirical evidence that China has emerged as the global driving force in QC. Considering China is the premier driving force in global QC research, findings from the second phase of analysis provide an understanding of China’s QC research themes, which can provide clarity into how QC technologies might take shape. QC and science and technology

Quantum correlation properties in Matrix Product States of finite-number spin rings

NASA Astrophysics Data System (ADS)

Zhu, Jing-Min; He, Qi-Kai

2018-02-01

The organization and structure of quantum correlation (QC) of quantum spin-chains are very rich and complex. Hence the depiction and measures about the QC of finite-number spin rings deserved to be investigated intensively by using Matrix Product States(MPSs) in addition to the case with infinite-number. Here the dependencies of the geometric quantum discord(GQD) of two spin blocks on the total spin number, the spacing spin number and the environment parameter are presented in detail. We also compare the GQD with the total correlation(TC) and the classical correlation(CC) and illustrate its characteristics. Predictably, our findings may provide the potential of designing the optimal QC experimental detection proposals and pave the way for the designation of optimal quantum information processing schemes.

Quantum correlations in a family of bipartite separable qubit states

NASA Astrophysics Data System (ADS)

Xie, Chuanmei; Liu, Yimin; Chen, Jianlan; Zhang, Zhanjun

2017-03-01

Quantum correlations (QCs) in some separable states have been proposed as a key resource for certain quantum communication tasks and quantum computational models without entanglement. In this paper, a family of nine-parameter separable states, obtained from arbitrary mixture of two sets of bi-qubit product pure states, is considered. QCs in these separable states are studied analytically or numerically using four QC quantifiers, i.e., measurement-induced disturbance (Luo in Phys Rev A77:022301, 2008), ameliorated MID (Girolami et al. in J Phys A Math Theor 44:352002, 2011),quantum dissonance (DN) (Modi et al. in Phys Rev Lett 104:080501, 2010), and new quantum dissonance (Rulli in Phys Rev A 84:042109, 2011), respectively. First, an inherent symmetry in the concerned separable states is revealed, that is, any nine-parameter separable states concerned in this paper can be transformed to a three-parameter kernel state via some certain local unitary operation. Then, four different QC expressions are concretely derived with the four QC quantifiers. Furthermore, some comparative studies of the QCs are presented, discussed and analyzed, and some distinct features about them are exposed. We find that, in the framework of all the four QC quantifiers, the more mixed the original two pure product states, the bigger QCs the separable states own. Our results reveal some intrinsic features of QCs in separable systems in quantum information.

QA/QC in the laboratory. Session F

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

Hood, F.C.

1992-05-01

Quality assurance and quality control (QA/QC) of analytical chemistry laboratory activities are essential to the validity and usefulness of resultant data. However, in themselves, conventional QA/QC measures will not always ensure that fraudulent data are not generated. Conventional QA/QC measures are based on the assumption that work will be done in good faith; to assure against fraudulent practices, QA/QC measures must be tailored to specific analyses protocols in anticipation of intentional misapplication of those protocols. Application of specific QA/QC measures to ensure against fraudulent practices result in an increased administrative burden being placed on the analytical process; accordingly, in keepingmore » with graded QA philosophy, data quality objectives must be used to identify specific points of concern for special control to minimize the administrative impact.« less

Quantum Testbeds Stakeholder Workshop (QTSW) Report meeting purpose and agenda.

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

Hebner, Gregory A.

Quantum computing (QC) is a promising early-stage technology with the potential to provide scientific computing capabilities far beyond what is possible with even an Exascale computer in specific problems of relevance to the Office of Science. These include (but are not limited to) materials modeling, molecular dynamics, and quantum chromodynamics. However, commercial QC systems are not yet available and the technical maturity of current QC hardware, software, algorithms, and systems integration is woefully incomplete. Thus, there is a significant opportunity for DOE to define the technology building blocks, and solve the system integration issues to enable a revolutionary tool. Oncemore » realized, QC will have world changing impact on economic competitiveness, the scientific enterprise, and citizen well-being. Prior to this workshop, DOE / Office of Advanced Scientific Computing Research (ASCR) hosted a workshop in 2015 to explore QC scientific applications. The goal of that workshop was to assess the viability of QC technologies to meet the computational requirements in support of DOE’s science and energy mission and to identify the potential impact of these technologies.« less

A field-deployable compound-specific isotope analyzer based on quantum cascade laser and hollow waveguide

NASA Astrophysics Data System (ADS)

Wu, Sheng; Deev, Andrei

2013-01-01

A field deployable Compound Specific Isotope Analyzer (CSIA) coupled with capillary chromatogrpahy based on Quantum Cascade (QC) lasers and Hollow Waveguide (HWG) with precision and chemical resolution matching mature Mass Spectroscopy has been achieved in our laboratory. The system could realize 0.3 per mil accuracy for 12C/13C for a Gas Chromatography (GC) peak lasting as short as 5 seconds with carbon molar concentration in the GC peak less than 0.5%. Spectroscopic advantages of HWG when working with QC lasers, i.e. single mode transmission, noiseless measurement and small sample volume, are compared with traditional free space and multipass spectroscopy methods.

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry.

PubMed

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

2014-03-11

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

Quantum cost optimized design of 4-bit reversible universal shift register using reduced number of logic gate

NASA Astrophysics Data System (ADS)

Maity, H.; Biswas, A.; Bhattacharjee, A. K.; Pal, A.

In this paper, we have proposed the design of quantum cost (QC) optimized 4-bit reversible universal shift register (RUSR) using reduced number of reversible logic gates. The proposed design is very useful in quantum computing due to its low QC, less no. of reversible logic gate and less delay. The QC, no. of gates, garbage outputs (GOs) are respectively 64, 8 and 16 for proposed work. The improvement of proposed work is also presented. The QC is 5.88% to 70.9% improved, no. of gate is 60% to 83.33% improved with compared to latest reported result.

Quantum mechanics over sets

NASA Astrophysics Data System (ADS)

Ellerman, David

2014-03-01

In models of QM over finite fields (e.g., Schumacher's ``modal quantum theory'' MQT), one finite field stands out, Z2, since Z2 vectors represent sets. QM (finite-dimensional) mathematics can be transported to sets resulting in quantum mechanics over sets or QM/sets. This gives a full probability calculus (unlike MQT with only zero-one modalities) that leads to a fulsome theory of QM/sets including ``logical'' models of the double-slit experiment, Bell's Theorem, QIT, and QC. In QC over Z2 (where gates are non-singular matrices as in MQT), a simple quantum algorithm (one gate plus one function evaluation) solves the Parity SAT problem (finding the parity of the sum of all values of an n-ary Boolean function). Classically, the Parity SAT problem requires 2n function evaluations in contrast to the one function evaluation required in the quantum algorithm. This is quantum speedup but with all the calculations over Z2 just like classical computing. This shows definitively that the source of quantum speedup is not in the greater power of computing over the complex numbers, and confirms the idea that the source is in superposition.

Structure and Bonding in Uranyl(VI) Peroxide and Crown Ether Complexes; Comparison of Quantum Chemical and Experimental Data.

PubMed

Vallet, Valérie; Grenthe, Ingmar

2017-12-18

The structure, chemical bonding, and thermodynamics of alkali ions in M[12-crown-4] + , M[15-crown-5] + , and M[18-crown-6] + , M[UO 2 (O 2 )(OH 2 ) 2 ] + 4,5 , and M[UO 2 (O 2 )(OH)(OH 2 )] n 1-n (n = 4, 5) complexes have been explored by using quantum chemical (QC) calculations at the ab initio level. The chemical bonding has been studied in the gas phase in order to eliminate solvent effects. QTAIM analysis demonstrates features that are very similar in all complexes and typical for electrostatic M-O bonds, but with the M-O bonds in the uranyl peroxide systems about 20 kJ mol -1 stronger than in the corresponding crown ether complexes. The regular decrease in bond strength with increasing M-O bond distance is consistent with predominantly electrostatic contributions. Energy decomposition of the reaction energies in the gas phase and solvent demonstrates that the predominant component of the total attractive (ΔE elec + ΔE orb ) energy contribution is the electrostatic component. There are no steric constraints for coordination of large cations to small rings, because the M + ions are located outside the ring plane, [O n ], formed by the oxygen donors in the ligands; coordination of ions smaller than the ligand cavity results in longer than normal M-O distances or in a change in the number of bonds, both resulting in weaker complexes. The Gibbs energies, enthalpies, and entropies of reaction calculated using the conductor-like screening model, COSMO, to account for solvent effects deviate significantly from experimental values in water, while those in acetonitrile are in much better agreement. Factors that might affect the selectivity are discussed, but our conclusion is that present QC methods are not accurate enough to describe the rather small differences in selectivity, which only amount to 5-10 kJ mol -1 . We can, however, conclude on the basis of QC and experimental data that M[crown ether] + complexes in the strongly coordinating water solvent are of

The Quixote project: Collaborative and Open Quantum Chemistry data management in the Internet age.

PubMed

Adams, Sam; de Castro, Pablo; Echenique, Pablo; Estrada, Jorge; Hanwell, Marcus D; Murray-Rust, Peter; Sherwood, Paul; Thomas, Jens; Townsend, Joe

2011-10-14

Computational Quantum Chemistry has developed into a powerful, efficient, reliable and increasingly routine tool for exploring the structure and properties of small to medium sized molecules. Many thousands of calculations are performed every day, some offering results which approach experimental accuracy. However, in contrast to other disciplines, such as crystallography, or bioinformatics, where standard formats and well-known, unified databases exist, this QC data is generally destined to remain locally held in files which are not designed to be machine-readable. Only a very small subset of these results will become accessible to the wider community through publication.In this paper we describe how the Quixote Project is developing the infrastructure required to convert output from a number of different molecular quantum chemistry packages to a common semantically rich, machine-readable format and to build respositories of QC results. Such an infrastructure offers benefits at many levels. The standardised representation of the results will facilitate software interoperability, for example making it easier for analysis tools to take data from different QC packages, and will also help with archival and deposition of results. The repository infrastructure, which is lightweight and built using Open software components, can be implemented at individual researcher, project, organisation or community level, offering the exciting possibility that in future many of these QC results can be made publically available, to be searched and interpreted just as crystallography and bioinformatics results are today.Although we believe that quantum chemists will appreciate the contribution the Quixote infrastructure can make to the organisation and and exchange of their results, we anticipate that greater rewards will come from enabling their results to be consumed by a wider community. As the respositories grow they will become a valuable source of chemical data for use by other

The Quixote project: Collaborative and Open Quantum Chemistry data management in the Internet age

PubMed Central

2011-01-01

Computational Quantum Chemistry has developed into a powerful, efficient, reliable and increasingly routine tool for exploring the structure and properties of small to medium sized molecules. Many thousands of calculations are performed every day, some offering results which approach experimental accuracy. However, in contrast to other disciplines, such as crystallography, or bioinformatics, where standard formats and well-known, unified databases exist, this QC data is generally destined to remain locally held in files which are not designed to be machine-readable. Only a very small subset of these results will become accessible to the wider community through publication. In this paper we describe how the Quixote Project is developing the infrastructure required to convert output from a number of different molecular quantum chemistry packages to a common semantically rich, machine-readable format and to build respositories of QC results. Such an infrastructure offers benefits at many levels. The standardised representation of the results will facilitate software interoperability, for example making it easier for analysis tools to take data from different QC packages, and will also help with archival and deposition of results. The repository infrastructure, which is lightweight and built using Open software components, can be implemented at individual researcher, project, organisation or community level, offering the exciting possibility that in future many of these QC results can be made publically available, to be searched and interpreted just as crystallography and bioinformatics results are today. Although we believe that quantum chemists will appreciate the contribution the Quixote infrastructure can make to the organisation and and exchange of their results, we anticipate that greater rewards will come from enabling their results to be consumed by a wider community. As the respositories grow they will become a valuable source of chemical data for use by other

Polarization tracking system for free-space optical communication, including quantum communication

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

Nordholt, Jane Elizabeth; Newell, Raymond Thorson; Peterson, Charles Glen

Quantum communication transmitters include beacon lasers that transmit a beacon optical signal in a predetermined state of polarization such as one of the states of polarization of a quantum communication basis. Changes in the beacon polarization are detected at a receiver, and a retarder is adjusted so that the states of polarization in a received quantum communication optical signal are matched to basis polarizations. The beacon and QC signals can be at different wavelengths so that the beacon does not interfere with detection and decoding of the QC optical signal.

Design, fabrication, and optimization of quantum cascade laser cavities and spectroscopy of the intersubband gain

NASA Astrophysics Data System (ADS)

Dirisu, Afusat Olayinka

Quantum Cascade (QC) lasers are intersubband light sources operating in the wavelength range of ˜ 3 to 300 mum and are used in applications such as sensing (environmental, biological, and hazardous chemical), infrared countermeasures, and free-space infrared communications. The mid-infrared range (i.e. lambda ˜ 3-30 mum) is of particular importance in sensing because of the strong interaction of laser radiation with various chemical species, while in free space communications the atmospheric windows of 3-5 mum and 8-12 mum are highly desirable for low loss transmission. Some of the requirements of these applications include, (1) high output power for improved sensitivity; (2) high operating temperatures for compact and cost-effective systems; (3) wide tunability; (4) single mode operation for high selectivity. In the past, available mid-infrared sources, such as the lead-salt and solid-state lasers, were bulky, expensive, or emit low output power. In recent years, QC lasers have been explored as cost-effective and compact sources because of their potential to satisfy and exceed all the above requirements. Also, the ultrafast carrier lifetimes of intersubband transitions in QC lasers are promising for high bandwidth free-space infrared communication. This thesis was focused on the improvement of QC lasers through the design and optimization of the laser cavity and characterization of the laser gain medium. The optimization of the laser cavity included, (1) the design and fabrication of high reflection Bragg gratings and subwavelength antireflection gratings, by focused ion beam milling, to achieve tunable, single mode and high power QC lasers, and (2) modeling of slab-coupled optical waveguide QC lasers for high brightness output beams. The characterization of the QC laser gain medium was carried out using the single-pass transmission experiment, a sensitive measurement technique, for probing the intersubband transitions and the electron distribution of QC lasers

Quantum Computing in Fock Space Systems

NASA Astrophysics Data System (ADS)

Berezin, Alexander A.

1997-04-01

Fock space system (FSS) has unfixed number (N) of particles and/or degrees of freedom. In quantum computing (QC) main requirement is sustainability of coherent Q-superpositions. This normally favoured by low noise environment. High excitation/high temperature (T) limit is hence discarded as unfeasible for QC. Conversely, if N is itself a quantized variable, the dimensionality of Hilbert basis for qubits may increase faster (say, N-exponentially) than thermal noise (likely, in powers of N and T). Hence coherency may win over T-randomization. For this type of QC speed (S) of factorization of long integers (with D digits) may increase with D (for 'ordinary' QC speed polynomially decreases with D). This (apparent) paradox rests on non-monotonic bijectivity (cf. Georg Cantor's diagonal counting of rational numbers). This brings entire aleph-null structurality ("Babylonian Library" of infinite informational content of integer field) to superposition determining state of quantum analogue of Turing machine head. Structure of integer infinititude (e.g. distribution of primes) results in direct "Platonic pressure" resembling semi-virtual Casimir efect (presure of cut-off vibrational modes). This "effect", the embodiment of Pythagorean "Number is everything", renders Godelian barrier arbitrary thin and hence FSS-based QC can in principle be unlimitedly efficient (e.g. D/S may tend to zero when D tends to infinity).

Hybrid spin and valley quantum computing with singlet-triplet qubits.

PubMed

Rohling, Niklas; Russ, Maximilian; Burkard, Guido

2014-10-24

The valley degree of freedom in the electronic band structure of silicon, graphene, and other materials is often considered to be an obstacle for quantum computing (QC) based on electron spins in quantum dots. Here we show that control over the valley state opens new possibilities for quantum information processing. Combining qubits encoded in the singlet-triplet subspace of spin and valley states allows for universal QC using a universal two-qubit gate directly provided by the exchange interaction. We show how spin and valley qubits can be separated in order to allow for single-qubit rotations.

Application of clinical assay quality control (QC) to multivariate proteomics data: a workflow exemplified by 2-DE QC.

PubMed

Jackson, David; Bramwell, David

2013-12-16

Proteomics technologies can be effective for the discovery and assay of protein forms altered with disease. However, few examples of successful biomarker discovery yet exist. Critical to addressing this is the widespread implementation of appropriate QC (quality control) methodology. Such QC should combine the rigour of clinical laboratory assays with a suitable treatment of the complexity of the proteome by targeting separate assignable causes of variation. We demonstrate an approach, metric and example workflow for users to develop such targeted QC rules systematically and objectively, using a publicly available plasma DIGE data set. Hierarchical clustering analysis of standard channels is first used to discover correlated groups of features corresponding to specific assignable sources of technical variation. These effects are then quantified using a statistical distance metric, and followed on control charts. This allows measurement of process drift and the detection of runs that outlie for any given effect. A known technical issue on originally rejected gels was detected validating this approach, and relevant novel effects were also detected and classified effectively. Our approach was effective for 2-DE QC. Whilst we demonstrated this in a retrospective DIGE experiment, the principles would apply to ongoing QC and other proteomic technologies. This work asserts that properly carried out QC is essential to proteomics discovery experiments. Its significance is that it provides one possible novel framework for applying such methods, with a particular consideration of how to handle the complexity of the proteome. It not only focusses on 2DE-based methodology but also demonstrates general principles. A combination of results and discussion based upon a publicly available data set is used to illustrate the approach and allows a structured discussion of factors that experimenters may wish to bear in mind in other situations. The demonstration is on retrospective data

ChronQC: a quality control monitoring system for clinical next generation sequencing.

PubMed

Tawari, Nilesh R; Seow, Justine Jia Wen; Perumal, Dharuman; Ow, Jack L; Ang, Shimin; Devasia, Arun George; Ng, Pauline C

2018-05-15

ChronQC is a quality control (QC) tracking system for clinical implementation of next-generation sequencing (NGS). ChronQC generates time series plots for various QC metrics to allow comparison of current runs to historical runs. ChronQC has multiple features for tracking QC data including Westgard rules for clinical validity, laboratory-defined thresholds and historical observations within a specified time period. Users can record their notes and corrective actions directly onto the plots for long-term recordkeeping. ChronQC facilitates regular monitoring of clinical NGS to enable adherence to high quality clinical standards. ChronQC is freely available on GitHub (https://github.com/nilesh-tawari/ChronQC), Docker (https://hub.docker.com/r/nileshtawari/chronqc/) and the Python Package Index. ChronQC is implemented in Python and runs on all common operating systems (Windows, Linux and Mac OS X). tawari.nilesh@gmail.com or pauline.c.ng@gmail.com. Supplementary data are available at Bioinformatics online.

WE-AB-206-00: Diagnostic QA/QC Hands-On Workshop

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

NONE

The involvement of medical physicists in diagnostic ultrasound imaging service is increasing due to QC and accreditation requirements. The goal of this ultrasound hands-on workshop is to demonstrate quality control (QC) testing in diagnostic ultrasound and to provide updates in ACR ultrasound accreditation requirements. The first half of this workshop will include two presentations reviewing diagnostic ultrasound QA/QC and ACR ultrasound accreditation requirements. The second half of the workshop will include live demonstrations of basic QC tests. An array of ultrasound testing phantoms and ultrasound scanners will be available for attendees to learn diagnostic ultrasound QC in a hands-on environmentmore » with live demonstrations and on-site instructors. The targeted attendees are medical physicists in diagnostic imaging. Learning Objectives: Gain familiarity with common elements of a QA/QC program for diagnostic ultrasound imaging dentify QC tools available for testing diagnostic ultrasound systems and learn how to use these tools Learn ACR ultrasound accreditation requirements Jennifer Walter is an employee of American College of Radiology on Ultrasound Accreditation.« less

Single mode terahertz quantum cascade amplifier

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

Ren, Y., E-mail: yr235@cam.ac.uk; Wallis, R.; Shah, Y. D.

2014-10-06

A terahertz (THz) optical amplifier based on a 2.9 THz quantum cascade laser (QCL) structure has been demonstrated. By depositing an antireflective coating on the QCL facet, the laser mirror losses are enhanced to fully suppress the lasing action, creating a THz quantum cascade (QC) amplifier. Terahertz radiation amplification has been obtained, by coupling a separate multi-mode THz QCL of the same active region design to the QC amplifier. A bare cavity gain is achieved and shows excellent agreement with the lasing spectrum from the original QCL without the antireflective coating. Furthermore, a maximum optical gain of ∼30 dB with single-modemore » radiation output is demonstrated.« less

Terahertz metasurface quantum-cascade VECSELs: theory and performance

DOE PAGES

Xu, Luyao; Curwen, Christopher; Chen, Daguan; ...

2017-04-12

A longstanding challenge for terahertz quantum-cascade (QC) lasers is achieving both a high power and high-quality beam pattern, this is due in part due to their use of sub-wavelength metallic waveguides. Recently, the vertical-external-cavity surface-emitting laser (VECSEL) concept was demonstrated for the first time in the terahertz range and for a QC-laser. This is enabled by the development of an amplifying metasurface reflector capable of coupling incident free-space THz radiation to the QC-laser material such that it is amplified and re-radiated. The THz metasurface QC-VECSEL initiates a new approach for making QC-lasers with high power and excellent beam pattern. Furthermore,more » the ability to engineer the electromagnetic phase, amplitude, and polarization response of the metasurface enables lasers with new functionality. Our article provides an overview of the fundamental theory, design considerations, and recent results for high-performance THz QC-VECSELs.« less

Spectral gain measurements of quantum confined emitters, and design and fabrication of intersubband quantum box laser structures

NASA Astrophysics Data System (ADS)

Tsvid, Gene

Semiconductor laser active regions are commonly characterized by photo- and electro-luminescence (PL, EL) and cavity length analysis. However quantitative spectral information is not readily extracted from PL and EL data and comparison of different active region materials can be difficult. More quantifiable spectral information is contained in the optical gain spectra. This work reports on spectral gain studies, using multi-segmented interband devices, of InGaAs quantum well and quantum dot active regions grown by metalorganic chemical vapor deposition (MOCVD). Using the fundamental connection between gain and spontaneous emission spectra, the spontaneous radiative current and spontaneous radiative efficiency is evaluated for these active regions. The spectral gain and spontaneous radiative efficiency measurements of 980 nm emitting InGaAs quantum well (QW) material provides a benchmark comparison to previous results obtained on highly-strained, 1200 nm emitting InGaAs QW material. These studies provide insight into carrier recombination and the role of the current injection efficiency in InGaAs QW lasers. The spectral gain of self-assembled MOCVD grown InGaAs quantum dots (QD) active regions are also investigated, allowing for comparison to InGaAs QW material. The second part of my talk will cover intersubband-transition QW and quantum-box (QB) lasers. Quantum cascade (QC) lasers have emerged as compact and technologically important light sources in the mid-infrared (IR) and far-IR wavelength ranges infringing on the near-IR and terahertz spectral regions respectively. However, the overall power conversion efficiency, so-called wallplug efficiency, of the best QC lasers, emitting around 5 microns, is ˜9% in CW operation and very unlikely to exceed 15%. In order to dramatically improve the wallplug efficiency of mid-IR lasers (i.e., to about 50%), intersubband QB (IQB) lasers have been proposed. The basic idea, the optimal design and the progress towards the

Creation of backdoors in quantum communications via laser damage

NASA Astrophysics Data System (ADS)

Makarov, Vadim; Bourgoin, Jean-Philippe; Chaiwongkhot, Poompong; Gagné, Mathieu; Jennewein, Thomas; Kaiser, Sarah; Kashyap, Raman; Legré, Matthieu; Minshull, Carter; Sajeed, Shihan

2016-09-01

Practical quantum communication (QC) protocols are assumed to be secure provided implemented devices are properly characterized and all known side channels are closed. We show that this is not always true. We demonstrate a laser-damage attack capable of modifying device behavior on demand. We test it on two practical QC systems for key distribution and coin tossing, and show that newly created deviations lead to side channels. This reveals that laser damage is a potential security risk to existing QC systems, and necessitates their testing to guarantee security.

Model dynamics for quantum computing

NASA Astrophysics Data System (ADS)

Tabakin, Frank

2017-08-01

A model master equation suitable for quantum computing dynamics is presented. In an ideal quantum computer (QC), a system of qubits evolves in time unitarily and, by virtue of their entanglement, interfere quantum mechanically to solve otherwise intractable problems. In the real situation, a QC is subject to decoherence and attenuation effects due to interaction with an environment and with possible short-term random disturbances and gate deficiencies. The stability of a QC under such attacks is a key issue for the development of realistic devices. We assume that the influence of the environment can be incorporated by a master equation that includes unitary evolution with gates, supplemented by a Lindblad term. Lindblad operators of various types are explored; namely, steady, pulsed, gate friction, and measurement operators. In the master equation, we use the Lindblad term to describe short time intrusions by random Lindblad pulses. The phenomenological master equation is then extended to include a nonlinear Beretta term that describes the evolution of a closed system with increasing entropy. An external Bath environment is stipulated by a fixed temperature in two different ways. Here we explore the case of a simple one-qubit system in preparation for generalization to multi-qubit, qutrit and hybrid qubit-qutrit systems. This model master equation can be used to test the stability of memory and the efficacy of quantum gates. The properties of such hybrid master equations are explored, with emphasis on the role of thermal equilibrium and entropy constraints. Several significant properties of time-dependent qubit evolution are revealed by this simple study.

Quantum-chemical insights from deep tensor neural networks

PubMed Central

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

2017-01-01

Learning from data has led to paradigm shifts in a multitude of disciplines, including web, text and image search, speech recognition, as well as bioinformatics. Can machine learning enable similar breakthroughs in understanding quantum many-body systems? Here we develop an efficient deep learning approach that enables spatially and chemically resolved insights into quantum-mechanical observables of molecular systems. We unify concepts from many-body Hamiltonians with purpose-designed deep tensor neural networks, which leads to size-extensive and uniformly accurate (1 kcal mol−1) predictions in compositional and configurational chemical space for molecules of intermediate size. As an example of chemical relevance, the model reveals a classification of aromatic rings with respect to their stability. Further applications of our model for predicting atomic energies and local chemical potentials in molecules, reliable isomer energies, and molecules with peculiar electronic structure demonstrate the potential of machine learning for revealing insights into complex quantum-chemical systems. PMID:28067221

Quantum-chemical insights from deep tensor neural networks.

PubMed

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

2017-01-09

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

Quantum-chemical insights from deep tensor neural networks

NASA Astrophysics Data System (ADS)

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

2017-01-01

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

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 ...

Exploration of bulk and interface behavior of gas molecules and 1-butyl-3-methylimidazolium tetrafluoroborate ionic liquid using equilibrium and nonequilibrium molecular dynamics simulation and quantum chemical calculation.

PubMed

Yang, Quan; Achenie, Luke E K

2018-04-18

Ionic liquids (ILs) show brilliant performance in separating gas impurities, but few researchers have performed an in-depth exploration of the bulk and interface behavior of penetrants and ILs thoroughly. In this research, we have performed a study on both molecular dynamics (MD) simulation and quantum chemical (QC) calculation to explore the transport of acetylene and ethylene in the bulk and interface regions of 1-butyl-3-methylimidazolium tetrafluoroborate ([BMIM]-[BF4]). The diffusivity, solubility and permeability of gas molecules in the bulk were researched with MD simulation first. The subdiffusion behavior of gas molecules is induced by coupling between the motion of gas molecules and the ions, and the relaxation processes of the ions after the disturbance caused by gas molecules. Then, QC calculation was performed to explore the optical geometry of ions, ion pairs and complexes of ions and penetrants, and interaction potential for pairs and complexes. Finally, nonequilibrium MD simulation was performed to explore the interface structure and properties of the IL-gas system and gas molecule behavior in the interface region. The research results may be used in the design of IL separation media.

Single-mode, narrow-linewidth external cavity quantum cascade laser through optical feedback from a partial-reflector.

PubMed

Cendejas, Richard A; Phillips, Mark C; Myers, Tanya L; Taubman, Matthew S

2010-12-06

An external-cavity (EC) quantum cascade (QC) laser using optical feedback from a partial-reflector is reported. With this configuration, the otherwise multi-mode emission of a Fabry-Perot QC laser was made single-mode with optical output powers exceeding 40 mW. A mode-hop free tuning range of 2.46 cm(-1) was achieved by synchronously tuning the EC length and QC laser current. The linewidth of the partial-reflector EC-QC laser was measured for integration times from 100 μs to 4 seconds, and compared to a distributed feedback QC laser. Linewidths as small as 480 kHz were recorded for the EC-QC laser.

Quantum Cascade Laser Measurements of Stratospheric Methane (CHsub4) and Nitrous Oxide (NSub20)

NASA Technical Reports Server (NTRS)

Webster, C.; Flesch, G.; Scott, D.; Swanson, J.; May, R.; Gmachl, S.; Capasso, F.; Sivco, D.; Baillargeon, J.; Hutchinson, A.;

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.

Quality Control (QC) System Development for the Pell Grant Program: A Conceptual Framework.

ERIC Educational Resources Information Center

Advanced Technology, Inc., Reston, VA.

The objectives of the Pell Grant quality control (QC) system and the general definition of QC are considered. Attention is also directed to: the objectives of the Stage II Pell Grant QC system design and testing project, the approach used to develop the QC system, and the interface of the QC system and the Pell Grant delivery system. The…

Multi-factor authentication using quantum communication

DOEpatents

Hughes, Richard John; Peterson, Charles Glen; Thrasher, James T.; Nordholt, Jane E.; Yard, Jon T.; Newell, Raymond Thorson; Somma, Rolando D.

2018-02-06

Multi-factor authentication using quantum communication ("QC") includes stages for enrollment and identification. For example, a user enrolls for multi-factor authentication that uses QC with a trusted authority. The trusted authority transmits device factor information associated with a user device (such as a hash function) and user factor information associated with the user (such as an encrypted version of a user password). The user device receives and stores the device factor information and user factor information. For multi-factor authentication that uses QC, the user device retrieves its stored device factor information and user factor information, then transmits the user factor information to the trusted authority, which also retrieves its stored device factor information. The user device and trusted authority use the device factor information and user factor information (more specifically, information such as a user password that is the basis of the user factor information) in multi-factor authentication that uses QC.

QSPIN: A High Level Java API for Quantum Computing Experimentation

NASA Technical Reports Server (NTRS)

Barth, Tim

2017-01-01

QSPIN is a high level Java language API for experimentation in QC models used in the calculation of Ising spin glass ground states and related quadratic unconstrained binary optimization (QUBO) problems. The Java API is intended to facilitate research in advanced QC algorithms such as hybrid quantum-classical solvers, automatic selection of constraint and optimization parameters, and techniques for the correction and mitigation of model and solution errors. QSPIN includes high level solver objects tailored to the D-Wave quantum annealing architecture that implement hybrid quantum-classical algorithms [Booth et al.] for solving large problems on small quantum devices, elimination of variables via roof duality, and classical computing optimization methods such as GPU accelerated simulated annealing and tabu search for comparison. A test suite of documented NP-complete applications ranging from graph coloring, covering, and partitioning to integer programming and scheduling are provided to demonstrate current capabilities.

Entanglement-assisted quantum quasicyclic low-density parity-check codes

NASA Astrophysics Data System (ADS)

Hsieh, Min-Hsiu; Brun, Todd A.; Devetak, Igor

2009-03-01

We investigate the construction of quantum low-density parity-check (LDPC) codes from classical quasicyclic (QC) LDPC codes with girth greater than or equal to 6. We have shown that the classical codes in the generalized Calderbank-Skor-Steane construction do not need to satisfy the dual-containing property as long as preshared entanglement is available to both sender and receiver. We can use this to avoid the many four cycles which typically arise in dual-containing LDPC codes. The advantage of such quantum codes comes from the use of efficient decoding algorithms such as sum-product algorithm (SPA). It is well known that in the SPA, cycles of length 4 make successive decoding iterations highly correlated and hence limit the decoding performance. We show the principle of constructing quantum QC-LDPC codes which require only small amounts of initial shared entanglement.

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.

40 CFR 98.44 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Monitoring and QA/QC requirements. 98.44 Section 98.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electricity Generation § 98.44 Monitoring and QA/QC...

40 CFR 98.44 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Monitoring and QA/QC requirements. 98.44 Section 98.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electricity Generation § 98.44 Monitoring and QA/QC...

40 CFR 98.44 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Monitoring and QA/QC requirements. 98.44 Section 98.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electricity Generation § 98.44 Monitoring and QA/QC...

40 CFR 98.44 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Monitoring and QA/QC requirements. 98.44 Section 98.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electricity Generation § 98.44 Monitoring and QA/QC...

40 CFR 98.44 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98.44 Section 98.44 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electricity Generation § 98.44 Monitoring and QA/QC...

40 CFR 98.64 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Monitoring and QA/QC requirements. 98.64 Section 98.64 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Aluminum Production § 98.64 Monitoring and QA/QC requirements...

40 CFR 98.334 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Zinc Production § 98.334 Monitoring and QA/QC requirements. If..., belt weigh feeders, weighed purchased quantities in shipments or containers, combination of bulk...

40 CFR 98.334 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Zinc Production § 98.334 Monitoring and QA/QC requirements. If..., belt weigh feeders, weighed purchased quantities in shipments or containers, combination of bulk...

40 CFR 98.334 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Zinc Production § 98.334 Monitoring and QA/QC requirements. If..., belt weigh feeders, weighed purchased quantities in shipments or containers, combination of bulk...

40 CFR 98.334 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Zinc Production § 98.334 Monitoring and QA/QC requirements. If..., belt weigh feeders, weighed purchased quantities in shipments or containers, combination of bulk...

40 CFR 98.64 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Monitoring and QA/QC requirements. 98.64 Section 98.64 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Aluminum Production § 98.64 Monitoring and QA/QC requirements...

40 CFR 98.84 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Monitoring and QA/QC requirements. 98.84 Section 98.84 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Cement Production § 98.84 Monitoring and QA/QC requirements...

Optimization of cw-QC lasers for Doppler and sub-Doppler molecular spectroscopy

NASA Astrophysics Data System (ADS)

Kelly, James F.; Disselkamp, Robert S.; Sams, Robert L.; Blake, Thomas A.; Sharpe, Steven W.; Richter, Dirk A.; Fried, Alan

2002-09-01

Inter-subband (Type I) quantum-cascade (QC) lasers have shown the potential to generate tunable mid-IR radiation with narrow intrinsic linewidths (< 160 KHz in 15 mSec sweeps) and excellent amplitude stability (< 3 ppm averaged over minutes). Our bench-scale efforts to develop the Type I distributed feedback (DFB)-QC lasers for fieldable atmospheric chemistry campaigns, where multipass (Herriot or White) cells are used to enhance path-length, have not yet realized performance to the low intrinsic noise levels seen in these devices. By comparison, many operational systems' levels of noise-equivalent-absorbance (NEA) using Pb-salt lasers can routinely achieve at least one-order of magnitude better cw-performance, and with much lower powers. We have found that instability effets from weak back-scattered laser light -primarily from the Herriot cell- results in feedback-implicated technical noise well above the thermal and shot-noise of standard IR detectors. Of more fundamental concern is the fact that planar-stripe DFB-QC lasers undergo beam steering and transverse spatial-mode competitions during current tuning. It is the development of fully automated sub-ppbV sensitive IR chem-sensors. It is possible to reach low-ppm levels of absorptance change-detection (ΔI/I0) over small wavelength regions with careful alignment to 100 M Herriott cells, but extreme care in spatial filtering is critical. However in the case of optical configurations which preclude significant optical feedback and need for stringent mode coupling alignments, the cw-DFB-QC lasers show great promise to do high resolution sub-Doppler spectroscopy. By serendipitous events, a varient of 'mode- or level-crossing' spectroscopy was probably rediscovered, which may allow very high resolution, sub-Doppler features and/or hyperfine alignments to be probed with 'uni-directional' topologies. We will primarily discuss the basic features of the 'uni-directional' sub-Doppler spectroscopy concept in this report

40 CFR 98.94 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electronics Manufacturing § 98.94 Monitoring and QA/QC requirements. (a) For calendar year 2011 monitoring, you may follow the provisions in paragraphs (a)(1) through...

40 CFR 98.94 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electronics Manufacturing § 98.94 Monitoring and QA/QC requirements. (a) For calendar year 2011 monitoring, you may follow the provisions in paragraphs (a)(1) through...

40 CFR 98.94 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electronics Manufacturing § 98.94 Monitoring and QA/QC requirements. (a) For calendar year 2011 monitoring, you may follow the provisions in paragraphs (a)(1) through...

40 CFR 98.94 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Electronics Manufacturing § 98.94 Monitoring and QA/QC...-specific heel factors for each container type for each gas used, according to the procedures in paragraphs...

Quantum incompatibility of channels with general outcome operator algebras

NASA Astrophysics Data System (ADS)

Kuramochi, Yui

2018-04-01

A pair of quantum channels is said to be incompatible if they cannot be realized as marginals of a single channel. This paper addresses the general structure of the incompatibility of completely positive channels with a fixed quantum input space and with general outcome operator algebras. We define a compatibility relation for such channels by identifying the composite outcome space as the maximal (projective) C*-tensor product of outcome algebras. We show theorems that characterize this compatibility relation in terms of the concatenation and conjugation of channels, generalizing the recent result for channels with quantum outcome spaces. These results are applied to the positive operator valued measures (POVMs) by identifying each of them with the corresponding quantum-classical (QC) channel. We also give a characterization of the maximality of a POVM with respect to the post-processing preorder in terms of the conjugate channel of the QC channel. We consider another definition of compatibility of normal channels by identifying the composite outcome space with the normal tensor product of the outcome von Neumann algebras. We prove that for a given normal channel, the class of normally compatible channels is upper bounded by a special class of channels called tensor conjugate channels. We show the inequivalence of the C*- and normal compatibility relations for QC channels, which originates from the possibility and impossibility of copying operations for commutative von Neumann algebras in C*- and normal compatibility relations, respectively.

40 CFR 98.424 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Carbon Dioxide § 98.424 Monitoring and QA/QC... determine quantity in accordance with this paragraph. (i) Reporters that supply CO2 in containers using...

40 CFR 98.424 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Carbon Dioxide § 98.424 Monitoring and QA/QC... determine quantity in accordance with this paragraph. (i) Reporters that supply CO2 in containers using...

40 CFR 98.424 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... 40 Protection of Environment 21 2011-07-01 2011-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Carbon Dioxide § 98.424 Monitoring and QA/QC... determine quantity in accordance with this paragraph. (i) Reporters that supply CO2 in containers using...

40 CFR 98.424 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Carbon Dioxide § 98.424 Monitoring and QA/QC... determine quantity in accordance with this paragraph. (i) Reporters that supply CO2 in containers using...

QA/QC requirements for physical properties sampling and analysis

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

Innis, B.E.

1993-07-21

This report presents results of an assessment of the available information concerning US Environmental Protection Agency (EPA) quality assurance/quality control (QA/QC) requirements and guidance applicable to sampling, handling, and analyzing physical parameter samples at Comprehensive Environmental Restoration, Compensation, and Liability Act (CERCLA) investigation sites. Geotechnical testing laboratories measure the following physical properties of soil and sediment samples collected during CERCLA remedial investigations (RI) at the Hanford Site: moisture content, grain size by sieve, grain size by hydrometer, specific gravity, bulk density/porosity, saturated hydraulic conductivity, moisture retention, unsaturated hydraulic conductivity, and permeability of rocks by flowing air. Geotechnical testing laboratories alsomore » measure the following chemical parameters of soil and sediment samples collected during Hanford Site CERCLA RI: calcium carbonate and saturated column leach testing. Physical parameter data are used for (1) characterization of vadose and saturated zone geology and hydrogeology, (2) selection of monitoring well screen sizes, (3) to support modeling and analysis of the vadose and saturated zones, and (4) for engineering design. The objectives of this report are to determine the QA/QC levels accepted in the EPA Region 10 for the sampling, handling, and analysis of soil samples for physical parameters during CERCLA RI.« less

40 CFR 98.474 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Injection of Carbon Dioxide § 98.474 Monitoring and QA/QC.... (2) You must determine the quarterly mass or volume of contents in all containers if you receive CO2...

40 CFR 98.474 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Injection of Carbon Dioxide § 98.474 Monitoring and QA/QC.... (2) You must determine the quarterly mass or volume of contents in all containers if you receive CO2...

40 CFR 98.474 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Injection of Carbon Dioxide § 98.474 Monitoring and QA/QC.... (2) You must determine the quarterly mass or volume of contents in all containers if you receive CO2...

40 CFR 98.424 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Carbon Dioxide § 98.424 Monitoring and QA/QC... containers shall measure the mass in each CO2 container using weigh bills, scales, or load cells and sum the...

Fast terahertz imaging using a quantum cascade amplifier

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

Ren, Yuan, E-mail: yr235@cam.ac.uk; Wallis, Robert; Jessop, David Stephen

2015-07-06

A terahertz (THz) imaging scheme based on the effect of self-mixing in a 2.9 THz quantum cascade (QC) amplifier has been demonstrated. By coupling an antireflective-coated silicon lens to the facet of a QC laser, with no external optical feedback, the laser mirror losses are enhanced to fully suppress lasing action, creating a THz QC amplifier. The addition of reflection from an external target to the amplifier creates enough optical feedback to initiate lasing action and the resulting emission enhances photon-assisted transport, which in turn reduces the voltage across the device. At the peak gain point, the maximum photon densitymore » coupled back leads to a prominent self-mixing effect in the QC amplifier, leading to a high sensitivity, with a signal to noise ratio up to 55 dB, along with a fast data acquisition speed of 20 000 points per second.« less

Joint design of QC-LDPC codes for coded cooperation system with joint iterative decoding

NASA Astrophysics Data System (ADS)

Zhang, Shunwai; Yang, Fengfan; Tang, Lei; Ejaz, Saqib; Luo, Lin; Maharaj, B. T.

2016-03-01

In this paper, we investigate joint design of quasi-cyclic low-density-parity-check (QC-LDPC) codes for coded cooperation system with joint iterative decoding in the destination. First, QC-LDPC codes based on the base matrix and exponent matrix are introduced, and then we describe two types of girth-4 cycles in QC-LDPC codes employed by the source and relay. In the equivalent parity-check matrix corresponding to the jointly designed QC-LDPC codes employed by the source and relay, all girth-4 cycles including both type I and type II are cancelled. Theoretical analysis and numerical simulations show that the jointly designed QC-LDPC coded cooperation well combines cooperation gain and channel coding gain, and outperforms the coded non-cooperation under the same conditions. Furthermore, the bit error rate performance of the coded cooperation employing jointly designed QC-LDPC codes is better than those of random LDPC codes and separately designed QC-LDPC codes over AWGN channels.

Underlying Information Technology Tailored Quantum Error Correction

DTIC Science & Technology

2006-07-28

typically constructed by using an optical beam splitter . • We used a decoherence-free-subspace encoding to reduce the sensitivity of an optical Deutsch...simplification of design constraints in solid state QC (incl. quantum dots and superconducting qubits), hybrid quantum error correction and prevention methods...process tomography on one- and two-photon polarisation states, from full and partial data "• Accomplished complete two-photon QPT. "• Discovered surprising

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

AfterQC: automatic filtering, trimming, error removing and quality control for fastq data.

PubMed

Chen, Shifu; Huang, Tanxiao; Zhou, Yanqing; Han, Yue; Xu, Mingyan; Gu, Jia

2017-03-14

Some applications, especially those clinical applications requiring high accuracy of sequencing data, usually have to face the troubles caused by unavoidable sequencing errors. Several tools have been proposed to profile the sequencing quality, but few of them can quantify or correct the sequencing errors. This unmet requirement motivated us to develop AfterQC, a tool with functions to profile sequencing errors and correct most of them, plus highly automated quality control and data filtering features. Different from most tools, AfterQC analyses the overlapping of paired sequences for pair-end sequencing data. Based on overlapping analysis, AfterQC can detect and cut adapters, and furthermore it gives a novel function to correct wrong bases in the overlapping regions. Another new feature is to detect and visualise sequencing bubbles, which can be commonly found on the flowcell lanes and may raise sequencing errors. Besides normal per cycle quality and base content plotting, AfterQC also provides features like polyX (a long sub-sequence of a same base X) filtering, automatic trimming and K-MER based strand bias profiling. For each single or pair of FastQ files, AfterQC filters out bad reads, detects and eliminates sequencer's bubble effects, trims reads at front and tail, detects the sequencing errors and corrects part of them, and finally outputs clean data and generates HTML reports with interactive figures. AfterQC can run in batch mode with multiprocess support, it can run with a single FastQ file, a single pair of FastQ files (for pair-end sequencing), or a folder for all included FastQ files to be processed automatically. Based on overlapping analysis, AfterQC can estimate the sequencing error rate and profile the error transform distribution. The results of our error profiling tests show that the error distribution is highly platform dependent. Much more than just another new quality control (QC) tool, AfterQC is able to perform quality control, data

Intersubband spectroscopy of ZnO/ZnMgO quantum wells grown on m-plane ZnO substrates for quantum cascade device applications (Conference Presentation)

NASA Astrophysics Data System (ADS)

Quach, Patrick; Jollivet, Arnaud; Isac, Nathalie; Bousseksou, Adel; Ariel, Frédéric; Tchernycheva, Maria; Julien, François H.; Montes Bajo, Miguel; Tamayo-Arriola, Julen; Hierro, Adrián.; Le Biavan, Nolwenn; Hugues, Maxime; Chauveau, Jean-Michel

2017-03-01

Quantum cascade (QC) lasers opens new prospects for powerful sources operating at THz frequencies. Up to now the best THz QC lasers are based on intersubband emission in GaAs/AlGaAs quantum well (QW) heterostructures. The maximum operating temperature is 200 K, which is too low for wide-spread applications. This is due to the rather low LO-phonon energy (36 meV) of GaAs-based materials. Indeed, thermal activation allows non-radiative path through electron-phonon interaction which destroys the population inversion. Wide band gap materials such as ZnO have been predicted to provide much higher operating temperatures because of the high value of their LO-phonon energy. However, despite some observations of intersubband absorption in c-plane ZnO/ZnMgO quantum wells, little is known on the fundamental parameters such as the conduction band offset in such heterostructures. In addition the internal field inherent to c-plane grown heterostuctures is an handicap for the design of QC lasers and detectors. In this talk, we will review a systematic investigation of ZnO/ZnMgO QW heterostructures with various Mg content and QW thicknesses grown by plasma molecular beam epitaxy on low-defect m-plane ZnO substrates. We will show that most samples exhibit TM-polarized intersubband absorption at room temperature linked either to bound-to-quasi bound inter-miniband absorption or to bound-to bound intersubband absorption depending on the Mg content of the barrier material. This systematic study allows for the first time to estimate the conduction band offset of ZnO/ZnMgO heterostructures, opening prospects for the design of QC devices operating at THz frequencies. This was supported by the European Union's Horizon 2020 research and innovation programme under grant agreement #665107.

Quantum communications system with integrated photonic devices

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

Nordholt, Jane E.; Peterson, Charles Glen; Newell, Raymond Thorson

Security is increased in quantum communication (QC) systems lacking a true single-photon laser source by encoding a transmitted optical signal with two or more decoy-states. A variable attenuator or amplitude modulator randomly imposes average photon values onto the optical signal based on data input and the predetermined decoy-states. By measuring and comparing photon distributions for a received QC signal, a single-photon transmittance is estimated. Fiber birefringence is compensated by applying polarization modulation. A transmitter can be configured to transmit in conjugate polarization bases whose states of polarization (SOPs) can be represented as equidistant points on a great circle on themore » Poincare sphere so that the received SOPs are mapped to equidistant points on a great circle and routed to corresponding detectors. Transmitters are implemented in quantum communication cards and can be assembled from micro-optical components, or transmitter components can be fabricated as part of a monolithic or hybrid chip-scale circuit.« less

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.

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

NASA Astrophysics Data System (ADS)

Sayin, Koray; Karakaş, Duran

2018-04-01

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

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

Quantum Cosmology

NASA Astrophysics Data System (ADS)

Bojowald, Martin

The universe, ultimately, is to be described by quantum theory. Quantum aspects of all there is, including space and time, may not be significant for many purposes, but are crucial for some. And so a quantum description of cosmology is required for a complete and consistent worldview. At any rate, even if we were not directly interested in regimes where quantum cosmology plays a role, a complete physical description could not stop at a stage before the whole universe is reached. Quantum theory is essential in the microphysics of particles, atoms, molecules, solids, white dwarfs and neutron stars. Why should one expect this ladder of scales to end at a certain size? If regimes are sufficiently violent and energetic, quantum effects are non-negligible even on scales of the whole cosmos; this is realized at least once in the history of the universe: at the big bang where the classical theory of general relativity would make energy densities diverge. 1.Lachieze-Rey, M., Luminet, J.P.: Phys. Rept. 254,135 (1995), gr-qc/9605010 2.BSDeWitt1967Phys. Rev.160511131967PhRv..160.1113D0158.4650410.1103/PhysRev.160.1113DeWitt, B.S.: Phys. Rev. 160(5), 1113 (1967) 3.Wiltshire, D.L.: In: Robson B., Visvanathan N., Woolcock W.S. (eds.) Cosmology: The Physics of the Universe, pp. 473-531. World Scientific, Singapore (1996

Quantum paraelectricity in copper-titanates: Magnetic-order driven vitrification

NASA Astrophysics Data System (ADS)

Kumar, Jitender; Awasthi, A. M.

2015-07-01

Quantum-paraelectric (QP) family character is emergent from shared low-temperature characteristics of SrCu3Ti4O12 (SCTO), CaCu3Ti4O12 (CCTO), and Ca0.9Li0.1Cu3Ti4O12 (CLCTO) A1/4A'3/4BO3 structures featuring antiferro-tilted Ti-O6 octahedra. Above their magnetic ordering temperatures TN, permittivity of SCTO and CLCTO follow typical Barrett form, whereas in CCTO, quantum paraelectricity is masked by the huge ɛ'-step. Hidden QP in CCTO gets revealed by Li-doping at the Ca-site, which considerably up-shifts the temperature scale (from ˜100 K to ˜250 K) of the dielectric step-anomaly in CLCTO. Competing magneto-electricity and quantum fluctuations result in glassy-arrest of the QP degrees of freedom near TN; manifest as dispersive-deviation of the permittivity (in SCTO and CLCTO) from the low-temperature Barrett saturation. However, quantum criticality (QC) regime being well above TN registers its presence nevertheless, as the ˜T2 behaviour of their inverse dielectric susceptibility. Non-compliance to the usual behaviours of dispersive-response vs. bias-field and temperature unambiguously rule out a relaxor origin of the glassy state. We determine a dimensionless thermal window (0.3 ≤ T/T1 ≤ 0.6) of QC signature, covering typical quantum-paraelectrics.

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.

First-Order Phase Transition in the Quantum Adiabatic Algorithm

DTIC Science & Technology

2010-01-14

London) 400, 133 (1999). [19] T. Jörg, F. Krzakala, G . Semerjian, and F. Zamponi, arXiv:0911.3438. PRL 104, 020502 (2010) P HY S I CA L R EV I EW LE T T E R S week ending 15 JANUARY 2010 020502-4 ...Box 12211 Research Triangle Park, NC 27709-2211 15. SUBJECT TERMS Quantum Adiabatic Algorithm, Monte Carlo, Quantum Phase Transition A. P . Young, V...documentation. Approved for public release; distribution is unlimited. ... 56290.2-PH-QC First-Order Phase Transition in the Quantum Adiabatic Algorithm A. P

Investigating Quantum Modulation States

DTIC Science & Technology

2016-03-01

Coherent state quantum data encryption is highly interoperable with current classical optical infrastructure in both fiber and free space optical networks...hub’s field of regard has a transmit/receive module that are endpoints of the Lyot filter stage tree within the hub’s backend electro-optics control... mobile airborne and space-borne networking. Just like any laser communication technology, QC links are affected by several sources of distortions

Adiabatic Quantum Transistors (Open Access, Publisher’s Version)

DTIC Science & Technology

2013-06-14

states are the entangled states originally used to perform measurement-based quantum computation [9,19]. To de- fine the Hamiltonian of our system, we need...carries over to our model. Note that fault-tolerant QC requires expunging entropy (usually via measurement), but this can always be placed at the end... entropy of quantum er- rors, and the latter is important for building architectures that are modular and synchronous. A. Adiabatic measurement amplifier

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.

Fast QC-LDPC code for free space optical communication

NASA Astrophysics Data System (ADS)

Wang, Jin; Zhang, Qi; Udeh, Chinonso Paschal; Wu, Rangzhong

2017-02-01

Free Space Optical (FSO) Communication systems use the atmosphere as a propagation medium. Hence the atmospheric turbulence effects lead to multiplicative noise related with signal intensity. In order to suppress the signal fading induced by multiplicative noise, we propose a fast Quasi-Cyclic (QC) Low-Density Parity-Check (LDPC) code for FSO Communication systems. As a linear block code based on sparse matrix, the performances of QC-LDPC is extremely near to the Shannon limit. Currently, the studies on LDPC code in FSO Communications is mainly focused on Gauss-channel and Rayleigh-channel, respectively. In this study, the LDPC code design over atmospheric turbulence channel which is nether Gauss-channel nor Rayleigh-channel is closer to the practical situation. Based on the characteristics of atmospheric channel, which is modeled as logarithmic-normal distribution and K-distribution, we designed a special QC-LDPC code, and deduced the log-likelihood ratio (LLR). An irregular QC-LDPC code for fast coding, of which the rates are variable, is proposed in this paper. The proposed code achieves excellent performance of LDPC codes and can present the characteristics of high efficiency in low rate, stable in high rate and less number of iteration. The result of belief propagation (BP) decoding shows that the bit error rate (BER) obviously reduced as the Signal-to-Noise Ratio (SNR) increased. Therefore, the LDPC channel coding technology can effectively improve the performance of FSO. At the same time, the BER, after decoding reduces with the increase of SNR arbitrarily, and not having error limitation platform phenomenon with error rate slowing down.

Droplet Digital™ PCR Next-Generation Sequencing Library QC Assay.

PubMed

Heredia, Nicholas J

2018-01-01

Digital PCR is a valuable tool to quantify next-generation sequencing (NGS) libraries precisely and accurately. Accurately quantifying NGS libraries enable accurate loading of the libraries on to the sequencer and thus improve sequencing performance by reducing under and overloading error. Accurate quantification also benefits users by enabling uniform loading of indexed/barcoded libraries which in turn greatly improves sequencing uniformity of the indexed/barcoded samples. The advantages gained by employing the Droplet Digital PCR (ddPCR™) library QC assay includes the precise and accurate quantification in addition to size quality assessment, enabling users to QC their sequencing libraries with confidence.

FPGA implementation of high-performance QC-LDPC decoder for optical communications

NASA Astrophysics Data System (ADS)

Zou, Ding; Djordjevic, Ivan B.

2015-01-01

Forward error correction is as one of the key technologies enabling the next-generation high-speed fiber optical communications. Quasi-cyclic (QC) low-density parity-check (LDPC) codes have been considered as one of the promising candidates due to their large coding gain performance and low implementation complexity. In this paper, we present our designed QC-LDPC code with girth 10 and 25% overhead based on pairwise balanced design. By FPGAbased emulation, we demonstrate that the 5-bit soft-decision LDPC decoder can achieve 11.8dB net coding gain with no error floor at BER of 10-15 avoiding using any outer code or post-processing method. We believe that the proposed single QC-LDPC code is a promising solution for 400Gb/s optical communication systems and beyond.

Quality control in urodynamics and the role of software support in the QC procedure.

PubMed

Hogan, S; Jarvis, P; Gammie, A; Abrams, P

2011-11-01

This article aims to identify quality control (QC) best practice, to review published QC audits in order to identify how closely good practice is followed, and to carry out a market survey of the software features that support QC offered by urodynamics machines available in the UK. All UK distributors of urodynamic systems were contacted and asked to provide information on the software features relating to data quality of the products they supply. The results of the market survey show that the features offered by manufacturers differ greatly. Automated features, which can be turned off in most cases, include: cough recognition, detrusor contraction detection, and high pressure alerts. There are currently no systems that assess data quality based on published guidelines. A literature review of current QC guidelines for urodynamics was carried out; QC audits were included in the literature review to see how closely guidelines were being followed. This review highlights the fact that basic QC is not being carried out effectively by urodynamicists. Based on the software features currently available and the results of the literature review there is both the need and capacity for a greater degree of automation in relation to urodynamic data quality and accuracy assessment. Some progress has been made in this area and certain manufacturers have already developed automated cough detection. Copyright © 2011 Wiley Periodicals, Inc.

A novel construction scheme of QC-LDPC codes based on the RU algorithm for optical transmission systems

NASA Astrophysics Data System (ADS)

Yuan, Jian-guo; Liang, Meng-qi; Wang, Yong; Lin, Jin-zhao; Pang, Yu

2016-03-01

A novel lower-complexity construction scheme of quasi-cyclic low-density parity-check (QC-LDPC) codes for optical transmission systems is proposed based on the structure of the parity-check matrix for the Richardson-Urbanke (RU) algorithm. Furthermore, a novel irregular QC-LDPC(4 288, 4 020) code with high code-rate of 0.937 is constructed by this novel construction scheme. The simulation analyses show that the net coding gain ( NCG) of the novel irregular QC-LDPC(4 288,4 020) code is respectively 2.08 dB, 1.25 dB and 0.29 dB more than those of the classic RS(255, 239) code, the LDPC(32 640, 30 592) code and the irregular QC-LDPC(3 843, 3 603) code at the bit error rate ( BER) of 10-6. The irregular QC-LDPC(4 288, 4 020) code has the lower encoding/decoding complexity compared with the LDPC(32 640, 30 592) code and the irregular QC-LDPC(3 843, 3 603) code. The proposed novel QC-LDPC(4 288, 4 020) code can be more suitable for the increasing development requirements of high-speed optical transmission systems.

High performance terahertz metasurface quantum-cascade VECSEL with an intra-cryostat cavity

DOE PAGES

Xu, Luyao; Curwen, Christopher A.; Reno, John L.; ...

2017-09-04

A terahertz quantum-cascade (QC) vertical-external-cavity surface-emitting-laser (VECSEL) is demonstrated with over 5 mW power in continuous-wave and single-mode operation above 77 K, in combination with a near-Gaussian beam pattern with full-width half-max divergence as narrow as ~5° × 5°, with no evidence of thermal lensing. This is realized by creating an intra-cryostat VECSEL cavity to reduce the cavity loss and designing an active focusing metasurface reflector with low power dissipation for efficient heat removal. Compared with a conventional quantumcascade laser based on a metal-metal waveguide, the intra-cryostat QC-VECSEL exhibits significant improvements in both output power level and beam pattern. Also,more » the intra-cryostat configuration newly allows evaluation of QC-VECSEL operation vs. temperature, showing a maximum pulsed mode operating temperature of 129 K. While the threshold current density in the QC-VECSEL is worse in comparison to a conventional edge-emitting metal-metal waveguide QClaser, the beam quality, slope efficiency, maximum power, and thermal resistance are all significantly improved.« less

Quantum paraelectricity in copper-titanates: Magnetic-order driven vitrification

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

Kumar, Jitender; Awasthi, A. M., E-mail: amawasthi@csr.res.in

2015-07-21

Quantum-paraelectric (QP) family character is emergent from shared low-temperature characteristics of SrCu{sub 3}Ti{sub 4}O{sub 12} (SCTO), CaCu{sub 3}Ti{sub 4}O{sub 12} (CCTO), and Ca{sub 0.9}Li{sub 0.1}Cu{sub 3}Ti{sub 4}O{sub 12} (CLCTO) A{sub 1/4}A′{sub 3/4}BO{sub 3} structures featuring antiferro-tilted Ti-O{sub 6} octahedra. Above their magnetic ordering temperatures T{sub N}, permittivity of SCTO and CLCTO follow typical Barrett form, whereas in CCTO, quantum paraelectricity is masked by the huge ε′-step. Hidden QP in CCTO gets revealed by Li-doping at the Ca-site, which considerably up-shifts the temperature scale (from ∼100 K to ∼250 K) of the dielectric step-anomaly in CLCTO. Competing magneto-electricity and quantum fluctuations result inmore » glassy-arrest of the QP degrees of freedom near T{sub N}; manifest as dispersive-deviation of the permittivity (in SCTO and CLCTO) from the low-temperature Barrett saturation. However, quantum criticality (QC) regime being well above T{sub N} registers its presence nevertheless, as the ∼T{sup 2} behaviour of their inverse dielectric susceptibility. Non-compliance to the usual behaviours of dispersive-response vs. bias-field and temperature unambiguously rule out a relaxor origin of the glassy state. We determine a dimensionless thermal window (0.3 ≤ T/T{sub 1} ≤ 0.6) of QC signature, covering typical quantum-paraelectrics.« less

A novel construction method of QC-LDPC codes based on CRT for optical communications

NASA Astrophysics Data System (ADS)

Yuan, Jian-guo; Liang, Meng-qi; Wang, Yong; Lin, Jin-zhao; Pang, Yu

2016-05-01

A novel construction method of quasi-cyclic low-density parity-check (QC-LDPC) codes is proposed based on Chinese remainder theory (CRT). The method can not only increase the code length without reducing the girth, but also greatly enhance the code rate, so it is easy to construct a high-rate code. The simulation results show that at the bit error rate ( BER) of 10-7, the net coding gain ( NCG) of the regular QC-LDPC(4 851, 4 546) code is respectively 2.06 dB, 1.36 dB, 0.53 dB and 0.31 dB more than those of the classic RS(255, 239) code in ITU-T G.975, the LDPC(32 640, 30 592) code in ITU-T G.975.1, the QC-LDPC(3 664, 3 436) code constructed by the improved combining construction method based on CRT and the irregular QC-LDPC(3 843, 3 603) code constructed by the construction method based on the Galois field ( GF( q)) multiplicative group. Furthermore, all these five codes have the same code rate of 0.937. Therefore, the regular QC-LDPC(4 851, 4 546) code constructed by the proposed construction method has excellent error-correction performance, and can be more suitable for optical transmission systems.

Measurement of the quantum capacitance from two-dimensional surface state of a topological insulator at room temperature

NASA Astrophysics Data System (ADS)

Choi, Hyunwoo; Kim, Tae Geun; Shin, Changhwan

2017-06-01

A topological insulator (TI) is a new kind of material that exhibits unique electronic properties owing to its topological surface state (TSS). Previous studies focused on the transport properties of the TSS, since it can be used as the active channel layer in metal-oxide-semiconductor field-effect transistors (MOSFETs). However, a TI with a negative quantum capacitance (QC) effect can be used in the gate stack of MOSFETs, thereby facilitating the creation of ultra-low power electronics. Therefore, it is important to study the physics behind the QC in TIs in the absence of any external magnetic field, at room temperature. We fabricated a simple capacitor structure using a TI (TI-capacitor: Au-TI-SiO2-Si), which shows clear evidence of QC at room temperature. In the capacitance-voltage (C-V) measurement, the total capacitance of the TI-capacitor increases in the accumulation regime, since QC is the dominant capacitive component in the series capacitor model (i.e., CT-1 = CQ-1 + CSiO2-1). Based on the QC model of the two-dimensional electron systems, we quantitatively calculated the QC, and observed that the simulated C-V curve theoretically supports the conclusion that the QC of the TI-capacitor is originated from electron-electron interaction in the two-dimensional surface state of the TI.

Hybrid MC/QC simulations of water-assisted proton transfer in nucleosides. Guanosine and its analog acyclovir.

PubMed

Markova, Nadezhda; Pejov, Ljupco; Stoyanova, Nina; Enchev, Venelin

2017-05-01

To provide an in-depth insight into the molecular basis of spontaneous tautomerism in DNA and RNA base pairs, a hybrid Monte Carlo (MC)-quantum chemical (QC) methodology is implemented to map two-dimensional potential energy surfaces along the reaction coordinates of solvent-assisted proton transfer processes in guanosine and its analog acyclovir in aqueous solution. The solvent effects were simulated by explicit inclusion of water molecules that model the relevant part of the first hydration shell around the solute. The position of these water molecules was estimated by carrying out a classical Metropolis Monte Carlo simulation of dilute water solutions of the guanosine (Gs) and acyclovir (ACV) and subsequently analyzing solute-solvent intermolecular interactions in the statistically-independent MC-generated configurations. The solvent-assisted proton transfer processes were further investigated using two different ab initio MP2 quantum chemical approaches. In the first one, potential energy surfaces of the 'bare' finite solute-solvent clusters containing Gs/ACV and four water molecules (MP2/6-31+G(d,p) level) were explored, while within the second approach, these clusters were embedded in 'bulk' solvent treated as polarizable continuum (C-PCM/MP2/6-31+G(d,p) level of theory). It was found that in the gas phase and in water solution, the most stable tautomer for guanosine and acyclovir is the 1H-2-amino-6-oxo form followed by the 2-amino-6-(sZ)-hydroxy form. The energy barriers of the water-assisted proton transfer reaction in guanosine and in acyclovir are found to be very similar - 11.74 kcal mol -1 for guanosine and 11.16 kcal mol -1 for acyclovir, and the respective rate constants (k = 1.5 × 10 1 s -1 , guanosine and k = 4.09 × 10 1 s -1 , acyclovir), are sufficiently large to generate the 2-amino-6-(sZ)-hydroxy tautomer. The analysis of the reaction profiles in both compounds shows that the proton transfer processes occur through the

Development of the QA/QC Procedures for a Neutron Interrogation System

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

Obhodas, Jasmina; Sudac, Davorin; Valkovic, Vladivoj

In order to perform QA/QC procedures for a system dedicated to the neutron interrogation of objects for the presence of threat materials one needs to perform measurements of reference materials (RM) having the same (or similar) atomic ratios as real materials. It is well known that explosives, drugs, and various other benign materials, contain chemical elements such as hydrogen, oxygen, carbon and nitrogen in distinctly different quantities. For example, a high carbon-to-oxygen ratio (C/O) is characteristic of drugs. Explosives can be differentiated by measurement of both C/O and nitrogen-to-oxygen (N/O) ratios. The C/N ratio of the chemical warfare agents, coupledmore » with the measurement of elements such as fluorine and phosphorus, clearly differentiate them from the conventional explosives. Correlations between theoretical values and experimental results obtained in laboratory conditions for C/O and N/C ratios of simulants of hexogen (RDX), TNT, DLM2, TATP, cocaine, heroin, yperite, tetranitromethane, peroxide methylethyl-ketone, nitromethane and ethyleneglycol dinitrate are presented. (authors)« less

An efficient matrix product operator representation of the quantum chemical Hamiltonian

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

Keller, Sebastian, E-mail: sebastian.keller@phys.chem.ethz.ch; Reiher, Markus, E-mail: markus.reiher@phys.chem.ethz.ch; Dolfi, Michele, E-mail: dolfim@phys.ethz.ch

We describe how to efficiently construct the quantum chemical Hamiltonian operator in matrix product form. We present its implementation as a density matrix renormalization group (DMRG) algorithm for quantum chemical applications. Existing implementations of DMRG for quantum chemistry are based on the traditional formulation of the method, which was developed from the point of view of Hilbert space decimation and attained higher performance compared to straightforward implementations of matrix product based DMRG. The latter variationally optimizes a class of ansatz states known as matrix product states, where operators are correspondingly represented as matrix product operators (MPOs). The MPO construction schememore » presented here eliminates the previous performance disadvantages while retaining the additional flexibility provided by a matrix product approach, for example, the specification of expectation values becomes an input parameter. In this way, MPOs for different symmetries — abelian and non-abelian — and different relativistic and non-relativistic models may be solved by an otherwise unmodified program.« less

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.

Intrinsic Atomic Orbitals: An Unbiased Bridge between Quantum Theory and Chemical Concepts.

PubMed

Knizia, Gerald

2013-11-12

Modern quantum chemistry can make quantitative predictions on an immense array of chemical systems. However, the interpretation of those predictions is often complicated by the complex wave function expansions used. Here we show that an exceptionally simple algebraic construction allows for defining atomic core and valence orbitals, polarized by the molecular environment, which can exactly represent self-consistent field wave functions. This construction provides an unbiased and direct connection between quantum chemistry and empirical chemical concepts, and can be used, for example, to calculate the nature of bonding in molecules, in chemical terms, from first principles. In particular, we find consistency with electronegativities (χ), C 1s core-level shifts, resonance substituent parameters (σR), Lewis structures, and oxidation states of transition-metal complexes.

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.

Quantum chemical parameters in QSAR: what do I use when?

USGS Publications Warehouse

Hickey, James P.; Ostrander, Gary K.

1996-01-01

This chapter provides a brief overview of the numerous quantum chemical parameters that have been/are currently being used in quantitative structure activity relationships (QSAR), along with a representative bibliography. The parameters will be grouped according to their mechanistic interpretations, and representative biological and physical chemical applications will be mentioned. Parmater computation methods and the appropriate software are highlighted, as are sources for software.

40 CFR 98.74 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Ammonia Manufacturing § 98.74 Monitoring and QA/QC... (c)(8) of this section. (f) [Reserved] (g) If CO2 from ammonia production is used to produce urea at...

40 CFR 98.74 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Ammonia Manufacturing § 98.74 Monitoring and QA/QC... (c)(8) of this section. (f)[Reserved] (g) If CO2 from ammonia production is used to produce urea at...

40 CFR 98.74 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Ammonia Manufacturing § 98.74 Monitoring and QA/QC... (c)(8) of this section. (f)[Reserved] (g) If CO2 from ammonia production is used to produce urea at...

40 CFR 98.74 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Ammonia Manufacturing § 98.74 Monitoring and QA/QC... (c)(8) of this section. (f) [Reserved] (g) If CO2 from ammonia production is used to produce urea at...

Construction method of QC-LDPC codes based on multiplicative group of finite field in optical communication

NASA Astrophysics Data System (ADS)

Huang, Sheng; Ao, Xiang; Li, Yuan-yuan; Zhang, Rui

2016-09-01

In order to meet the needs of high-speed development of optical communication system, a construction method of quasi-cyclic low-density parity-check (QC-LDPC) codes based on multiplicative group of finite field is proposed. The Tanner graph of parity check matrix of the code constructed by this method has no cycle of length 4, and it can make sure that the obtained code can get a good distance property. Simulation results show that when the bit error rate ( BER) is 10-6, in the same simulation environment, the net coding gain ( NCG) of the proposed QC-LDPC(3 780, 3 540) code with the code rate of 93.7% in this paper is improved by 2.18 dB and 1.6 dB respectively compared with those of the RS(255, 239) code in ITU-T G.975 and the LDPC(3 2640, 3 0592) code in ITU-T G.975.1. In addition, the NCG of the proposed QC-LDPC(3 780, 3 540) code is respectively 0.2 dB and 0.4 dB higher compared with those of the SG-QC-LDPC(3 780, 3 540) code based on the two different subgroups in finite field and the AS-QC-LDPC(3 780, 3 540) code based on the two arbitrary sets of a finite field. Thus, the proposed QC-LDPC(3 780, 3 540) code in this paper can be well applied in optical communication systems.

jqcML: an open-source java API for mass spectrometry quality control data in the qcML format.

PubMed

Bittremieux, Wout; Kelchtermans, Pieter; Valkenborg, Dirk; Martens, Lennart; Laukens, Kris

2014-07-03

The awareness that systematic quality control is an essential factor to enable the growth of proteomics into a mature analytical discipline has increased over the past few years. To this aim, a controlled vocabulary and document structure have recently been proposed by Walzer et al. to store and disseminate quality-control metrics for mass-spectrometry-based proteomics experiments, called qcML. To facilitate the adoption of this standardized quality control routine, we introduce jqcML, a Java application programming interface (API) for the qcML data format. First, jqcML provides a complete object model to represent qcML data. Second, jqcML provides the ability to read, write, and work in a uniform manner with qcML data from different sources, including the XML-based qcML file format and the relational database qcDB. Interaction with the XML-based file format is obtained through the Java Architecture for XML Binding (JAXB), while generic database functionality is obtained by the Java Persistence API (JPA). jqcML is released as open-source software under the permissive Apache 2.0 license and can be downloaded from https://bitbucket.org/proteinspector/jqcml .

40 CFR 98.434 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... Contained in Pre-Charged Equipment or Closed-Cell Foams § 98.434 Monitoring and QA/QC requirements. (a) For... equipment or closed-cell foam in the correct quantities (metric tons) and units (kg per piece of equipment...

40 CFR 98.434 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... Contained in Pre-Charged Equipment or Closed-Cell Foams § 98.434 Monitoring and QA/QC requirements. (a) For... equipment or closed-cell foam in the correct quantities (metric tons) and units (kg per piece of equipment...

40 CFR 98.434 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... Contained in Pre-Charged Equipment or Closed-Cell Foams § 98.434 Monitoring and QA/QC requirements. (a) For... equipment or closed-cell foam in the correct quantities and units. [74 FR 56374, Oct. 30, 2009, as amended...

Temperature-insensitive long-wavelength (λ ≈14 µm) Quantum Cascade lasers with low threshold.

PubMed

Huang, Xue; Charles, William O; Gmachl, Claire

2011-04-25

We demonstrate high-performance, long-wavelength (λ ≈14 µm) Quantum Cascade (QC) lasers based on a diagonal optical transition and a "two-phonon-continuum" depletion scheme in which the lower laser level is depopulated by resonant longitudinal optical phonon scattering followed by scattering to a lower energy level continuum. A 2.8 mm long QC laser shows a low threshold current density of 2.0 kA/cm2, a peak output power of ~336 mW, and a slope efficiency of 375 mW/A, all at 300 K, with a high characteristic temperature T0 ~310 K over a wide temperature range from 240 K to 390 K.

A novel QC-LDPC code based on the finite field multiplicative group for optical communications

NASA Astrophysics Data System (ADS)

Yuan, Jian-guo; Xu, Liang; Tong, Qing-zhen

2013-09-01

A novel construction method of quasi-cyclic low-density parity-check (QC-LDPC) code is proposed based on the finite field multiplicative group, which has easier construction, more flexible code-length code-rate adjustment and lower encoding/decoding complexity. Moreover, a regular QC-LDPC(5334,4962) code is constructed. The simulation results show that the constructed QC-LDPC(5334,4962) code can gain better error correction performance under the condition of the additive white Gaussian noise (AWGN) channel with iterative decoding sum-product algorithm (SPA). At the bit error rate (BER) of 10-6, the net coding gain (NCG) of the constructed QC-LDPC(5334,4962) code is 1.8 dB, 0.9 dB and 0.2 dB more than that of the classic RS(255,239) code in ITU-T G.975, the LDPC(32640,30592) code in ITU-T G.975.1 and the SCG-LDPC(3969,3720) code constructed by the random method, respectively. So it is more suitable for optical communication systems.

Protein-protected luminescent noble metal quantum clusters: an emerging trend in atomic cluster nanoscience

PubMed Central

Xavier, Paulrajpillai Lourdu; Chaudhari, Kamalesh; Baksi, Ananya; Pradeep, Thalappil

2012-01-01

Noble metal quantum clusters (NMQCs) are the missing link between isolated noble metal atoms and nanoparticles. NMQCs are sub-nanometer core sized clusters composed of a group of atoms, most often luminescent in the visible region, and possess intriguing photo-physical and chemical properties. A trend is observed in the use of ligands, ranging from phosphines to functional proteins, for the synthesis of NMQCs in the liquid phase. In this review, we briefly overview recent advancements in the synthesis of protein protected NMQCs with special emphasis on their structural and photo-physical properties. In view of the protein protection, coupled with direct synthesis and easy functionalization, this hybrid QC-protein system is expected to have numerous optical and bioimaging applications in the future, pointers in this direction are visible in the literature. PMID:22312454

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.

40 CFR 98.434 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98.434 Section 98.434 Protection of Environment ENVIRONMENTAL PROTECTION AGENCY (CONTINUED) AIR PROGRAMS (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Importers and Exporters of Fluorinated Greenhouse Gases...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... by Gas Chromatography (incorporated by reference see § 98.7). All gas composition monitors shall be...-90 (Reapproved 2006) Standard Practice for Analysis of Reformed Gas by Gas Chromatography... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... by Gas Chromatography (incorporated by reference see § 98.7). All gas composition monitors shall be...-90 (Reapproved 2006) Standard Practice for Analysis of Reformed Gas by Gas Chromatography... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements...

40 CFR 98.164 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Hydrogen Production § 98.164 Monitoring and QA/QC requirements. The GHG emissions data for hydrogen production process units must be quality-assured as specified in... Instrumental Determination of Carbon, Hydrogen, and Nitrogen in Petroleum Products and Lubricants (incorporated...

QC operator’s nonneutral posture against musculoskeletal disorder’s (MSDs) risks

NASA Astrophysics Data System (ADS)

Kautsar, F.; Gustopo, D.; Achmadi, F.

2018-04-01

Musculoskeletal disorders refer to a gamut of inflammatory and degenerative disorders aggravated largely by the performance of work. It is the major cause of pain, disability, absenteeism and reduced productivity among workers worldwide. Although it is not fatal, MSDs have the potential to develop into serious injuries in the musculoskeletal system if ignored. QC operators work in nonneutral body posture. This cross-sectional study was condusted in order to investigate correlation between risk assessment results of QEC and body posture calculation of mannequin pro. Statistical analysis was condusted using SPSS version 16.0. Validity test, Reliability test and Regression analysis were conducted to compare the risk assessment output of applied method and nonneutral body posture simulation. All of QEC’s indicator classified as valid and reliable. The result of simple regression anlysis are back (0.326<4.32), shoulder/arm (8.489>4.32), wrist/hand (4.86 >4.32) and neck (1.298 <4.32). Result of this study shows that there is an influence between nonneutral body posture of the QC operator during work with risk of musculoskeletal disorders. The potential risk of musculoskeletal disorders is in the shoulder/arm and wrist/hand of the QC operator, whereas the back and neck are not affected.

40 CFR 98.164 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Hydrogen Production § 98.164 Monitoring and QA/QC requirements. The GHG emissions data for hydrogen production process units must be quality-assured as specified in..., Hydrogen, and Nitrogen in Petroleum Products and Lubricants (incorporated by reference, see § 98.7). (xi...

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.

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

PubMed

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

2018-06-13

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

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.

40 CFR 98.84 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Cement Production § 98.84 Monitoring and QA/QC requirements..., shale, iron oxide, and alumina). Facilities that opt to use the default total organic carbon factor... quantity of each category of raw materials consumed by the facility (e.g., limestone, sand, shale, iron...

40 CFR 98.84 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Cement Production § 98.84 Monitoring and QA/QC requirements..., shale, iron oxide, and alumina). Facilities that opt to use the default total organic carbon factor... quantity of each category of raw materials consumed by the facility (e.g., limestone, sand, shale, iron...

40 CFR 98.84 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Cement Production § 98.84 Monitoring and QA/QC requirements..., shale, iron oxide, and alumina). Facilities that opt to use the default total organic carbon factor... quantity of each category of raw materials consumed by the facility (e.g., limestone, sand, shale, iron...

40 CFR 98.144 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Glass Production § 98.144 Monitoring and QA/QC requirements. (a) You must measure annual amounts of carbonate-based raw materials charged to each continuous glass... calibrated scales or weigh hoppers. Total annual mass charged to glass melting furnaces at the facility shall...

40 CFR 98.74 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... Relative Molecular Mass of Petroleum Oils from Viscosity Measurements (incorporated by reference, see § 98... Weight) of Hydrocarbons by Thermoelectric Measurement of Vapor Pressure (incorporated by reference, see... measurements according to the monitoring and QA/QC requirements for the Tier 3 methodology in § 98.34(b). (e...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... or operator shall document the procedures used to ensure the accuracy of gas flow rate, gas... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements... fraction of total manure managed in each system component. (c) The CH4 concentration of gas from digesters...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... or operator shall document the procedures used to ensure the accuracy of gas flow rate, gas... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements... fraction of total manure managed in each system component. (c) The CH4 concentration of gas from digesters...

40 CFR 98.364 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... or operator shall document the procedures used to ensure the accuracy of gas flow rate, gas... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Manure Management § 98.364 Monitoring and QA/QC requirements... fraction of total manure managed in each system component. (c) The CH4 concentration of gas from digesters...

40 CFR 98.414 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... 40 Protection of Environment 20 2010-07-01 2010-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Industrial Greenhouse Gases § 98.414 Monitoring... or better. If the mass in paragraph (a) of this section is measured by weighing containers that...

40 CFR 98.394 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Petroleum Products § 98.394 Monitoring and QA/QC requirements. (a) Determination of quantity. (1) The quantity of petroleum products, natural gas liquids... product or natural gas liquid on any day of each calendar month of the reporting year in which the...

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.

RNA-SeQC: RNA-seq metrics for quality control and process optimization.

PubMed

DeLuca, David S; Levin, Joshua Z; Sivachenko, Andrey; Fennell, Timothy; Nazaire, Marc-Danie; Williams, Chris; Reich, Michael; Winckler, Wendy; Getz, Gad

2012-06-01

RNA-seq, the application of next-generation sequencing to RNA, provides transcriptome-wide characterization of cellular activity. Assessment of sequencing performance and library quality is critical to the interpretation of RNA-seq data, yet few tools exist to address this issue. We introduce RNA-SeQC, a program which provides key measures of data quality. These metrics include yield, alignment and duplication rates; GC bias, rRNA content, regions of alignment (exon, intron and intragenic), continuity of coverage, 3'/5' bias and count of detectable transcripts, among others. The software provides multi-sample evaluation of library construction protocols, input materials and other experimental parameters. The modularity of the software enables pipeline integration and the routine monitoring of key measures of data quality such as the number of alignable reads, duplication rates and rRNA contamination. RNA-SeQC allows investigators to make informed decisions about sample inclusion in downstream analysis. In summary, RNA-SeQC provides quality control measures critical to experiment design, process optimization and downstream computational analysis. See www.genepattern.org to run online, or www.broadinstitute.org/rna-seqc/ for a command line tool.

Comparison of Chain Conformation of Poly(vinyl alcohol) in Solutions and Melts from Quantum Chemistry Based Molecular Dynamics Simulations

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Han, Jie; Matsuda, Tsunetoshi; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

Confirmations of 2,4-dihydroxypentane (DHP), a model molecule for poly(vinyl alcohol), have been studied by quantum chemistry (QC) calculations and molecular dynamics (MD) simulations. QC calculations at the 6-311G MP2 level show the meso tt conformer to be lowest in energy followed by the racemic tg, due to intramolecular hydrogen bond between the hydroxy groups. The Dreiding force field has been modified to reproduce the QC conformer energies for DHP. MD simulations using this force field have been carried out for DHP molecules in the gas phase, melt, and CHCl3 and water solutions. Extensive intramolecular hydrogen bonding is observed for the gas phase and CHCl3 solution, but not for the melt or aqueous solution, Such a condensed phase effect due to intermolecular interactions results in a drastic change in chain conformations, in agreement with experiments.

40 CFR 98.444 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... 40 Protection of Environment 22 2012-07-01 2012-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Geologic Sequestration of Carbon Dioxide § 98.444 Monitoring... volume of contents in all containers if you receive CO2 in containers by following the most appropriate...

40 CFR 98.444 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... 40 Protection of Environment 21 2014-07-01 2014-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Geologic Sequestration of Carbon Dioxide § 98.444 Monitoring... volume of contents in all containers if you receive CO2 in containers by following the most appropriate...

40 CFR 98.444 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... 40 Protection of Environment 22 2013-07-01 2013-07-01 false Monitoring and QA/QC requirements. 98... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Geologic Sequestration of Carbon Dioxide § 98.444 Monitoring... volume of contents in all containers if you receive CO2 in containers by following the most appropriate...

40 CFR 98.394 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2011 CFR

2011-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Petroleum Products § 98.394 Monitoring and QA/QC requirements. (a) Determination of quantity. (1) The quantity of petroleum products, natural gas liquids, and... each petroleum product or natural gas liquid on any day of each calendar month of the reporting year in...

40 CFR 98.394 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2013 CFR

2013-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Petroleum Products § 98.394 Monitoring and QA/QC requirements. (a) Determination of quantity. (1) The quantity of petroleum products, natural gas liquids, and... each petroleum product or natural gas liquid on any day of each calendar month of the reporting year in...

40 CFR 98.394 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2014 CFR

2014-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Petroleum Products § 98.394 Monitoring and QA/QC requirements. (a) Determination of quantity. (1) The quantity of petroleum products, natural gas liquids, and... or natural gas liquid on any day of each calendar month of the reporting year in which the quantity...

40 CFR 98.394 - Monitoring and QA/QC requirements.

Code of Federal Regulations, 2012 CFR

2012-07-01

... (CONTINUED) MANDATORY GREENHOUSE GAS REPORTING Suppliers of Petroleum Products § 98.394 Monitoring and QA/QC requirements. (a) Determination of quantity. (1) The quantity of petroleum products, natural gas liquids, and... each petroleum product or natural gas liquid on any day of each calendar month of the reporting year in...

qcML: An Exchange Format for Quality Control Metrics from Mass Spectrometry Experiments*

PubMed Central

Walzer, Mathias; Pernas, Lucia Espona; Nasso, Sara; Bittremieux, Wout; Nahnsen, Sven; Kelchtermans, Pieter; Pichler, Peter; van den Toorn, Henk W. P.; Staes, An; Vandenbussche, Jonathan; Mazanek, Michael; Taus, Thomas; Scheltema, Richard A.; Kelstrup, Christian D.; Gatto, Laurent; van Breukelen, Bas; Aiche, Stephan; Valkenborg, Dirk; Laukens, Kris; Lilley, Kathryn S.; Olsen, Jesper V.; Heck, Albert J. R.; Mechtler, Karl; Aebersold, Ruedi; Gevaert, Kris; Vizcaíno, Juan Antonio; Hermjakob, Henning; Kohlbacher, Oliver; Martens, Lennart

2014-01-01

Quality control is increasingly recognized as a crucial aspect of mass spectrometry based proteomics. Several recent papers discuss relevant parameters for quality control and present applications to extract these from the instrumental raw data. What has been missing, however, is a standard data exchange format for reporting these performance metrics. We therefore developed the qcML format, an XML-based standard that follows the design principles of the related mzML, mzIdentML, mzQuantML, and TraML standards from the HUPO-PSI (Proteomics Standards Initiative). In addition to the XML format, we also provide tools for the calculation of a wide range of quality metrics as well as a database format and interconversion tools, so that existing LIMS systems can easily add relational storage of the quality control data to their existing schema. We here describe the qcML specification, along with possible use cases and an illustrative example of the subsequent analysis possibilities. All information about qcML is available at http://code.google.com/p/qcml. PMID:24760958

qcML: an exchange format for quality control metrics from mass spectrometry experiments.

PubMed

Walzer, Mathias; Pernas, Lucia Espona; Nasso, Sara; Bittremieux, Wout; Nahnsen, Sven; Kelchtermans, Pieter; Pichler, Peter; van den Toorn, Henk W P; Staes, An; Vandenbussche, Jonathan; Mazanek, Michael; Taus, Thomas; Scheltema, Richard A; Kelstrup, Christian D; Gatto, Laurent; van Breukelen, Bas; Aiche, Stephan; Valkenborg, Dirk; Laukens, Kris; Lilley, Kathryn S; Olsen, Jesper V; Heck, Albert J R; Mechtler, Karl; Aebersold, Ruedi; Gevaert, Kris; Vizcaíno, Juan Antonio; Hermjakob, Henning; Kohlbacher, Oliver; Martens, Lennart

2014-08-01

Quality control is increasingly recognized as a crucial aspect of mass spectrometry based proteomics. Several recent papers discuss relevant parameters for quality control and present applications to extract these from the instrumental raw data. What has been missing, however, is a standard data exchange format for reporting these performance metrics. We therefore developed the qcML format, an XML-based standard that follows the design principles of the related mzML, mzIdentML, mzQuantML, and TraML standards from the HUPO-PSI (Proteomics Standards Initiative). In addition to the XML format, we also provide tools for the calculation of a wide range of quality metrics as well as a database format and interconversion tools, so that existing LIMS systems can easily add relational storage of the quality control data to their existing schema. We here describe the qcML specification, along with possible use cases and an illustrative example of the subsequent analysis possibilities. All information about qcML is available at http://code.google.com/p/qcml. © 2014 by The American Society for Biochemistry and Molecular Biology, Inc.

Building a QC Database of Meteorological Data from NASA KSC and the United States Air Force's Eastern Range

NASA Technical Reports Server (NTRS)

Brenton, J. C.; Barbre, R. E.; Decker, R. K.; Orcutt, J. M.

2018-01-01

The National Aeronautics and Space Administration's (NASA) Marshall Space Flight Center (MSFC) Natural Environments Branch (EV44) provides atmospheric databases and analysis in support of space vehicle design and day-of-launch operations for NASA and commercial launch vehicle programs launching from the NASA Kennedy Space Center (KSC), co-located on the United States Air Force's Eastern Range (ER) at the Cape Canaveral Air Force Station. The ER complex is one of the most heavily instrumented sites in the United States with over 31 towers measuring various atmospheric parameters on a continuous basis. An inherent challenge with large datasets consists of ensuring erroneous data are removed from databases, and thus excluded from launch vehicle design analyses. EV44 has put forth great effort in developing quality control (QC) procedures for individual meteorological instruments, however no standard QC procedures for all databases currently exists resulting in QC databases that have inconsistencies in variables, development methodologies, and periods of record. The goal of this activity is to use the previous efforts to develop a standardized set of QC procedures from which to build meteorological databases from KSC and the ER, while maintaining open communication with end users from the launch community to develop ways to improve, adapt and grow the QC database. Details of the QC procedures will be described. As the rate of launches increases with additional launch vehicle programs, It is becoming more important that weather databases are continually updated and checked for data quality before use in launch vehicle design and certification analyses.

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

Quantum Chemically Estimated Abraham Solute Parameters Using Multiple Solvent-Water Partition Coefficients and Molecular Polarizability.

PubMed

Liang, Yuzhen; Xiong, Ruichang; Sandler, Stanley I; Di Toro, Dominic M

2017-09-05

Polyparameter Linear Free Energy Relationships (pp-LFERs), also called Linear Solvation Energy Relationships (LSERs), are used to predict many environmentally significant properties of chemicals. A method is presented for computing the necessary chemical parameters, the Abraham parameters (AP), used by many pp-LFERs. It employs quantum chemical calculations and uses only the chemical's molecular structure. The method computes the Abraham E parameter using density functional theory computed molecular polarizability and the Clausius-Mossotti equation relating the index refraction to the molecular polarizability, estimates the Abraham V as the COSMO calculated molecular volume, and computes the remaining AP S, A, and B jointly with a multiple linear regression using sixty-five solvent-water partition coefficients computed using the quantum mechanical COSMO-SAC solvation model. These solute parameters, referred to as Quantum Chemically estimated Abraham Parameters (QCAP), are further adjusted by fitting to experimentally based APs using QCAP parameters as the independent variables so that they are compatible with existing Abraham pp-LFERs. QCAP and adjusted QCAP for 1827 neutral chemicals are included. For 24 solvent-water systems including octanol-water, predicted log solvent-water partition coefficients using adjusted QCAP have the smallest root-mean-square errors (RMSEs, 0.314-0.602) compared to predictions made using APs estimated using the molecular fragment based method ABSOLV (0.45-0.716). For munition and munition-like compounds, adjusted QCAP has much lower RMSE (0.860) than does ABSOLV (4.45) which essentially fails for these compounds.

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

Mid-infrared Photoconductive Response in AlGaN/GaN Step Quantum Wells

PubMed Central

Rong, X.; Wang, X. Q.; Chen, G.; Zheng, X. T.; Wang, P.; Xu, F. J.; Qin, Z. X.; Tang, N.; Chen, Y. H.; Sang, L. W.; Sumiya, M.; Ge, W. K.; Shen, B.

2015-01-01

AlGaN/GaN quantum structure is an excellent candidate for high speed infrared detectors based on intersubband transitions. However, fabrication of AlGaN/GaN quantum well infrared detectors suffers from polarization-induced internal electric field, which greatly limits the carrier vertical transport. In this article, a step quantum well is proposed to attempt solving this problem, in which a novel spacer barrier layer is used to balance the internal electric field. As a result, a nearly flat band potential profile is obtained in the step barrier layers of the AlGaN/GaN step quantum wells and a bound-to-quasi-continuum (B-to-QC) type intersubband prototype device with detectable photocurrent at atmosphere window (3–5 μm) is achieved in such nitride semiconductors. PMID:26395756

Influence of chemical and mechanical polishing on water sorption and solubility of denture base acrylic resins.

PubMed

Rahal, Juliana Saab; Mesquita, Marcelo Ferraz; Henriques, Guilherme Elias Pessanha; Nóbilo, Mauro Antonio Arruda

2004-01-01

Influence of polishing methods on water sorption and solubility of denture base acrylic resins was studied. Eighty samples were divided into groups: Classico (CL), and QC 20 (QC) - hot water bath cured; Acron MC (AC), and Onda Cryl (ON) - microwave cured; and submitted to mechanical polishing (MP) - pumice slurry, chalk powder, soft brush and felt cone in a bench vise; or chemical polishing (CP) - heated monomer fluid in a chemical polisher. The first desiccation process was followed by storage in distilled water at 37 +/- 1 degrees C for 1 h, 1 day, 1, 2, 3 and 4 weeks. Concluding each period, water sorption was measured. After the fourth week, a second desiccation process was done to calculate solubility. Data were submitted to analysis of variance, followed by Tukey test (pQC-MP: 2.31 and -0.05; QC-CP: 2.32 and 0.25; AC-MP: 2.45 and -0.07; AC-CP: 2.43 and 0.41; ON-MP: 2.32 and -0.06; ON-CP: 2.34 and 0.27. Mechanical polishing promoted significantly lower solubility of acrylic resins; initially, water sorption values were higher for chemically polished samples, however, after 4 weeks all groups were similar.

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.

From quantum cascade to super cascade laser a new laser design paradigm for broad spectral emission & a re-examination of current spreading

NASA Astrophysics Data System (ADS)

Le, Loan T.

Over the span of more than 20 years of development, the Quantum Cascade (QC) laser has positioned itself as the most viable mid-infrared (mid-IR) light source. Today's QC lasers emit watts of continuous wave power at room temperature. Despite significant progress, the mid-IR region remains vastly under-utilized. State-of-the-art QC lasers are found in high power defense applications and detection of trace gases with narrow absorption lines. A large number of applications, however, do not require so much power, but rather, a broadly tunable laser source to detect molecules with broad absorption features. As such, a QC laser that is broadly tunable over the entire biochemical fingerprinting region remains the missing link to markets such as non- invasive biomedical diagnostics, food safety, and stand-off detection in turbid media. In this thesis, we detail how we utilized the inherent flexibility of the QC design space to conceive a new type of laser with the potential to bridge that missing link of the QC laser to large commercial markets. Our design concept, the Super Cascade (SC) laser, works contrary to conventional laser design principle by supporting multiple independent optical transitions, each contributing to broadening the gain spectrum. We have demonstrated a room temperature laser gain medium with electroluminescence spanning 3.3-12.5 ?m and laser emission from 6.2-12.5 ?m, the record spectral width for any solid state laser gain medium. This gain bandwidth covers the entire biochemical fingerprinting region. The achievement of such a spectrally broad gain medium presents engineering challenges of how to optimally utilize the bandwidth. As of this work, a monolithi- cally integrated array of Distributed Feedback QC (DFB-QC) lasers is one of the most promising ways to fully utilize the SC gain bandwidth. Therefore, in this thesis, we explore ways of improving the yield and ease of fabrication of DFB-QC lasers, including a re-examination of the role of

Development of concrete QC/QA specifications for highway construction in Kentucky.

DOT National Transportation Integrated Search

2001-08-01

There is a growing trend toward quality-based specifications in highway construction. A large number of quality control/quality assurance (QC/QA) specifications shift the responsibility of day-to-day testing from the state DOH to the contractor. This...

Construction of type-II QC-LDPC codes with fast encoding based on perfect cyclic difference sets

NASA Astrophysics Data System (ADS)

Li, Ling-xiang; Li, Hai-bing; Li, Ji-bi; Jiang, Hua

2017-09-01

In view of the problems that the encoding complexity of quasi-cyclic low-density parity-check (QC-LDPC) codes is high and the minimum distance is not large enough which leads to the degradation of the error-correction performance, the new irregular type-II QC-LDPC codes based on perfect cyclic difference sets (CDSs) are constructed. The parity check matrices of these type-II QC-LDPC codes consist of the zero matrices with weight of 0, the circulant permutation matrices (CPMs) with weight of 1 and the circulant matrices with weight of 2 (W2CMs). The introduction of W2CMs in parity check matrices makes it possible to achieve the larger minimum distance which can improve the error- correction performance of the codes. The Tanner graphs of these codes have no girth-4, thus they have the excellent decoding convergence characteristics. In addition, because the parity check matrices have the quasi-dual diagonal structure, the fast encoding algorithm can reduce the encoding complexity effectively. Simulation results show that the new type-II QC-LDPC codes can achieve a more excellent error-correction performance and have no error floor phenomenon over the additive white Gaussian noise (AWGN) channel with sum-product algorithm (SPA) iterative decoding.

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.

STM images and STS for a rectangular quantum corral constructed with δ-function barriers and the effect of an adsorbed atom on STM images and STS

NASA Astrophysics Data System (ADS)

Mitsuoka, Shigenori; Tamura, Akira

2012-04-01

Assuming that an electron confined by double δ-function barriers is in a quasi-stationary state, we derived eigenfunctions and eigenenergies of the electron. Applying this point of view to the electron confined in a rectangular quantum corral (QC), we obtained scanning tunneling microscopic (STM) images and scanning tunneling spectrum (STS). Our results are consistent with experimental ones, which confirms validity of the present model. Comparing with the treatment in which the corral potential is chosen to be of square-barrier type, the present treatment has an advantage that the eigenvalue equations are simple and the number of parameters that specify the potential barrier is only one except the bottom of the potential well. On the basis of a Dyson equation for the Green function we calculated STM images and STS of the QC having an adsorbed atom inside. Our results are consistent with experimental STM images and STS. In contrast to a previous viewpoint that the STS profile is reversed with that of the empty QC, we concluded the STS peaks of the adsorbed QC are shifted downward from those of the empty QC.

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.

Building a QC Database of Meteorological Data From NASA KSC and the United States Air Force's Eastern Range

NASA Technical Reports Server (NTRS)

Brenton, James C.; Barbre, Robert E.; Orcutt, John M.; Decker, Ryan K.

2018-01-01

The National Aeronautics and Space Administration's (NASA) Marshall Space Flight Center (MSFC) Natural Environments Branch (EV44) has provided atmospheric databases and analysis in support of space vehicle design and day-of-launch operations for NASA and commercial launch vehicle programs launching from the NASA Kennedy Space Center (KSC), co-located on the United States Air Force's Eastern Range (ER) at the Cape Canaveral Air Force Station. The ER is one of the most heavily instrumented sites in the United States measuring various atmospheric parameters on a continuous basis. An inherent challenge with the large databases that EV44 receives from the ER consists of ensuring erroneous data are removed from the databases, and thus excluded from launch vehicle design analyses. EV44 has put forth great effort in developing quality control (QC) procedures for individual meteorological instruments; however, no standard QC procedures for all databases currently exist resulting in QC databases that have inconsistencies in variables, methodologies, and periods of record. The goal of this activity is to use the previous efforts by EV44 to develop a standardized set of QC procedures from which to build flags within the meteorological databases from KSC and the ER, while maintaining open communication with end users from the launch community to develop ways to improve, adapt and grow the QC database. Details of the QC checks are described. The flagged data points will be plotted in a graphical user interface (GUI) as part of a manual confirmation that the flagged data do indeed need to be removed from the archive. As the rate of launches increases with additional launch vehicle programs, more emphasis is being placed to continually update and check weather databases for data quality before use in launch vehicle design and certification analyses.

Spectroscopic and chemical reactivity analysis of D-Myo-Inositol using quantum chemical approach and its experimental verification

NASA Astrophysics Data System (ADS)

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

2017-07-01

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

FQC Dashboard: integrates FastQC results into a web-based, interactive, and extensible FASTQ quality control tool

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

Brown, Joseph; Pirrung, Meg; McCue, Lee Ann

FQC is software that facilitates quality control of FASTQ files by carrying out a QC protocol using FastQC, parsing results, and aggregating quality metrics into an interactive dashboard designed to richly summarize individual sequencing runs. The dashboard groups samples in dropdowns for navigation among the data sets, utilizes human-readable configuration files to manipulate the pages and tabs, and is extensible with CSV data.

FQC Dashboard: integrates FastQC results into a web-based, interactive, and extensible FASTQ quality control tool

DOE PAGES

Brown, Joseph; Pirrung, Meg; McCue, Lee Ann

2017-06-09

FQC is software that facilitates quality control of FASTQ files by carrying out a QC protocol using FastQC, parsing results, and aggregating quality metrics into an interactive dashboard designed to richly summarize individual sequencing runs. The dashboard groups samples in dropdowns for navigation among the data sets, utilizes human-readable configuration files to manipulate the pages and tabs, and is extensible with CSV data.

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.

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

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

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

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

AmeriFlux CA-Qc2 Quebec - 1975 Harvested Black Spruce (HBS75)

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

Margolis, Hank

This is the AmeriFlux version of the carbon flux data for the site CA-Qc2 Quebec - 1975 Harvested Black Spruce (HBS75). Site Description - Quebec - Eastern Boreal; Black Spruce forest harvested in 1975.

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-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.

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

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.

Portland cement concrete pavement review of QC/QA data 2000 through 2009.

DOT National Transportation Integrated Search

2011-04-01

This report analyzes the Quality Control/Quality Assurance (QC/QA) data for Portland cement concrete pavement : (PCCP) awarded in the years 2000 through 2009. Analysis of the overall performance of the projects is accomplished by : reviewing the Calc...

From field notes to data portal - An operational QA/QC framework for tower networks

NASA Astrophysics Data System (ADS)

Sturtevant, C.; Hackley, S.; Meehan, T.; Roberti, J. A.; Holling, G.; Bonarrigo, S.

2016-12-01

Quality assurance and control (QA/QC) is one of the most important yet challenging aspects of producing research-quality data. This is especially so for environmental sensor networks collecting numerous high-frequency measurement streams at distributed sites. Here, the quality issues are multi-faceted, including sensor malfunctions, unmet theoretical assumptions, and measurement interference from the natural environment. To complicate matters, there are often multiple personnel managing different sites or different steps in the data flow. For large, centrally managed sensor networks such as NEON, the separation of field and processing duties is in the extreme. Tower networks such as Ameriflux, ICOS, and NEON continue to grow in size and sophistication, yet tools for robust, efficient, scalable QA/QC have lagged. Quality control remains a largely manual process relying on visual inspection of the data. In addition, notes of observed measurement interference or visible problems are often recorded on paper without an explicit pathway to data flagging during processing. As such, an increase in network size requires a near-proportional increase in personnel devoted to QA/QC, quickly stressing the human resources available. There is a need for a scalable, operational QA/QC framework that combines the efficiency and standardization of automated tests with the power and flexibility of visual checks, and includes an efficient communication pathway from field personnel to data processors to end users. Here we propose such a framework and an accompanying set of tools in development, including a mobile application template for recording tower maintenance and an R/shiny application for efficiently monitoring and synthesizing data quality issues. This framework seeks to incorporate lessons learned from the Ameriflux community and provide tools to aid continued network advancements.

Maintaining High Quality Data and Consistency Across a Diverse Flux Network: The Ameriflux QA/QC Technical Team

NASA Astrophysics Data System (ADS)

Chan, S.; Billesbach, D. P.; Hanson, C. V.; Biraud, S.

2014-12-01

The AmeriFlux quality assurance and quality control (QA/QC) technical team conducts short term (<2 weeks) intercomparisons using a portable eddy covariance system (PECS) to maintain high quality data observations and data consistency across the AmeriFlux network (http://ameriflux.lbl.gov/). Site intercomparisons identify discrepancies between the in situ and portable measurements and calculated fluxes. Findings are jointly discussed by the site staff and the QA/QC team to improve in the situ observations. Despite the relatively short duration of an individual site intercomparison, the accumulated record of all site visits (numbering over 100 since 2002) is a unique dataset. The ability to deploy redundant sensors provides a rare opportunity to identify, quantify, and understand uncertainties in eddy covariance and ancillary measurements. We present a few specific case studies from QA/QC site visits to highlight and share new and relevant findings related to eddy covariance instrumentation and operation.

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.

Support vector machine regression (LS-SVM)--an alternative to artificial neural networks (ANNs) for the analysis of quantum chemistry data?

PubMed

Balabin, Roman M; Lomakina, Ekaterina I

2011-06-28

A multilayer feed-forward artificial neural network (MLP-ANN) with a single, hidden layer that contains a finite number of neurons can be regarded as a universal non-linear approximator. Today, the ANN method and linear regression (MLR) model are widely used for quantum chemistry (QC) data analysis (e.g., thermochemistry) to improve their accuracy (e.g., Gaussian G2-G4, B3LYP/B3-LYP, X1, or W1 theoretical methods). In this study, an alternative approach based on support vector machines (SVMs) is used, the least squares support vector machine (LS-SVM) regression. It has been applied to ab initio (first principle) and density functional theory (DFT) quantum chemistry data. So, QC + SVM methodology is an alternative to QC + ANN one. The task of the study was to estimate the Møller-Plesset (MPn) or DFT (B3LYP, BLYP, BMK) energies calculated with large basis sets (e.g., 6-311G(3df,3pd)) using smaller ones (6-311G, 6-311G*, 6-311G**) plus molecular descriptors. A molecular set (BRM-208) containing a total of 208 organic molecules was constructed and used for the LS-SVM training, cross-validation, and testing. MP2, MP3, MP4(DQ), MP4(SDQ), and MP4/MP4(SDTQ) ab initio methods were tested. Hartree-Fock (HF/SCF) results were also reported for comparison. Furthermore, constitutional (CD: total number of atoms and mole fractions of different atoms) and quantum-chemical (QD: HOMO-LUMO gap, dipole moment, average polarizability, and quadrupole moment) molecular descriptors were used for the building of the LS-SVM calibration model. Prediction accuracies (MADs) of 1.62 ± 0.51 and 0.85 ± 0.24 kcal mol(-1) (1 kcal mol(-1) = 4.184 kJ mol(-1)) were reached for SVM-based approximations of ab initio and DFT energies, respectively. The LS-SVM model was more accurate than the MLR model. A comparison with the artificial neural network approach shows that the accuracy of the LS-SVM method is similar to the accuracy of ANN. The extrapolation and interpolation results show that LS-SVM is

Develop a Methodology to Evaluate the Effectiveness of QC/QA Specifications (Phase II)

DOT National Transportation Integrated Search

1998-08-01

The Texas Department of Transportation (TxDOT) has been implementing statistically based quality control/quality assurance (QC/QA) specifications for hot mix asphalt concrete pavements since the early 1990s. These specifications have been continuousl...

Passive and active mid-infrared semiconductor nanostructures: Three-dimensional metamaterials and high wall plug efficiency quantum cascade lasers

NASA Astrophysics Data System (ADS)

Hoffman, Anthony J.

Every instant, light and matter are interacting in ways that shape the world around us. This dissertation examines the interaction of mid-infrared light with stacks of thin semiconductor layers. The work is divided into two parts: mid-infrared metamaterials and high wall plug efficiency (WPE) Quantum Cascade (QC) lasers. The mid-infrared metamaterials represent an entirely new class of material and have great potential for enabling highly-desired applications such as sub-diffraction imaging, confinement, and waveguiding. High WPE QC lasers greatly enhance the commercial feasibility of sensing, infrared countermeasures and free-space infrared communications. The first part of this dissertation describes the first three-dimensional, optical metamaterial. The all-semiconductor metamaterial is based on a strongly anisotropic dielectric function and exhibits negative refraction for a large bandwidth in the mid-infrared. The underlying theory of strongly anisotropic metamaterials is discussed, detailed characterization of several metamaterials is presented, and a macroscopic beam experiment is employed to demonstrate negative refraction. A detailed study of waveguides with strongly anisotropic cores is also presented and the low-order mode cutoff for such left-handed waveguides is observed. The second part of this dissertation discusses improvements in QC laser WPE through improved processing, packaging, and design. Devices using conventional QC design strategies processed as buried heterostructures operate with 5% WPE at room temperature in continuous wave mode, a significant improvement over previous generation devices. To further improve WPE, QC lasers based on ultra-strong coupling between the injector and upper-laser levels are designed and characterized. These devices operate with nearly 50% pulsed WPE---a true milestone for QC technology. A new type of QC laser design incorporating heterogeneous injector regions to reduce the voltage defect and thus improve WPE is

From Field Notes to Data Portal - A Scalable Data QA/QC Framework for Tower Networks: Progress and Preliminary Results

NASA Astrophysics Data System (ADS)

Sturtevant, C.; Hackley, S.; Lee, R.; Holling, G.; Bonarrigo, S.

2017-12-01

Quality assurance and control (QA/QC) is one of the most important yet challenging aspects of producing research-quality data. Data quality issues are multi-faceted, including sensor malfunctions, unmet theoretical assumptions, and measurement interference from humans or the natural environment. Tower networks such as Ameriflux, ICOS, and NEON continue to grow in size and sophistication, yet tools for robust, efficient, scalable QA/QC have lagged. Quality control remains a largely manual process heavily relying on visual inspection of data. In addition, notes of measurement interference are often recorded on paper without an explicit pathway to data flagging. As such, an increase in network size requires a near-proportional increase in personnel devoted to QA/QC, quickly stressing the human resources available. We present a scalable QA/QC framework in development for NEON that combines the efficiency and standardization of automated checks with the power and flexibility of human review. This framework includes fast-response monitoring of sensor health, a mobile application for electronically recording maintenance activities, traditional point-based automated quality flagging, and continuous monitoring of quality outcomes and longer-term holistic evaluations. This framework maintains the traceability of quality information along the entirety of the data generation pipeline, and explicitly links field reports of measurement interference to quality flagging. Preliminary results show that data quality can be effectively monitored and managed for a multitude of sites with a small group of QA/QC staff. Several components of this framework are open-source, including a R-Shiny application for efficiently monitoring, synthesizing, and investigating data quality issues.

QSTR of the toxicity of some organophosphorus compounds by using the quantum chemical and topological descriptors.

PubMed

Senior, Samir A; Madbouly, Magdy D; El massry, Abdel-Moneim

2011-09-01

Quantum chemical and topological descriptors of some organophosphorus compounds (OP) were correlated with their toxicity LD(50) as a dermal. The quantum chemical parameters were obtained using B3LYP/LANL2DZdp-ECP optimization. Using linear regression analysis, equations were derived to calculate the theoretical LD(50) of the studied compounds. The inclusion of quantum parameters, having both charge indices and topological indices, affects the toxicity of the studied compounds resulting in high correlation coefficient factors for the obtained equations. Two of the new four firstly supposed descriptors give higher correlation coefficients namely the Heteroatom Corrected Extended Connectivity Randic index ((1)X(HCEC)) and the Density Randic index ((1)X(Den)). The obtained linear equations were applied to predict the toxicity of some related structures. It was found that the sulfur atoms in these compounds must be replaced by oxygen atoms to achieve improved toxicity. Copyright © 2011 Elsevier Ltd. All rights reserved.

Contactless electroreflectance study of strained Zn0.79Cd0.21Se/ZnSe double quantum wells

NASA Astrophysics Data System (ADS)

Tu, R. C.; Su, Y. K.; Lin, D. Y.; Li, C. F.; Huang, Y. S.; Lan, W. H.; Tu, S. L.; Chang, S. J.; Chou, S. C.; Chou, W. C.

1998-01-01

We have studied various excitonic transitions of strained Zn0.79Cd0.21Se/ZnSe double quantum wells, grown by molecular beam epitaxy on (100) GaAs substrates, using contactless electroreflectance (CER) at 15 and 300 K. A number of intersub-band transitions in the CER spectra from the sample have been observed. An analysis of the CER spectra has led to the identification of various excitonic transitions, mnH(L), between the mth conduction band state and the nth heavy (light)-hole band state. The conduction-band offset Qc is used as an adjustable parameter to study the band offset in the strained Zn0.79Cd0.21Se/ZnSe system. The value of Qc is determined to be 0.67±0.03.

Improvement of the customer satisfaction through Quality Assurance Matrix and QC-Story methods: A case study from automotive industry

NASA Astrophysics Data System (ADS)

Sicoe, G. M.; Belu, N.; Rachieru, N.; Nicolae, E. V.

2017-10-01

Presently, in the automotive industry, the tendency is to adapt permanently to the changes and introduce the market tendency in the new products that leads of the customer satisfaction. Many quality techniques were adopted in this field to continuous improvement of product and process quality and advantages were also gained. The present paper has focused on possibilities that offers the use of Quality Assurance Matrix (QAM) and Quality Control Story (QC Story) to provide largest protection against nonconformities in the production process, throughout a case study in the automotive industry. There is a direct relationship from the QAM to a QC Story analysis. The failures identified using QAM are treated with QC Story methodology. Using this methods, will help to decrease the PPM values and will increase the quality performance and the customer satisfaction.

QC/QA differences between hot mix asphalt (HMA) and warm mix asphalt (WMA).

DOT National Transportation Integrated Search

2013-01-01

WMA represents a group of technologies which allow a reduction in temperatures at which asphalt mixtures are produced and placed on the road. ODOT Materials Division has conducted preliminary inquiries into QC/QA testing for WMA. Some respondents ind...

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.

Hot mix asphalt voids acceptance review of QC/QA data 2000 through 2004.

DOT National Transportation Integrated Search

2006-07-01

This report analyzes the Quality Control/Quality Assurance (QC/QA) data for hot mix asphalt using voids acceptance as : the testing criteria for the years 2000 through 2004. Analysis of the overall quality of the HMA is accomplished by : reviewing th...

Hot mix asphalt voids acceptance review of QC/QA data 2000 through 2010.

DOT National Transportation Integrated Search

2011-10-01

This report analyzes the quality control/quality assurance (QC/QA) data for hot mix asphalt (HMA) using : voids acceptance as the testing criteria awarded in the years 2000 through 2010. Analysis of the overall : performance of the projects is accomp...

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 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.

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.

A model for tracking concentration of chemical compounds within a tank of an automatic film processor.

PubMed

Sobol, Wlad T

2002-01-01

A simple kinetic model that describes the time evolution of the chemical concentration of an arbitrary compound within the tank of an automatic film processor is presented. It provides insights into the kinetics of chemistry concentration inside the processor's tank; the results facilitate the tasks of processor tuning and quality control (QC). The model has successfully been used in several troubleshooting sessions of low-volume mammography processors for which maintaining consistent QC tracking was difficult due to fluctuations of bromide levels in the developer tank.

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.

QC-ART: A tool for real-time quality control assessment of mass spectrometry-based proteomics data.

PubMed

Stanfill, Bryan A; Nakayasu, Ernesto S; Bramer, Lisa M; Thompson, Allison M; Ansong, Charles K; Clauss, Therese; Gritsenko, Marina A; Monroe, Matthew E; Moore, Ronald J; Orton, Daniel J; Piehowski, Paul D; Schepmoes, Athena A; Smith, Richard D; Webb-Robertson, Bobbie-Jo; Metz, Thomas O

2018-04-17

Liquid chromatography-mass spectrometry (LC-MS)-based proteomics studies of large sample cohorts can easily require from months to years to complete. Acquiring consistent, high-quality data in such large-scale studies is challenging because of normal variations in instrumentation performance over time, as well as artifacts introduced by the samples themselves, such as those due to collection, storage and processing. Existing quality control methods for proteomics data primarily focus on post-hoc analysis to remove low-quality data that would degrade downstream statistics; they are not designed to evaluate the data in near real-time, which would allow for interventions as soon as deviations in data quality are detected.  In addition to flagging analyses that demonstrate outlier behavior, evaluating how the data structure changes over time can aide in understanding typical instrument performance or identify issues such as a degradation in data quality due to the need for instrument cleaning and/or re-calibration.  To address this gap for proteomics, we developed Quality Control Analysis in Real-Time (QC-ART), a tool for evaluating data as they are acquired in order to dynamically flag potential issues with instrument performance or sample quality.  QC-ART has similar accuracy as standard post-hoc analysis methods with the additional benefit of real-time analysis.  We demonstrate the utility and performance of QC-ART in identifying deviations in data quality due to both instrument and sample issues in near real-time for LC-MS-based plasma proteomics analyses of a sample subset of The Environmental Determinants of Diabetes in the Young cohort. We also present a case where QC-ART facilitated the identification of oxidative modifications, which are often underappreciated in proteomic experiments. Published under license by The American Society for Biochemistry and Molecular Biology, Inc.

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.

Gas Phase Photoacoustic Sensor at 8.41 mu m Using Quartz Tuning Forks and Amplitude Modulated Quantum Cascade Lasers

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

Wojcik, Michael D.; Phillips, Mark C.; Cannon, Bret D.

2006-10-01

We demonstrate the performance of a novel long-wave infrared photoacoustic laser absorbance spectrometer for gas-phase species using an amplitude modulated (AM) quantum cascade (QC) laser and a quartz tuning fork microphone. Photoacoustic signal was generated by focusing the output of a Fabry-Perot QC laser operating at 8.41 ?m between the legs of a quartz tuning fork which served as a transducer for the transient acoustic pressure wave. The QC laser was modulated at the resonant frequency of the tuning fork (32.8 kHz) and delivered a modest 5.3 mW at the tuning fork. This spectrometer was calibrated using the infrared absorbermore » Freon-134a by performing a simultaneous absorption measurement using a 35 cm absorption cell. The NEAS of this instrument was determined to be 2 x 10{sup -8} W cm-1 Hz{sup -1/2}. A corresponding theoretical analysis of the instrument sensitivity is presented and is capable of quantitatively reproducing the experimental NEAS, indicating that the fundamental sensitivity of this technique is limited by the noise floor of the tuning fork itself.« less

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.

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.

FQC Dashboard: integrates FastQC results into a web-based, interactive, and extensible FASTQ quality control tool.

PubMed

Brown, Joseph; Pirrung, Meg; McCue, Lee Ann

2017-06-09

FQC is software that facilitates quality control of FASTQ files by carrying out a QC protocol using FastQC, parsing results, and aggregating quality metrics into an interactive dashboard designed to richly summarize individual sequencing runs. The dashboard groups samples in dropdowns for navigation among the data sets, utilizes human-readable configuration files to manipulate the pages and tabs, and is extensible with CSV data. FQC is implemented in Python 3 and Javascript, and is maintained under an MIT license. Documentation and source code is available at: https://github.com/pnnl/fqc . joseph.brown@pnnl.gov. © The Author(s) 2017. Published by Oxford University Press.

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.

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.

Overexpression of the Qc-SNARE gene OsSYP71 enhances tolerance to oxidative stress and resistance to rice blast in rice (Oryza sativa L.).

PubMed

Bao, Yong-Mei; Sun, Shu-Jing; Li, Meng; Li, Li; Cao, Wen-Lei; Luo, Jia; Tang, Hai-Juan; Huang, Ji; Wang, Zhou-Fei; Wang, Jian-Fei; Zhang, Hong-Sheng

2012-08-10

OsSYP71 is an oxidative stress and rice blast response gene that encodes a Qc-SNARE protein in rice. Qc-SNARE proteins belong to the superfamily of SNAREs (soluble N-ethylmaleimide-sensitive factor attachment protein receptors), which function as important components of the vesicle trafficking machinery in eukaryotic cells. In this paper, 12 Qc-SNARE genes were isolated from rice, and expression patterns of 9 genes were detected in various tissues and in seedlings challenged with oxidative stresses and inoculated with rice blast. The expression of OsSYP71 was clearly up-regulated under these stresses. Overexpression of OsSYP71 in rice showed more tolerance to oxidative stress and resistance to rice blast than wild-type plants. These results indicate that Qc-SNAREs play an important role in rice response to environmental stresses, and OsSYP71 is useful in engineering crop plants with enhanced tolerance to oxidative stress and resistance to rice blast. Copyright © 2012 Elsevier B.V. All rights reserved.

On the error in the nucleus-centered multipolar expansion of molecular electron density and its topology: A direct-space computational study.

PubMed

Michael, J Robert; Koritsanszky, Tibor

2017-05-28

The convergence of nucleus-centered multipolar expansion of the quantum-chemical electron density (QC-ED), gradient, and Laplacian is investigated in terms of numerical radial functions derived by projecting stockholder atoms onto real spherical harmonics at each center. The partial sums of this exact one-center expansion are compared with the corresponding Hansen-Coppens pseudoatom (HC-PA) formalism [Hansen, N. K. and Coppens, P., "Testing aspherical atom refinements on small-molecule data sets," Acta Crystallogr., Sect. A 34, 909-921 (1978)] commonly utilized in experimental electron density studies. It is found that the latter model, due to its inadequate radial part, lacks pointwise convergence and fails to reproduce the local topology of the target QC-ED even at a high-order expansion. The significance of the quantitative agreement often found between HC-PA-based (quadrupolar-level) experimental and extended-basis QC-EDs can thus be challenged.

On the error in the nucleus-centered multipolar expansion of molecular electron density and its topology: A direct-space computational study

NASA Astrophysics Data System (ADS)

Michael, J. Robert; Koritsanszky, Tibor

2017-05-01

The convergence of nucleus-centered multipolar expansion of the quantum-chemical electron density (QC-ED), gradient, and Laplacian is investigated in terms of numerical radial functions derived by projecting stockholder atoms onto real spherical harmonics at each center. The partial sums of this exact one-center expansion are compared with the corresponding Hansen-Coppens pseudoatom (HC-PA) formalism [Hansen, N. K. and Coppens, P., "Testing aspherical atom refinements on small-molecule data sets," Acta Crystallogr., Sect. A 34, 909-921 (1978)] commonly utilized in experimental electron density studies. It is found that the latter model, due to its inadequate radial part, lacks pointwise convergence and fails to reproduce the local topology of the target QC-ED even at a high-order expansion. The significance of the quantitative agreement often found between HC-PA-based (quadrupolar-level) experimental and extended-basis QC-EDs can thus be challenged.

Anamorphic quasiperiodic universes in modified and Einstein gravity with loop quantum gravity corrections

NASA Astrophysics Data System (ADS)

Amaral, Marcelo M.; Aschheim, Raymond; Bubuianu, Laurenţiu; Irwin, Klee; Vacaru, Sergiu I.; Woolridge, Daniel

2017-09-01

The goal of this work is to elaborate on new geometric methods of constructing exact and parametric quasiperiodic solutions for anamorphic cosmology models in modified gravity theories, MGTs, and general relativity, GR. There exist previously studied generic off-diagonal and diagonalizable cosmological metrics encoding gravitational and matter fields with quasicrystal like structures, QC, and holonomy corrections from loop quantum gravity, LQG. We apply the anholonomic frame deformation method, AFDM, in order to decouple the (modified) gravitational and matter field equations in general form. This allows us to find integral varieties of cosmological solutions determined by generating functions, effective sources, integration functions and constants. The coefficients of metrics and connections for such cosmological configurations depend, in general, on all spacetime coordinates and can be chosen to generate observable (quasi)-periodic/aperiodic/fractal/stochastic/(super) cluster/filament/polymer like (continuous, stochastic, fractal and/or discrete structures) in MGTs and/or GR. In this work, we study new classes of solutions for anamorphic cosmology with LQG holonomy corrections. Such solutions are characterized by nonlinear symmetries of generating functions for generic off-diagonal cosmological metrics and generalized connections, with possible nonholonomic constraints to Levi-Civita configurations and diagonalizable metrics depending only on a time like coordinate. We argue that anamorphic quasiperiodic cosmological models integrate the concept of quantum discrete spacetime, with certain gravitational QC-like vacuum and nonvacuum structures. And, that of a contracting universe that homogenizes, isotropizes and flattens without introducing initial conditions or multiverse problems.

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

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.

Quantum-chemistry based calibration of the alkali metal cation series (Li(+)-Cs(+)) for large-scale polarizable molecular mechanics/dynamics simulations.

PubMed

Dudev, Todor; Devereux, Mike; Meuwly, Markus; Lim, Carmay; Piquemal, Jean-Philip; Gresh, Nohad

2015-02-15

The alkali metal cations in the series Li(+)-Cs(+) act as major partners in a diversity of biological processes and in bioinorganic chemistry. In this article, we present the results of their calibration in the context of the SIBFA polarizable molecular mechanics/dynamics procedure. It relies on quantum-chemistry (QC) energy-decomposition analyses of their monoligated complexes with representative O-, N-, S-, and Se- ligands, performed with the aug-cc-pVTZ(-f) basis set at the Hartree-Fock level. Close agreement with QC is obtained for each individual contribution, even though the calibration involves only a limited set of cation-specific parameters. This agreement is preserved in tests on polyligated complexes with four and six O- ligands, water and formamide, indicating the transferability of the procedure. Preliminary extensions to density functional theory calculations are reported. © 2014 Wiley Periodicals, Inc.

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.

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.

The sensitivity of patient specific IMRT QC to systematic MLC leaf bank offset errors.

PubMed

Rangel, Alejandra; Palte, Gesa; Dunscombe, Peter

2010-07-01

Patient specific IMRT QC is performed routinely in many clinics as a safeguard against errors and inaccuracies which may be introduced during the complex planning, data transfer, and delivery phases of this type of treatment. The purpose of this work is to evaluate the feasibility of detecting systematic errors in MLC leaf bank position with patient specific checks. 9 head and neck (H&N) and 14 prostate IMRT beams were delivered using MLC files containing systematic offsets (+/- 1 mm in two banks, +/- 0.5 mm in two banks, and 1 mm in one bank of leaves). The beams were measured using both MAPCHECK (Sun Nuclear Corp., Melbourne, FL) and the aS1000 electronic portal imaging device (Varian Medical Systems, Palo Alto, CA). Comparisons with calculated fields, without offsets, were made using commonly adopted criteria including absolute dose (AD) difference, relative dose difference, distance to agreement (DTA), and the gamma index. The criteria most sensitive to systematic leaf bank offsets were the 3% AD, 3 mm DTA for MAPCHECK and the gamma index with 2% AD and 2 mm DTA for the EPID. The criterion based on the relative dose measurements was the least sensitive to MLC offsets. More highly modulated fields, i.e., H&N, showed greater changes in the percentage of passing points due to systematic MLC inaccuracy than prostate fields. None of the techniques or criteria tested is sufficiently sensitive, with the population of IMRT fields, to detect a systematic MLC offset at a clinically significant level on an individual field. Patient specific QC cannot, therefore, substitute for routine QC of the MLC itself.

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 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.

Quantum chemical study of the inhibition of the corrosion of mild steel in H2SO4 by some antibiotics.

PubMed

Eddy, Nnabuk O; Ibok, Udo J; Ebenso, Eno E; El Nemr, Ahmed; El Ashry, El Sayed H

2009-09-01

The inhibition efficiency of some antibiotics against mild steel corrosion was studied using weight loss and quantum chemical techniques. Values of inhibition efficiency obtained from weight loss measurements correlated strongly with theoretical values obtained through semi empirical calculations. High correlation coefficients were also obtained between inhibition efficiency of the antibiotics and some quantum chemical parameters, including frontier orbital (E (HOMO) and E (LUMO)), dipole moment, log P, TNC and LSER parameters (critical volume and dipolar-polarisability factor), which indicated that these parameters affect the inhibition efficiency of the compounds. It was also found that quantitative structure activity relation can be used to adequately predict the inhibition effectiveness of these compounds.

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

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.

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

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).

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...

Study of the Q branch structure of the 14N and 15N isotopologues of the ν4 band of ammonia using frequency chirped quantum cascade lasers.

PubMed

Duxbury, Geoffrey; Wilson, David; Hay, Kenneth; Langford, Nigel

2013-10-03

Intrapulse quantum cascade (QC) laser spectrometers are able to produce both saturation and molecular alignment of a gas sample owing to the rapid sweep of the radiation through the absorption features. In the QC lasers used to study the (14)N and (15)N isotopologues of the ν4 band of ammonia centered near 1625 cm(-1), the variation of the chirp rate during the scan is very large, from ca. 85 to ca. 15 MHz ns(-1). In the rapid chirp zone the collisional interaction time of the laser radiation with the gas molecules is short, and large rapid passage effects are seen, whereas at the slow chirp end the line shape resembles that of a Doppler broadened line. The total scan range of the QC laser of ca. 10 cm(-1) is sufficient to allow the spectra of both isotopologues to be recorded and the rapid and slow interactions with the laser radiation to be seen. The rapid passage effects are enhanced by the use of an off axis Herriott cell with an effective path length of 62 m, which allows a buildup of polarization to occur. The effective resolution of the chirped QC laser is ca. 0.012 cm(-1) full width at half-maximum in the 1625 cm(-1) region. The results of these experiments are compared with those of other studies of the ν4 band of ammonia carried out using Fourier transform and Laser Stark spectroscopy. They also demonstrate the versatility of the down chirped QC laser for investigating collisional effects in low pressure gases using long absorbing path lengths.

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.

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.

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.

SprayQc: a real-time LC-MS/MS quality monitoring system to maximize uptime using off the shelf components.

PubMed

Scheltema, Richard A; Mann, Matthias

2012-06-01

With the advent of high-throughput mass spectrometry (MS)-based proteomics, the magnitude and complexity of the performed experiments has increased dramatically. Likewise, investments in chromatographic and MS instrumentation are a large proportion of the budget of proteomics laboratories. Guarding measurement quality and maximizing uptime of the LC-MS/MS systems therefore requires constant care despite automated workflows. We describe a real-time surveillance system, called SprayQc, that continuously monitors the status of the peripheral equipment to ensure that operational parameters are within an acceptable range. SprayQc is composed of multiple plug-in software components that use computer vision to analyze electrospray conditions, monitor the chromatographic device for stable backpressure, interact with a column oven to control pressure by temperature, and ensure that the mass spectrometer is still acquiring data. Action is taken when a failure condition has been detected, such as stopping the column oven and the LC flow, as well as automatically notifying the appropriate operator. Additionally, all defined metrics can be recorded synchronized on retention time with the MS acquisition file, allowing for later inspection and providing valuable information for optimization. SprayQc has been extensively tested in our laboratory, supports third-party plug-in development, and is freely available for download from http://sourceforge.org/projects/sprayqc .

A novel construction method of QC-LDPC codes based on the subgroup of the finite field multiplicative group for optical transmission systems

NASA Astrophysics Data System (ADS)

Yuan, Jian-guo; Zhou, Guang-xiang; Gao, Wen-chun; Wang, Yong; Lin, Jin-zhao; Pang, Yu

2016-01-01

According to the requirements of the increasing development for optical transmission systems, a novel construction method of quasi-cyclic low-density parity-check (QC-LDPC) codes based on the subgroup of the finite field multiplicative group is proposed. Furthermore, this construction method can effectively avoid the girth-4 phenomena and has the advantages such as simpler construction, easier implementation, lower encoding/decoding complexity, better girth properties and more flexible adjustment for the code length and code rate. The simulation results show that the error correction performance of the QC-LDPC(3 780,3 540) code with the code rate of 93.7% constructed by this proposed method is excellent, its net coding gain is respectively 0.3 dB, 0.55 dB, 1.4 dB and 1.98 dB higher than those of the QC-LDPC(5 334,4 962) code constructed by the method based on the inverse element characteristics in the finite field multiplicative group, the SCG-LDPC(3 969,3 720) code constructed by the systematically constructed Gallager (SCG) random construction method, the LDPC(32 640,30 592) code in ITU-T G.975.1 and the classic RS(255,239) code which is widely used in optical transmission systems in ITU-T G.975 at the bit error rate ( BER) of 10-7. Therefore, the constructed QC-LDPC(3 780,3 540) code is more suitable for optical transmission systems.

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.

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

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

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).

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.

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.

A sulfur hexafluoride sensor using quantum cascade and CO2 laser-based photoacoustic spectroscopy.

PubMed

Rocha, Mila; Sthel, Marcelo; Lima, Guilherme; da Silva, Marcelo; Schramm, Delson; Miklós, András; Vargas, Helion

2010-01-01

The increase in greenhouse gas emissions is a serious environmental problem and has stimulated the scientific community to pay attention to the need for detection and monitoring of gases released into the atmosphere. In this regard, the development of sensitive and selective gas sensors has been the subject of several research programs. An important greenhouse gas is sulphur hexafluoride, an almost non-reactive gas widely employed in industrial processes worldwide. Indeed it is estimated that it has a radiative forcing of 0.52 W/m(2). This work compares two photoacoustic spectrometers, one coupled to a CO(2) laser and another one coupled to a Quantum Cascade (QC) laser, for the detection of SF(6). The laser photoacoustic spectrometers described in this work have been developed for gas detection at small concentrations. Detection limits of 20 ppbv for CO(2) laser and 50 ppbv for quantum cascade laser were obtained.

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.

NHEXAS PHASE I ARIZONA STUDY--STANDARD OPERATING PROCEDURE FOR FORM QA/QC CHECKS (UA-C-2.0)

EPA Science Inventory

The purpose of this SOP is to outline the process of Field Quality Assurance and Quality Control checks. This procedure was followed to ensure consistent data retrieval during the Arizona NHEXAS project and the "Border" study. Keywords: custody; QA/QC; field checks.

The Nation...

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.

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

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.

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)

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.

Near-infrared quantum cutting in Yb3+ ion doped strontium vanadate

NASA Astrophysics Data System (ADS)

Sawala, N. S.; Bajaj, N. S.; Omanwar, S. K.

2016-05-01

The materials Sr3-x(VO4)2:xYb were successfully synthesized by co-precipitation method varying the concentration of Yb3+ ions from 0 to 0.06 mol. It was characterize by powder X-ray powder diffraction (XRD) and surface morphology was studied by scanning electronic microscope (SEM). The photoluminescence (PL) properties were studied by spectrophotometers in near infra red (NIR) and ultra violet visible (UV-VIS) region. The Yb3+ ion doped tristrontium vanadate (Sr3(VO4)2) phosphors that can convert a photon of UV region (349 nm) into photons of NIR region (978, 996 and 1026 nm). Hence this phosphor could be used as a quantum cutting (QC) luminescent convertor in front of crystalline silicon solar cell (c-Si) panels to reduce thermalization loss due to spectral mismatch of the solar cells. The theoretical value of quantum efficiency (QE) was calculated from steady time decay measurement and the maximum efficiency approached up to 144.43%. The Sr(3-x) (VO4)2:xYb can be potentiality used for betterment of photovoltaic (PV) technology.

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.

FQC Dashboard: integrates FastQC results into a web-based, interactive, and extensible FASTQ quality control tool

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

Brown, Joseph; Pirrung, Meg; McCue, Lee Ann

FQC is software that facilitates large-scale quality control of FASTQ files by carrying out a QC protocol, parsing results, and aggregating quality metrics within and across experiments into an interactive dashboard. The dashboard utilizes human-readable configuration files to manipulate the pages and tabs, and is extensible with CSV data.

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.

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.

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

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.

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.

Quantum clustering and network analysis of MD simulation trajectories to probe the conformational ensembles of protein-ligand interactions.

PubMed

Bhattacharyya, Moitrayee; Vishveshwara, Saraswathi

2011-07-01

In this article, we present a novel application of a quantum clustering (QC) technique to objectively cluster the conformations, sampled by molecular dynamics simulations performed on different ligand bound structures of the protein. We further portray each conformational population in terms of dynamically stable network parameters which beautifully capture the ligand induced variations in the ensemble in atomistic detail. The conformational populations thus identified by the QC method and verified by network parameters are evaluated for different ligand bound states of the protein pyrrolysyl-tRNA synthetase (DhPylRS) from D. hafniense. The ligand/environment induced re-distribution of protein conformational ensembles forms the basis for understanding several important biological phenomena such as allostery and enzyme catalysis. The atomistic level characterization of each population in the conformational ensemble in terms of the re-orchestrated networks of amino acids is a challenging problem, especially when the changes are minimal at the backbone level. Here we demonstrate that the QC method is sensitive to such subtle changes and is able to cluster MD snapshots which are similar at the side-chain interaction level. Although we have applied these methods on simulation trajectories of a modest time scale (20 ns each), we emphasize that our methodology provides a general approach towards an objective clustering of large-scale MD simulation data and may be applied to probe multistate equilibria at higher time scales, and to problems related to protein folding for any protein or protein-protein/RNA/DNA complex of interest with a known structure.

Proof of a Dain inequality with charge

NASA Astrophysics Data System (ADS)

Lopes Costa, João

2010-07-01

We prove an upper bound for angular momentum and charge in terms of the mass for electro-vacuum asymptotically flat axisymmetric initial data sets with simply connected orbit space. This completes the work started in (Chruściel and Costa 2009 Class. Quantum Grav. 26 235013 (arXiv:gr-qc/0909.5625)) where this charged Dain inequality was first presented but where the proof of the main result, based on the methods of Chruściel et al (Ann. Phys. 2008 323 2591-613 (arXiv:gr-qc/0712.4064v2)), was only sketched. Here we present a complete proof while simplifying the methods suggested by Chruściel and Costa (2009 Class. Quantum Grav. 26 235013 (arXiv:gr-qc/0909.5625)).

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

Novel Designs of Quantum Reversible Counters

NASA Astrophysics Data System (ADS)

Qi, Xuemei; Zhu, Haihong; Chen, Fulong; Zhu, Junru; Zhang, Ziyang

2016-11-01

Reversible logic, as an interesting and important issue, has been widely used in designing combinational and sequential circuits for low-power and high-speed computation. Though a significant number of works have been done on reversible combinational logic, the realization of reversible sequential circuit is still at premature stage. Reversible counter is not only an important part of the sequential circuit but also an essential part of the quantum circuit system. In this paper, we designed two kinds of novel reversible counters. In order to construct counter, the innovative reversible T Flip-flop Gate (TFG), T Flip-flop block (T_FF) and JK flip-flop block (JK_FF) are proposed. Based on the above blocks and some existing reversible gates, the 4-bit binary-coded decimal (BCD) counter and controlled Up/Down synchronous counter are designed. With the help of Verilog hardware description language (Verilog HDL), these counters above have been modeled and confirmed. According to the simulation results, our circuits' logic structures are validated. Compared to the existing ones in terms of quantum cost (QC), delay (DL) and garbage outputs (GBO), it can be concluded that our designs perform better than the others. There is no doubt that they can be used as a kind of important storage components to be applied in future low-power computing systems.

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

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

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.

Photoacoustic Spectroscopy with Quantum Cascade Lasers for Trace Gas Detection

PubMed Central

Elia, Angela; Di Franco, Cinzia; Lugarà, Pietro Mario; Scamarcio, Gaetano

2006-01-01

Various applications, such as pollution monitoring, toxic-gas detection, non invasive medical diagnostics and industrial process control, require sensitive and selective detection of gas traces with concentrations in the parts in 109 (ppb) and sub-ppb range. The recent development of quantum-cascade lasers (QCLs) has given a new aspect to infrared laser-based trace gas sensors. In particular, single mode distributed feedback QCLs are attractive spectroscopic sources because of their excellent properties in terms of narrow linewidth, average power and room temperature operation. In combination with these laser sources, photoacoustic spectroscopy offers the advantage of high sensitivity and selectivity, compact sensor platform, fast time-response and user friendly operation. This paper reports recent developments on quantum cascade laser-based photoacoustic spectroscopy for trace gas detection. In particular, different applications of a photoacoustic trace gas sensor employing a longitudinal resonant cell with a detection limit on the order of hundred ppb of ozone and ammonia are discussed. We also report two QC laser-based photoacoustic sensors for the detection of nitric oxide, for environmental pollution monitoring and medical diagnostics, and hexamethyldisilazane, for applications in semiconductor manufacturing process.

Computational Study of Field Initiated Surface Reactions for Synthesis of Diamond and Silicon

NASA Technical Reports Server (NTRS)

Musgrave, Charles Bruce

1999-01-01

This project involves using quantum chemistry to simulate surface chemical reactions in the presence of an electric field for nanofabrication of diamond and silicon. A field delivered by a scanning tunneling microscope (STM) to a nanometer scale region of a surface affects chemical reaction potential energy surfaces (PES) to direct atomic scale surface modification to fabricate sub-nanometer structures. Our original hypothesis is that the applied voltage polarizes the charge distribution of the valence electrons and that these distorted molecular orbitals can be manipulated with the STM so as to change the relative stabilities of the electronic configurations over the reaction coordinates and thus the topology of the PES and reaction kinetics. Our objective is to investigate the effect of applied bias on surface reactions and the extent to which STM delivered fields can be used to direct surface chemical reactions on an atomic scale on diamond and silicon. To analyze the fundamentals of field induced chemistry and to investigate the application of this technique for the fabrication of nanostructures, we have employed methods capable of accurately describing molecular electronic structure. The methods we employ are density functional theory (DFT) quantum chemical (QC) methods. To determine the effect of applied bias on surface reactions we have calculated the QC PESs in various applied external fields for various reaction steps for depositing or etching diamond and silicon. We have chosen reactions which are thought to play a role in etching and the chemical vapor deposition growth of Si and diamond. The PESs of the elementary reaction steps involved are then calculated under the applied fields, which we vary in magnitude and configuration. We pay special attention to the change in the reaction barriers, and transition state locations, and search for low energy reaction channels which were inaccessible without the applied bias.

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

Establishing daily quality control (QC) in screen-film mammography using leeds tor (max) phantom at the breast imaging unit of USTH-Benavides Cancer Institute

NASA Astrophysics Data System (ADS)

Acaba, K. J. C.; Cinco, L. D.; Melchor, J. N.

2016-03-01

Daily QC tests performed on screen film mammography (SFM) equipment are essential to ensure that both SFM unit and film processor are working in a consistent manner. The Breast Imaging Unit of USTH-Benavides Cancer Institute has been conducting QC following the test protocols in the IAEA Human Health Series No.2 manual. However, the availability of Leeds breast phantom (CRP E13039) in the facility made the task easier. Instead of carrying out separate tests on AEC constancy and light sensitometry, only one exposure of the phantom is done to accomplish the two tests. It was observed that measurements made on mAs output and optical densities (ODs) using the Leeds TOR (MAX) phantom are comparable with that obtained from the usual conduct of tests, taking into account the attenuation characteristic of the phantom. Image quality parameters such as low contrast and high contrast details were also evaluated from the phantom image. The authors recognize the usefulness of the phantom in determining technical factors that will help improve detection of smallest pathological details on breast images. The phantom is also convenient for daily QC monitoring and economical since less number of films is expended.

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.

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.

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.

High performance quantum cascade lasers: Loss, beam stability, and gain engineering

NASA Astrophysics Data System (ADS)

Bouzi, Pierre Michel

Quantum Cascade (QC) lasers are semiconductor devices emitting in the mid-infrared (3-30 micron) and terahertz (30-300 micron) regions of the electromagnetic spectrum. Since their first demonstration by Jerome Faist et. al. in 1994, they have evolved very quickly into high performance devices and given rise to many applications such as trace-gas sensing, medical diagnosis, free-space communication, and light detection and ranging (LIDAR). In this thesis, we investigate a further increase of the performance of QC devices and, through meticulous device modeling and characterizations, gain a deeper understanding of several of their unique characteristics, especially their carrier transport and lifetime, their characteristic temperature, their waveguide loss and modal gain, their leakage current, and their transverse mode profile. First, in our quest to achieve higher performance, we investigate the effect of growth asymmetries on device transport characteristics. This investigation stems from recent studies on the role of interface roughness on intersubband scattering and device performance. Through a symmetric active core design, we find that interface roughness and ionized impurity scattering induced by dopant migration play a significant role in carrier transport through the device. Understanding how interface roughness affects intersubband scattering, in turn, we engineer the gain in QC devices by placing monolayer barriers at specific locations within the device band structure. These strategically placed additional thin barrier layers introduce roughness scattering into the device active region, thereby selectively decreasing the lower laser state lifetime and increasing population inversion necessary for laser action. Preliminary measurement results from modified devices reveal a 50% decrease in the emission broadening compared to the control structures, which should lead to a two-fold increase in gain. A special class of so-called "strong coupling" QC lasers

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.

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.

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.

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.

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.

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.

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.

Analysis of CrIS/ATMS using AIRS Version-7 Retrieval and QC Methodology

NASA Astrophysics Data System (ADS)

Susskind, J.; Kouvaris, L. C.; Blaisdell, J. M.; Iredell, L. F.

2017-12-01

The objective of the proposed research is to develop, implement, test, and refine a CrIS/ATMS retrieval algorithm which will produce monthly mean data products that are compatible with those of the soon to be operational AIRS V7 retrieval algorithm. This is a necessary condition for CrIS/ATMS on NPP and future missions to serve as adequate follow-ons to AIRS for the monitoring of climate variability and trends. Of particular importance toward this end is achieving agreement of monthly mean fields of CrIS and AIRS geophysical parameters on a 1 deg by 1 deg spatial scale, and, more significantly, agreement of their interannual differences. Indications are that the best way to achieve this is to use scientific retrieval and Quality Control (QC) methodology for CrIS/ATMS which is analogous to that which will be used in AIRS V7. We refer to the current scientific candidate for AIRS V7 as AIRS Sounder Research Team (SRT) V6.42, which currently runs at JPL on the AIRS Team Leader Scientific Facility (TLSCF). We ported CrIS SRT V6.42 Level 2 (L2) retrieval code and QC methodology to run at the Sounder SIPS at JPL. The months of January and July 2015 were both processed at JPL using AIRS and CrIS at the TLSCF and SIPS respectively. This paper shows excellent agreement of AIRS and CrIS single day and monthly mean products on a 1 deg lat by 1 deg long spatial grid with each other and with the other satellites measures of the same products.

Evaluation of methods to reduce background using the Python-based ELISA_QC program.

PubMed

Webster, Rose P; Cohen, Cinder F; Saeed, Fatima O; Wetzel, Hanna N; Ball, William J; Kirley, Terence L; Norman, Andrew B

2018-05-01

Almost all immunological approaches [immunohistochemistry, enzyme-linked immunosorbent assay (ELISA), Western blot], that are used to quantitate specific proteins have had to address high backgrounds due to non-specific reactivity. We report here for the first time a quantitative comparison of methods for reduction of the background of commercial biotinylated antibodies using the Python-based ELISA_QC program. This is demonstrated using a recombinant humanized anti-cocaine monoclonal antibody. Several approaches, such as adjustment of the incubation time and the concentration of blocking agent, as well as the dilution of secondary antibodies, have been explored to address this issue. In this report, systematic comparisons of two different methods, contrasted with other more traditional methods to address this problem are provided. Addition of heparin (HP) at 1 μg/ml to the wash buffer prior to addition of the secondary biotinylated antibody reduced the elevated background absorbance values (from a mean of 0.313 ± 0.015 to 0.137 ± 0.002). A novel immunodepletion (ID) method also reduced the background (from a mean of 0.331 ± 0.010 to 0.146 ± 0.013). Overall, the ID method generated more similar results at each concentration of the ELISA standard curve to that using the standard lot 1 than the HP method, as analyzed by the Python-based ELISA_QC program. We conclude that the ID method, while more laborious, provides the best solution to resolve the high background seen with specific lots of biotinylated secondary antibody. Copyright © 2018. Published by Elsevier B.V.

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 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.

ZnCdMgSe as a Materials Platform for Advanced Photonic Devices: Broadband Quantum Cascade Detectors and Green Semiconductor Disk Lasers

NASA Astrophysics Data System (ADS)

De Jesus, Joel

The ZnCdMgSe family of II-VI materials has unique and promising characteristics that may be useful in practical applications. For example they can be grown lattice matched to InP substrates with lattice matched bandgaps that span from 2.1 to 3.5 eV, they can be successfully doped n-type, have a large conduction band offset (CBO) with no intervalley scattering present when strained, they have lower average phonon energies, and the InP lattice constant lies in the middle of the ZnSe and CdSe binaries compounds giving room to experiment with tensile and compressive stress. However they have not been studied in detail for use in practical devices. Here we have identified two types of devices that are being currently developed that benefit from the ZnCdMgSe-based material properties. These are the intersubband (ISB) quantum cascade (QC) detectors and optically pumped semiconductor lasers that emit in the visible range. The paucity for semiconductor lasers operating in the green-orange portion of the visible spectrum can be easily overcome with the ZnCdMgSe materials system developed in our research. The non-strain limited, large CBO available allows to expand the operating wavelength of ISB devices providing shorter and longer wavelengths than the currently commercially available devices. This property can also be exploited to develop broadband room temperature operation ISB detectors. The work presented here focused first on using the ZnCdMgSe-based material properties and parameter to understand and predict the interband and intersubband transitions of its heterostructures. We did this by studying an active region of a QC device by contactless electroreflectance, photoluminescence, FTIR transmittance and correlating the measurements to the quantum well structure by transfer matrix modeling. Then we worked on optimizing the ZnCdMgSe material heterostructures quality by studying the effects of growth interruptions on their optical and optoelectronic properties of

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.

Eddy covariance carbonyl sulfide flux measurements with a quantum cascade laser absorption spectrometer

NASA Astrophysics Data System (ADS)

Gerdel, Katharina; Spielmann, Felix M.; Hammerle, Albin; Wohlfahrt, Georg

2016-04-01

Carbonyl sulfide (COS) is the most abundant sulfur containing trace gas present in the troposphere at concentrations of around 500 ppt. Recent interest in COS by the ecosystem-physiological community has been sparked by the fact that COS co-diffuses into plant leaves pretty much the same way as carbon dioxide (CO2) does, but in contrast to CO2, COS is not known to be emitted by plants. Thus uptake of COS by vegetation has the potential to be used as a tracer for canopy gross photosynthesis, which cannot be measured directly, however represents a key term in the global carbon cycle. Since a few years, quantum cascade laser absorption spectrometers (QCLAS) are commercially available with the precision, sensitivity and time response suitable for eddy covariance (EC) flux measurements. While there exist a handful of published reports on EC flux measurements in the recent literature, no rigorous investigation of the applicability of QCLAS for EC COS flux measurements has been carried out so far, nor have been EC processing and QA/QC steps developed for carbon dioxide and water vapor flux measurements within FLUXNET been assessed for COS. The aim of this study is to close this knowledge gap, to discuss critical steps in the post-processing chain of COS EC flux measurements and to devise best-practice guidelines for COS EC flux data processing. To this end we collected EC COS (and CO2, H2O and CO) flux measurements above a temperate mountain grassland in Austria over the vegetation period 2015 with a commercially available QCLAS. We discuss various aspects of EC data post-processing, in particular issues with the time-lag estimation between sonic anemometer and QCLAS signals and QCLAS time series detrending, as well as QA/QC, in particular flux detection limits, random flux uncertainty, the interaction of various processing steps with common EC QA/QC filters (e.g. detrending and stationarity tests), u*-filtering, etc.

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.

Conformational analysis of a polyconjugated protein-binding ligand by joint quantum chemistry and polarizable molecular mechanics. Addressing the issues of anisotropy, conjugation, polarization, and multipole transferability.

PubMed

Goldwaser, Elodie; de Courcy, Benoit; Demange, Luc; Garbay, Christiane; Raynaud, Françoise; Hadj-Slimane, Reda; Piquemal, Jean-Philip; Gresh, Nohad

2014-11-01

We investigate the conformational properties of a potent inhibitor of neuropilin-1, a protein involved in cancer processes and macular degeneration. This inhibitor consists of four aromatic/conjugated fragments: a benzimidazole, a methylbenzene, a carboxythiourea, and a benzene-linker dioxane, and these fragments are all linked together by conjugated bonds. The calculations use the SIBFA polarizable molecular mechanics procedure. Prior to docking simulations, it is essential to ensure that variations in the ligand conformational energy upon rotations around its six main-chain torsional bonds are correctly represented (as compared to high-level ab initio quantum chemistry, QC). This is done in two successive calibration stages and one validation stage. In the latter, the minima identified following independent stepwise variations of each of the six main-chain torsion angles are used as starting points for energy minimization of all the torsion angles simultaneously. Single-point QC calculations of the minimized structures are then done to compare their relative energies ΔE conf to the SIBFA ones. We compare three different methods of deriving the multipoles and polarizabilities of the central, most critical moiety of the inhibitor: carboxythiourea (CTU). The representation that gives the best agreement with QC is the one that includes the effects of the mutual polarization energy E pol between the amide and thioamide moieties. This again highlights the critical role of this contribution. The implications and perspectives of these findings are discussed.

Quantitative competitive (QC) PCR for quantification of porcine DNA.

PubMed

Wolf, C; Lüthy, J

2001-02-01

Many meat products nowadays may contain several species in different proportions. To protect consumers from fraud and misdeclarations, not only a qualitative but also a quantitative monitoring of ingredients of complex food products is necessary. DNA based techniques like the polymerase chain reaction (PCR) are widely used for identification of species but no answer to the proportional amount of a certain species could be given using current techniques. In this study we report the development and evaluation of a quantitative competitive polymerase chain reaction (QC-PCR) for detection and quantification of porcine DNA using a new porcine specific PCR system based on the growth hormone gene of sus scrofa. A DNA competitor differing by 30 bp in length from the porcine target sequence was constructed and used for PCR together with the target DNA. Specificity of the new primers was evaluated with DNA from cattle, sheep, chicken and turkey. The competitor concentration was adjusted to porcine DNA contents of 2 or 20% by coamplification of mixtures containing porcine and corresponding amounts of bovine DNA in defined ratios.

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.

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.

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.

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.

U.S.-MEXICO BORDER PROGRAM ARIZONA BORDER STUDY--STANDARD OPERATING PROCEDURE FOR FORM QA AND QC CHECKS (UA-C-2.0)

EPA Science Inventory

The purpose of this SOP is to outline the process of field quality assurance and quality control checks. This procedure was followed to ensure consistent data retrieval during the Arizona NHEXAS project and the Border study. Keywords: custody; QA/QC; field checks.

The U.S.-Mex...

SU-E-T-473: A Patient-Specific QC Paradigm Based On Trajectory Log Files and DICOM Plan Files

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

DeMarco, J; McCloskey, S; Low, D

Purpose: To evaluate a remote QC tool for monitoring treatment machine parameters and treatment workflow. Methods: The Varian TrueBeamTM linear accelerator is a digital machine that records machine axis parameters and MLC leaf positions as a function of delivered monitor unit or control point. This information is saved to a binary trajectory log file for every treatment or imaging field in the patient treatment session. A MATLAB analysis routine was developed to parse the trajectory log files for a given patient, compare the expected versus actual machine and MLC positions as well as perform a cross-comparison with the DICOM-RT planmore » file exported from the treatment planning system. The parsing routine sorts the trajectory log files based on the time and date stamp and generates a sequential report file listing treatment parameters and provides a match relative to the DICOM-RT plan file. Results: The trajectory log parsing-routine was compared against a standard record and verify listing for patients undergoing initial IMRT dosimetry verification and weekly and final chart QC. The complete treatment course was independently verified for 10 patients of varying treatment site and a total of 1267 treatment fields were evaluated including pre-treatment imaging fields where applicable. In the context of IMRT plan verification, eight prostate SBRT plans with 4-arcs per plan were evaluated based on expected versus actual machine axis parameters. The average value for the maximum RMS MLC error was 0.067±0.001mm and 0.066±0.002mm for leaf bank A and B respectively. Conclusion: A real-time QC analysis program was tested using trajectory log files and DICOM-RT plan files. The parsing routine is efficient and able to evaluate all relevant machine axis parameters during a patient treatment course including MLC leaf positions and table positions at time of image acquisition and during treatment.« less

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

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

Xu, Luyao; Curwen, Christopher; Chen, Daguan

A longstanding challenge for terahertz quantum-cascade (QC) lasers is achieving both a high power and high-quality beam pattern, this is due in part due to their use of sub-wavelength metallic waveguides. Recently, the vertical-external-cavity surface-emitting laser (VECSEL) concept was demonstrated for the first time in the terahertz range and for a QC-laser. This is enabled by the development of an amplifying metasurface reflector capable of coupling incident free-space THz radiation to the QC-laser material such that it is amplified and re-radiated. The THz metasurface QC-VECSEL initiates a new approach for making QC-lasers with high power and excellent beam pattern. Furthermore,more » the ability to engineer the electromagnetic phase, amplitude, and polarization response of the metasurface enables lasers with new functionality. Our article provides an overview of the fundamental theory, design considerations, and recent results for high-performance THz QC-VECSELs.« less

Corrosion inhibition of mild steel in 1M HCl by D-glucose derivatives of dihydropyrido [2,3-d:6,5-d′] dipyrimidine-2, 4, 6, 8(1H,3H, 5H,7H)-tetraone

PubMed Central

Verma, Chandrabhan; Quraishi, M. A.; Kluza, K.; Makowska-Janusik, M.; Olasunkanmi, Lukman O.; Ebenso, Eno E.

2017-01-01

D-glucose derivatives of dihydropyrido-[2,3-d:6,5-d′]-dipyrimidine-2, 4, 6, 8(1H,3H, 5H,7H)-tetraone (GPHs) have been synthesized and investigated as corrosion inhibitors for mild steel in 1M HCl solution using gravimetric, electrochemical, surface, quantum chemical calculations and Monte Carlo simulations methods. The order of inhibition efficiencies is GPH-3 > GPH-2 > GPH-1. The results further showed that the inhibitor molecules with electron releasing (-OH, -OCH3) substituents exhibit higher efficiency than the parent molecule without any substituents. Polarization study suggests that the studied compounds are mixed-type but exhibited predominantly cathodic inhibitive effect. The adsorption of these compounds on mild steel surface obeyed the Langmuir adsorption isotherm. SEM, EDX and AFM analyses were used to confirm the inhibitive actions of the molecules on mild steel surface. Quantum chemical (QC) calculations and Monte Carlo (MC) simulations studies were undertaken to further corroborate the experimental results. PMID:28317849

Scaling behavior near the itinerant ferromagnetic quantum critical point (FQCP) of NiCoCrx for 0.8

NASA Astrophysics Data System (ADS)

Sales, Brian; Jin, Ke; Bei, Hongbin; Nichols, John; Chisholm, Matthew; May, Andrew; McGuire, Michael

Low temperature magnetization, resistivity and heat capacity data are reported for the concentrated solid solution NiCoCrx as a function of temperature and magnetic field. In the quantum critical region the low field (0.001-0.01 T) magnetic susceptibility, Chi, diverges as T- 1 / 2 and the magnetization data exhibits T/B scaling from 0.001 2 Tesla, the crossover temperature from the QC to Fermi liquid regime is no longer linear in B, and is better described by B0.75. This scaling behavior is particularly accurate in describing the normalized magnetoresistance data [Rho(B,T)-Rho(0,T)]/T, which is equivalent to the ratio of relaxation rates associated with magnetic field and temperature TauT/TauB. The location of the QCP is sensitive to the composition x and the strain generated during synthesis. These medium-entropy alloys are interesting model systems to explore the role of chemical disorder at FQCP. Research supported by the DOE Office of Science, Materials Science and Engineering Division, and the Energy Dissipation to Defect Evolution EFRC.